JP2000001645A - Anticorrosive coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an anticorrosive coating composition excellent in compatibility without causing separation in a reactional process of an epoxy resin, without causing the layer separation at all even when causing defective ventilation or carrying out thick coating and resultantly manifesting coating film performances comparable to those of a tar epoxy resin coating. SOLUTION: This anticorrosive coating composition comprises an epoxy resin, an amine-based curing agent and a hydroxyl group-containing terpene phenol resin. The composition contains the contained hydroxyl group-containing terpene phenol resin in an amount of 10-500 pts.wt. based on 100 pts.wt. of the solid content of the cured resin. Furthermore, the hydroxyl group-containing terpene phenol resin is preferably a terpene resin containing 1-3 hydroxyl groups in one molecule and the softening point thereof is preferably 20-180 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anticorrosion paint composition containing no tar and useful for coating the interior of ship ballast tanks and steel structures.

[0002]

2. Description of the Related Art Conventionally, tar epoxy paints have been used as anticorrosion paints for marine steel structures. Tar epoxy paints have excellent corrosion resistance, water resistance, chemical resistance, etc., but not only are there concerns about safety and health issues due to the inclusion of tar, it is difficult to maintain because it is black,
There were inconveniences such as danger in the work because it became dark in the sealed place. In order to solve this problem, non-tar was required.

A modified epoxy resin paint is dispersible in the state of a paint in which a third component such as a solvent is present, even if the compatibility between the epoxy resin and the modified resin is not perfect, and maintains a uniformly mixed and stable state. be able to. In the process of forming a coating film with this paint, as the epoxy resin and the amine curing agent undergo a polymerization reaction and become polymerized, the mixing stability of the modified resin is lost,
It becomes a state separated from the dispersion system. In particular, a tendency is seen for a modified resin having a poor compatibility with an epoxy resin to become larger.
As this separation progresses, the cohesive strength of the coating decreases and the coating cracks,
It is known that troubles such as adhesion failure may occur.

[0004] The ballast tank of a ship is generally coated with a modified epoxy resin paint twice. When a second layer of overcoat is applied repeatedly, layer separation of the denatured resin easily occurs, adhesion between layers is reduced, and delamination is likely to occur. In particular, there is a problem that the coating is easily influenced by the coating environment, and when poor ventilation or thick coating is performed, the layer separation is further promoted and delamination is likely to occur.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an epoxy resin which does not cause separation during the reaction process and has excellent compatibility. An object of the present invention is to provide an anticorrosion coating composition exhibiting the same coating performance as a resin coating.

[0006]

According to the present invention, an epoxy resin, an amine-based curing agent and a hydroxyl group-containing terpene phenol resin are used, and the hydroxyl group-containing terpene phenol resin is added in an amount of 10 to 500 parts by weight based on 100 parts by weight of the solid content of the cured resin. It is intended to provide an anticorrosive coating composition containing the same.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The epoxy resin used in the present invention has at least two epoxy groups in one molecule and has an epoxy equivalent of 150 to 600, preferably 13
Those with 0 to 300 are suitable. Examples of such epoxy resins include conventionally known bisphenol type epoxy resins, aliphatic epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, phenol novolak type epoxy resins, cresol type epoxy resins, and dimer acid modified epoxy resins. And these may be used alone or in combination of two or more.

As the amine curing agent used in the present invention, conventionally known curing agents for epoxy resins can be used.
For example, aliphatic polyamines such as metaxylenediamine, isophoronediamine, diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, alicyclic polyamines, and aromatic polyamines; epoxy resin adducts of polyamines, polyamideamines, and polyamide resins. Can be These can be used alone or in combination of two or more.

The mixing ratio of the epoxy resin and the amine curing agent component is appropriately selected depending on the type of use of both, and usually, the equivalent ratio of [active hydrogen equivalent in amine curing agent / epoxy equivalent in epoxy resin] is 0. It is appropriate to set the range of 0.5 to 1.0.

The hydroxyl group-containing terpene phenol resin used in the present invention preferably has a softening point of 20 to 20.
Those having a temperature of 180 ° C, more preferably 50 to 150 ° C, can be suitably used.

As the terpene phenol resin, for example, a terpene compound having two phenols represented by the following (1) can be mentioned as a typical example, and a terpene phenol copolymer such as (2) or (3) is exemplified. Coalescence is preferred from the point of weather resistance.

[0013]

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[0014]

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[0015]

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The content of the hydroxyl group in the hydroxyl group-containing terpene phenol resin is preferably 1 to 3, more preferably 1 to 1.5 per molecule of the terpene phenol resin. If the content is less than one in one molecule, the compatibility with the above-mentioned amine curing agent is reduced and the coating film performance is adversely affected. On the other hand, if the content is more than three, the water resistance is lowered, which is not desirable. If the softening point of the hydroxyl group-containing terpene phenol resin is lower than 20 ° C., the water resistance of the coating film is reduced, and the components may bleed on the coating film surface and the adhesiveness may remain.
On the other hand, when the temperature exceeds 180 ° C., the viscosity of the coating material is increased and the workability is lowered, and the physical properties of the coating film are lowered, which is not desirable.

The composition of the present invention contains the above hydroxyl group-containing terpene phenol resin in an amount of 10 to 500 parts by weight, preferably 30 to 300 parts by weight, based on 100 parts by weight of the solid content of the cured resin. If the content is less than 10 parts by weight, sufficient water resistance cannot be obtained, while if it exceeds 500 parts by weight, the coating film is brittle and good physical properties cannot be obtained, which is not preferable.

In the composition of the present invention, from the viewpoint of imparting flexibility, other liquid modifiers such as a xylene resin and a toluene resin; a reactive diluent such as an epoxy compound such as butyl glycidyl ether; A non-reactive diluent such as a condensation polymer may be added in a range of 50 parts by weight or less based on 100 parts by weight of the solid content of the cured resin. Of these, aromatic ones are preferably used from the viewpoint of maintaining water resistance.

The composition of the present invention may further contain, if necessary,
Pigments such as extender pigments, rust preventive pigments, color pigments, etc .; reactive diluents; for ordinary paints such as organic solvents, anti-settling agents, anti-sagging agents, wetting agents, reaction accelerators, adhesion promoters, dehydrating agents, etc. An additive or the like may be appropriately contained.

The composition of the present invention is a two-pack type paint comprising a main agent containing an epoxy resin and an amine-based curing agent, and is usually applied on a primary rust preventive coating such as a zinc primer. As the coating method of the paint, a conventionally known method such as air spray, airless spray, brush coating, and roller can be adopted, and the paint can be applied to a dry film thickness of 150 to 500 μm.

[0021]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. Note that “parts” and “%” indicate “parts by weight” and “% by weight”, respectively.

Example 1 In a 1-liter container, 70 parts of epoxy resin (Note 1), 30 parts of epoxy resin (Note 2), 80 parts of titanium oxide white, 100 parts of talc, terpene phenol diphenol resin (Note 3) 50 parts, plasticizer (Note 4) 1
0 parts, 10 parts of anti-sagging agent (Note 5), 10 parts of xylene, and 10 parts of methyl isobutyl ketone (MIBK) are added, mixed and stirred with a disper to form a main agent, and an amine curing agent (Note 6) 60 Was added immediately before coating and mixed and stirred to obtain an anticorrosive paint.

(Note 1) "Epon 1001": Yuka Shell Epoxy Co .; Epiquilol hydrin-bisphenol A resin, epoxy equivalent 475 (Note 2) "Epon 828": Yuka Shell Epoxy Co .;
Epichlorohydrin-bisphenol A resin, epoxy equivalent 190 (Note 3) “YP-90”: manufactured by Yashara Chemical Co .; terpene phenol resin (resin having two hydroxyl groups): softening point 120 ° C. (Note 4) “Nicanol L ( (Registered trademark) ": manufactured by Mitsubishi Gas Chemical Company; xylene resin (* 5)" Dispalon 6650 (registered trademark) ": manufactured by Kusumoto Chemicals; fatty acid amide wax (* 6)" Sunmide # 305X-90S ": Sanwa Chemical Company Polyamideamine, active hydrogen equivalent 450, solid content 90%

<Examples 2 to 6 and Comparative Examples 1 to 5> Each anticorrosive paint was obtained in the same manner as in Example 1 except that the composition and the amount were as shown in Table 1. (Note 7) to (Note 9) in Table 1 are as follows. As Comparative Example 5, "SDC coat SL200" (manufactured by Dainippon Paint Co., Ltd., tar epoxy resin paint) was used. Table 1 shows the solid content.

(Note 7) “YP-90L”: manufactured by Yashara Chemical Company; terpene phenol resin (resin mixture containing 1 to 3 hydroxyl groups): softening point 95 ° C. (Note 8) “Quinton 1500 (registered trademark)”: Nippon Zeon; cyclopentadiene petroleum resin (no hydroxyl group) (Note 9) "DSX 2200": Henkel Hakusui; modified polyamidoamine, active hydrogen equivalent 160 (solid content 55)
%)

<Performance Test> [Adhesion] Each anticorrosive paint was degreased and polished to a mild steel plate (150
About 70 × 0.8mm) by airless spray
μm (dry film thickness).
Each test coated plate was prepared by drying in an atmosphere of% RH for 7 days. A cross-cut of 5 mm square is performed on the coated plate in an atmosphere of 20 ° C., and nine cellotape tests are performed. ：: less than 5% of peeled area from iron base

[Bleedability] On a coated plate prepared in the same manner as described above, a chlorinated rubber-based overcoat white paint (manufactured by Dainippon Paint Co., Ltd .; rubber tight DV Marine White) was applied by airless spray so that the dry film thickness became about 35 μm. Apply. 65% humidity at 20 ° C
After drying for 7 days in an RH atmosphere, the discoloration of the painted surface is visually compared with a standard plate. ：: No discoloration was observed as compared with the standard plate. X: Extremely yellow discoloration was observed as compared with the standard plate.

[Adhesion between layers of recoating] Each anticorrosive paint was applied to a degreased polished mild steel plate (150 × 70 × 0.8 mm) by airless spray so as to have a thickness of about 150 μm (dry film thickness). And dried in an atmosphere of a humidity of 65% RH for 7 days. The same paint is applied on the coated plate by airless spray so that the dry film thickness becomes about 300 μm in total. Immediately after recoating, transfer to a sealed container and leave for 3 days to dry. The condition of the container is as follows:
° C. Take it out of the sealed container and place it at 20 ° C and humidity 6
After drying in an atmosphere of 5% RH for 4 days, the coated plate was heated at 20 ° C.
A cross cut of 5 mm square is performed in an atmosphere, and nine cellotape tests are performed. ：: those having a delamination area of less than 5% ×: those having a delamination area of 25% or more

[Flexibility] Each anticorrosive paint was applied to a degreased polished mild steel plate (150 × 70 × 0.8 mm) by airless spray to a thickness of about 250 μm (dry film thickness).
Each test plate was dried by drying in an atmosphere at 65 ° C. and a humidity of 65% RH for 7 days. Place the coated plate in a 20 ° C atmosphere with the coated side facing out.
The film was bent at 0 °, and the cracks of the coating film at the bent portion were visually evaluated. ：: no cracks △: slight cracks ×: considerable cracks

[Temperature difference water resistance] "Serarich: trade name" (Zinc silicate primer manufactured by Dainippon Paint Co., Ltd.) was applied to a shot-blasted steel plate (300 × 100 × 3.2 mm).
Is applied to a thickness of about 20 μm (dry film thickness) and dried for one day. In addition, each of the anticorrosion paints obtained above is applied by airless spray to a thickness of about 250 μm (dry film thickness). Each test coated plate was dried at 20 ° C. in an atmosphere of 65% RH for 7 days. After the coated surface of the coated plate was immersed in warm water of 40 ° C. and a back surface of which was in contact with water of 20 ° C. for 14 days, the coated surface condition was visually evaluated. ：: No abnormality Δ: Slight swelling and rusting are observed. ×: Significant swelling and rust occurred

[Seawater resistance] Each test plate obtained in the same manner as the above temperature difference water resistance was visually evaluated for the coated surface condition after immersion in seawater at 50 ° C for 3 months.

：: No abnormality Δ: Slight occurrence of blistering is recognized ×: Swelling is remarkably generated

[0033]

[Table 1]

[0034]

The anticorrosion coating composition of the present invention uses a specific amount of a hydroxyl group-containing petroleum resin instead of tar, so that it does not separate during the reaction of the epoxy resin, has excellent compatibility, and has poor ventilation and thick coating. Even without causing layer separation at all, as a result shows the same coating performance as tar epoxy resin paint,
It is very useful as an anticorrosion paint for ships and steel structures.

 ──────────────────────────────────────────────────続 き Continued from the front page F term (reference) 4J002 CD04W CD05W CD06W CD08W CD13W CD20W CD203 CE00X CL003 EN046 EN076 FD143 FD146 GH00 4J036 AD01 AF06 AF08 AG00 AH00 AJ08 CA23 DC03 DC03 DC06 DC09 DC10 DC18 FB08 FB1 DB1 DB1 DB1 DB392 DC002 DH002 GA03 JB04 JB05 JB07 KA03 MA13 NA23 NA27

Claims (2)

[Claims] 1. An epoxy resin, an amine-based curing agent, and a hydroxyl group-containing terpene phenol resin, wherein the hydroxyl group-containing terpene phenol resin is contained in an amount of 10 to 500 parts by weight based on 100 parts by weight of the solid content of the cured resin. Anticorrosion paint composition. 2. A terpene phenol resin having a hydroxyl group,
The anticorrosion coating composition according to claim 1, which is a terpene resin containing 1 to 3 hydroxyl groups in one molecule, and has a softening point of 20 to 180C.