JPS6019943B2 - Anticorrosive coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anti-corrosion coating composition that can form a tough film with excellent weather resistance and anti-corrosion properties on steel.

BACKGROUND ART Conventionally, resin coatings (linings) for the purpose of preventing corrosion and rust on metals have been widely used mainly in various pollution control devices and chemical equipment, as well as tanks, oil tanks of ships, ship bottoms, and the like. As the resin used for these resin linings, unsaturated polyester resin is used from the viewpoints of room temperature curability, on-site workability, and cost.The lining method is FRP lining, that is, adding organic hydroxide to the resin in advance before lining construction. Mix the oxides, apply a sheet-like base material made of glass fiber to the matrix to be lined, impregnate it with the resin using a felt roll or the like, and simultaneously defoam it,
It was common to harden it.

Recently, in addition to this method, a method that has been attracting attention is a method in which a composition made by blending extremely thin glass flakes with resin instead of glass fiber is applied onto the object using a trowel.
Flake lining) is already in practical use.

For example, the above-mentioned compositions include a protective and decorative coating composition containing fine glass flakes in an organic resin binder vehicle (Hakama Kosho 51-253 Iso Publication), or a corrosion-resistant coating composition in a lining resin. A lining material filled with glass flakes and glass fiber as a reinforcing material (Japanese Patent Application Laid-Open No. 52-30855) is known, and by treating the surface of flaky glass with an appropriate material, , plastics, paints, insulating paper, etc. that have been given hydrophobic reversibility and filled with the same (Special Publication Publication No. 47-
16821) is also known.

The application of the above composition was carried out in accordance with 2.
It is an extremely thick film that is thicker than a steel roof, and the construction cost is very high.Therefore, it is not often applied to general steel foundation additions, and is currently used for very limited special purposes as mentioned above. be.

If flake lining, which is currently used as a lining material, is used in a thin film of 2 yanagi or less in consideration of cost,
It was not possible to obtain the desired coating performance and it was not practical.

In particular, when used as a thin film, rust was generated from pinholes in the film, which was a serious problem.

In other words, rust that occurs in the pinhole area grows rapidly, and rust does not only occur in the pinhole area, but also progresses from that area between the coating and the base steel, and eventually causes large scale problems such as blistering and peeling of the coating. It becomes a defect. In addition, when used for bridges, offshore structures, etc., it is necessary to color the object to match the purpose of the coating. After the lining material is applied, a top coat of urethane-based, acrylic-based, or chlorinated rubber-based paint is applied. However, films made from ordinary colored pigments change color or fade after long-term use, so they cannot be used as lining materials in applications where a durability of 20 to 30 kg, or in some cases 50 to 60 kg, is required. During that period, the surface had to be repainted several times. The present invention eliminates the various drawbacks of the prior art as described above, and can provide a durable film with excellent rust prevention, adhesion, impact resistance, weather resistance, etc., and has long-term resistance to discoloration and fading. The present invention relates to an anticorrosion coating composition having the following properties.

That is, the present invention comprises 100 parts by weight of an unsaturated polyester resin, 10 to 150 parts by weight of uniformly colored glass flakes having a thickness of 0.5 to 10 mm and a size of 100 to 400 mm, and a necessary amount of a curing agent. The present invention relates to an anticorrosive coating composition comprising:

The unsaturated polyester resin used in the present invention is a resin that is liquid at room temperature without being diluted with a volatile solvent, and is a resin that hardens with a hardening agent or catalyst, and the cured coating film has excellent water resistance and chemical resistance. is suitable.

Examples of these resins include commercially available phthalic acid unsaturated polyester resins, bisphenol unsaturated polyester resins, and epoxy acrylate resins.

Examples of the unsaturated polyester resin include, for example, U-Pica 5523-45 (trade name) manufactured by Nippon U-Pica Co., Ltd., which is commercially available as a phthalic acid-based unsaturated polyester resin.
29: Product name Rigoratsuku 15-jo R manufactured by Showa Kobunshi Co., Ltd.
etc.: Commercially available bisphenol-based unsaturated polyester resin manufactured by Kao Atlas Co., Ltd., trade name Atlatsu 382-05; manufactured by Showa Kobunshi Co., Ltd., trade name RIGOLAC LP-1; manufactured by Nippon UPICA Co., Ltd., trade name UPICA 5834
etc.: Trade name Atrac G-657 manufactured by Kao Atlas Co., Ltd., which is generally commercially available as an epoxy acrylate resin.
5: Showa Kobunshi Co., Ltd., trade name: Lipoxy R-800: Nippon Spica Co., Ltd., trade name: Neopol 8250: Dainippon Ink & Chemicals Co., Ltd., trade name: Ditskrite 3505:
Product name Delakane 510 411 manufactured by Dow Chemical Co., Ltd.
etc.

These resins usually contain liquid Q, 6-monoethylenically unsaturated monomers such as styrene and methyl methacrylate from 10 to 10%.
It is commercially available containing 5% by weight.

Therefore, in the present invention, the unsaturated polyester resin includes monomers thereof. The glass flakes whose entire surface is uniformly colored (hereinafter referred to as colored glass flakes) used in the anticorrosive coating composition of the present invention have a thickness of 0.5 to 10 mm,
Preferably 1 to 6 peaks, 100 to 400 µm in size, preferably 150 to 300 µm glassy, extremely thin fan-shaped particles, which are uniformly colored not only on the surface but also inside. .

The colored glass flakes are layered in parallel to the material within the film, increasing the strength of the resin, and at the same time blocking the penetration of external vapors, moisture, and other environmental agents, as well as blocking ultraviolet rays. to shield. Furthermore, since the colored glass flakes have almost no deterioration due to ultraviolet rays, there is no discoloration or fading of the coating film using the colored glass flakes, and therefore, the effect is that the original color is maintained. Generally, the thinner the colored glass flakes are and the larger the diameter, the greater the inhibition effect, and this tendency is more pronounced in severe corrosive environments.
In the present invention, the mixing ratio of the unsaturated polyester resin and colored glass flakes is 1 resin (including styrene, etc.).
0 parts by weight, 10 to 15 parts by weight (particularly preferably 20 to 60 parts by weight) of colored glass flakes has corrosion resistance,
It is suitable from the viewpoint of stiffness resistance or physical properties.

In the above mixing ratio, if the amount of colored glass flakes is less than 10 parts by weight, it will not be possible to obtain the desired corrosion resistance or weather resistance of the coating, and conversely, if it exceeds 150 parts by weight, the baldness of the coating will deteriorate. This is not preferable because it deteriorates and becomes brittle.

When the composition of the present invention is used, a curing agent, a curing accelerator, etc. are used in a conventional manner. As the curing agent for the unsaturated polyester resin, ordinary peroxide etc. are used,
In particular, in the present invention, unsaturated polyester resin 100
Ketone peroxide 0.1 to 1.0% by weight. It is preferred to use 0.5 to 2.0 parts by weight of hydroperoxide and/or peroxyester. As the ketone peroxide, methyl ethyl ketone peroxide is suitable.

In addition, examples of hydroperoxide include t-butyl hydroperoxide, cumene hydroperoxide,
Examples include diisopropyl besozene hydroperoxide, /ramenthane hydro/gu oxide, 2,5-dimethyl-2,5-dihydroperoxyhexane, and in particular, use of cumene hydroperoxide and t-butyl hydroperoxide. is preferred. These may be used alone or as a mixture of two or more. Furthermore, peroxyesters include t-butyl peroxy phthalate, t-butyl peroxybenzoate, t-butyl peroxy laurate, t-butyl peroxy 2-ethyl hexa/ate, and t-butyl peroxy. pivalate,
Examples include t-butyl/guoxyacetate and t-butyl peroxyisobutyrate, with t-butyl peroxyphthate and t-butyl peroxylaurate being particularly preferred. These may be used alone or as a mixture of two or more. In the present invention, by using a combination of ketone peroxide, hydroperoxide and/or peroxyester, it is possible to control the release time of the composition, that is, the curing time of the coating film. As a result, the colored glass flakes become parallel in the coated film, forming a corrosion ion permeation suppressing layer arranged parallel to the substrate. The amount of ketone peroxide, hydroperoxide and/or peroxyester to be added is particularly preferably within the above range from the viewpoint of the above effects.

However, the amount of these compounds used is likely to be affected by the outside temperature at the time of coating. According to experiments conducted by the present inventors, ketone peroxide is approximately 0.6 parts by weight per 10 parts by weight of unsaturated polyester resin solids (including styrene, etc.) at a temperature of 5°C, and 20 parts by weight. The amount added is preferably around 0.3 parts by weight when the temperature is 30°C, and around 0.1 parts by weight when the temperature is 30°C.

In addition, hydroperoxide and/or peroxyester is about 1.4 parts by weight when the temperature is 5°C, and about 1.4 parts by weight when the temperature is 20°C, per 10 parts by weight of the solid content of the unsaturated polyester resin (including styrene, etc.). Approximately 0. Approximately 0. The amount added is preferably around $ parts by weight.

If the amount added at each temperature is too much more than the above amount, the release time will be shortened, making painting work difficult, and the coating film will harden in a short time, making it difficult for glass flakes to be arranged in parallel.

On the other hand, if the amount added is less than the above-mentioned amount, the drying time becomes too long, which is not preferable. Furthermore, extender pigments, suspending agents, dispersants, diluents, solvents, other flat pigments, etc. can be added to the composition of the present invention, if necessary.

The composition of the present invention thus obtained can be used for brushing, lo-fu,
It is applied to a steel material by a conventional method such as air spraying to a film thickness of 2 or less, preferably 300 or more, and then dried at room temperature or by heating. The coating film obtained after drying has excellent properties such as strength, corrosion resistance, and weather resistance. The details of the present invention will be explained below with reference to Examples and Comparative Examples.

Example 1 Formulation 1 (Main ingredient) Part by weight Isophthalic acid-based unsaturated polyester resin 40 [Rigolak 15 Seikm: Product name manufactured by Showa Kobunshi Co., Ltd.] Organic pentonite [Bentone #34: 20 Product name manufactured by National Red Co., Ltd.] styrene
32.5 cobalt naphthenate (contains 6% metallic cobalt 0.5) colored glass flakes [average size 150 25-200 µm thickness 3-
5r*〕100-〇(hardening agent) Methyl ethyl ketone peroxide 0.5*Preparation of colored glass flakes Part by weight Silica sand 50.0 Cryolite 2.0 Soda ash
19.0 bone ash 1.0 parts by weight
Part by weight Potassium carbonate 1.5 Salt 0.5 Borax 4.0 Selenium 1.0 Zinc white
7.5 Cadmium Sulfide 1.3.

The above composition was placed in a rubbo and heated and melted to 1200 to 1300 qo to create a colored glass puff. After attaching the above molten glass to the tip of a small-diameter pipe, air is blown from the opposite side to inflate it into a balloon shape and then cooled.Then, the balloon-shaped colored glass is crushed, and the crushed colored glass is classified using nodes. Colored glass flakes were created.

The unsaturated poly in the main ingredient of Formulation 1. After mixing ester resin and organic pentonite and kneading with a roller, other ingredients were added and mixed with a disper to prepare a base agent. 150×
After completely removing black scale, rust, and oil from a 50×1.6-sized mild steel plate (JIS-G-3141) by shot blasting, the paint made by adding a curing agent to the main ingredient of Formulation 1 was dried with air spray. It was coated to a film thickness of 500 mA and 50 mounds, and after drying for 7 days, it was subjected to a comparative test.

Example 2 Formulation 2 (Main ingredient) Parts by weight Pisphenol polyester resin 35 [Rigolac LP-1: Showa Kobunshi Co., Ltd. product name] Organic pentonite (same as Example 1) 3.0 Styrene 165 Cobalt naphthenate ( Same as Example 1 0.51) Colored glass flakes (Same as Example 1 45.01) 100-
〇 (Curing agent) Methyl ethyl ketone peroxide 0.2 Cumene hydroperoxide 0.3 The composition of Formulation 2, which was brazed in the same manner as in Example 1, was applied to the mystery piece prepared in the same manner as in Example 1. and was subjected to a comparative test.

Example 3 Blend 3 (Main ingredient) Part by weight Epoxy acrylate resin 40 [Lipoxy R
-800: Showa Kobunshi Co., Ltd. product name] Organic pentonite (same as Example 1) 1.0 Styrene 28.
5 Cobalt naphthenate (same as Example 1) 0.5 Colored glass flakes (same as Example 1) 30.01〇〇-〇 (hardening agent) Methyl ethyl ketone peroxide 0.2t
-Butyl/di-oxyphthalate 0.3 A sample prepared in the same manner as in Example 1 was coated with the composition of Formulation 3, which was kneaded in the same manner as in Example 1, and then dried and subjected to a comparative test.

Comparative Example 1 Blend 4 (Main ingredient) Part by weight Isophthalic acid-based unsaturated polyester resin 45 (Example 1
) Organic pentonite (same as Example 1) 2
．． 5 styrene
26.7 Azo red pigment
10.0 Cobalt naphthenate (same as Example 1) 0
．． 8 glass flakes (average size 150~1
5200 mm, thickness 3-5 mm) 100-〇 (hardening agent) Methyl ethyl ketone/g-oxide 0.6
The composition of Formulation 4 above was applied to a sample prepared in the same manner as in Example 1 so that the dry coating thickness was 500±50r,
After drying at room temperature for 7 days, it was subjected to a comparative test.

Comparative Example 2 10 parts by weight of glass flakes having an average size of 150 to 200 microns and an average thickness of 3 to 5 microns, 2 parts by weight of chromium oxide, and 2 parts by weight of a condensed aluminum phosphate-based inorganic binder were mixed.

Microscopic examination of the mixture showed that the glass flakes were crushed into a fine powder with an average size of 20-100 microns. When the mixture thus obtained was heated at 500°C for 1 hour, a green lump was obtained, but it could not be used as it was, so it was crushed in a mortar, passed through a sieve, and had an average size of 150°C. ~200
A micron powder was obtained. When this powder was examined under a microscope, it was found to be irregularly shaped granules, far from flakes. For comparison, a test piece was prepared in the same manner as in Example 1 instead of the glass flakes, and was subjected to the test. Comparative Example 3 In order to further clarify the difference between colored glass flakes and normal glass flakes, instead of colored glass flakes in the formulation of Example 1, an average size of 150 to 200 microns,
A test piece was prepared in the same manner using uncolored glass flakes having an average thickness of 3 to 5 microns, and was subjected to the test.

Comparative Example 4 Poppy seeds with an average particle size of 150 microns, 10 parts by weight of sand, 2 parts by weight of chromium oxide, and 2 parts by weight of condensed aluminum phosphate were mixed, and this was put into a kiln and heated to about 3 powders at a temperature of about 600 qC. After heating for a while, colored poppy/sand with a green color was obtained.

Using this colored poppy and sand, a paint was prepared according to the following formulation, and a test piece was prepared on the same machine as in Example i and subjected to a test. Unsaturated polyester resin (same as Example 1) 20 parts by weight Styrene 7.5 Methyl ethyl ketone peroxide (curing agent) 0.
5 Colored silica sand 7098.0 Tsune・R Toshin Q Suzuto Zenun Sardine wo Shizukukuma Poison RmS Division Military Ants Hebishi Rin Kurakuremi To ○ T.

* [Nada Word K Shout KKK] From the above comparison test result table, it is clear that the film obtained from the composition of the present invention is superior to the film obtained from the conventional lining composition. It is clear that the weather resistance (resistance to discoloration and fading) is significantly improved and the corrosion resistance is also excellent.

Claims (1)

[Claims] 1 100 parts by weight of unsaturated polyester resin, thickness 0.5
An anticorrosive coating composition comprising 10 to 150 parts by weight of uniformly colored glass flakes having a size of 100 to 400 microns and the required amount of a hardening agent.