JPS6260429B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an anti-corrosion lining composition capable of forming a strong coating with excellent anti-corrosion properties on coated objects, particularly steel. BACKGROUND ART Conventionally, resin linings for the purpose of preventing corrosion and rust of metals have been widely used in various pollution prevention devices and chemical equipment, as well as tanks, oil tanks of ships, ship bottoms, and the like. Unsaturated polyester resin is used as the resin for these resin linings due to its room temperature curability, on-site workability, cost, etc.
The lining method is FRP lining, i.e., before lining construction, resin is mixed with organic peroxide, a sheet-like base material made of glass fiber is applied to the base material to be lined, and the resin is applied with a felt roll or the like. A commonly used method is to impregnate the material, simultaneously defoaming it, and curing it. In addition to this method, a method that has recently been attracting attention is a method in which, instead of glass fiber, a composition made by blending extremely thin glass flakes with resin is applied onto the object using a trowel or the like (flake lining).
, and some of them have already been put into practical use. For example, such compositions include protective and decorative coating compositions containing fine glass flakes in an organic resin binder vehicle (Japanese Patent Publication No. 51-25368), or as corrosion-resistant coating compositions in a lining resin. Lining material filled with glass flakes and glass fibers as reinforcing material
30855), etc. are known. In addition, by treating the surface of flaky glass with an appropriate substance, it can be given hydrophobicity and leafing properties, and plastics, paints, insulating paper, etc.
-16821) is also known. However, considering the various performance aspects of the coating, the construction of the above compositions requires extremely thick films of 2 mm or more, and in addition, the construction cost is very high, so it is not applicable to general steel structures. The reality is that it is not used for a limited number of special purposes, as described above. Furthermore, if flake lining, which is currently used as a lining material, was used in a thin film of 2 mm or less in consideration of cost, it would not be possible to obtain the desired coating film performance, and it would be completely impractical. .
Particularly when used as a thin film, rusting occurs from pinholes in the film, which is an undesirable 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 leads to large defects such as blistering and peeling of the coating. It had a big problem of appearing as . In addition, some conventional unsaturated polyester resins have paraffin wax added to them due to their characteristics.
By floating this on the painted surface, it had the disadvantage that the surface would not harden unless the air was removed. Also, if paraffin wax is added and it floats on the surface enough, there is not a fatal problem, but in any case, since the wax is floating on the surface, there is a problem of delamination, and it is virtually impossible to recoat. Therefore, it was not suitable for cases where thick films required recoating or repairs were required. Furthermore, it is very difficult to appropriately control the floating of the paraffin wax, and depending on the operating conditions, the floating may become insufficient, resulting in defects such as uneven hardening. On the other hand, without adding paraffin wax,
Polybasic acids with sufficient surface drying properties,
Unsaturated polyester resins obtained by reacting polyhydric alcohols and polyhydric alcohol allyl ethers are widely used as air-drying paints for painting furniture, interior materials, household goods, etc. However, this type of resin has inferior corrosion resistance compared to conventional unsaturated polyester resins for heavy-duty corrosion protection, and cannot be used for heavy-duty corrosion protection. Furthermore, other types of resins allow styrene to volatilize without the addition of paraffin wax, thereby causing an apparent drying of the surface. However, since the surface layer of this type of material is not substantially cross-linked, when exposed to environmental fluids such as hot water, it swells, deteriorates, and exhibits a choking pattern, which not only makes the appearance unsightly, but also the inner surface of tanks, etc. In the case of a paint film, there is a risk of contaminating the contents, and it also has various other drawbacks, making it very inconvenient. The present invention can provide a novel composition that improves or eliminates the various drawbacks of the prior art as described above, that is, a coating that is excellent in rust prevention, adhesion, impact resistance, weather resistance, etc., and is durable. The present invention relates to an anticorrosive lining composition. The present invention relates to an anticorrosive lining composition comprising (a) 100 parts by weight of an epoxy resin-modified unsaturated polyester resin, (b) 10 to 70 parts by weight of glass flakes, and (c) 10 to 150 parts by weight of a flat metal pigment. . The epoxy resin-modified unsaturated polyester resin used in the composition of the present invention is: (1) an unsaturated polyester having an allyl ether group and a carboxyl group in the epoxy group in the bifunctional bisphenol A type epoxy resin; (hereinafter abbreviated as allyl ether group-containing unsaturated polyester) and a polymerizable monomer, or (2) bifunctional bisphenol A-type epoxy resin. Consists of an epoxy resin-modified unsaturated polyester obtained by bonding an allyl ether group-containing unsaturated polyester with acrylic acid or methacrylic acid (hereinafter abbreviated as (meth)acrylic acid) to an epoxy group, and a polymerizable monomer. In the above, the content of the epoxy resin-modified unsaturated polyester is usually 45 to 65% by weight. In the composition of the present invention, by using the former (1) epoxy resin-modified unsaturated polyester resin, it is possible to obtain a coating film that is recoatable and has excellent corrosion resistance and coating hardness. Furthermore, by using the latter epoxy resin-modified unsaturated polyester resin, in addition to the above-mentioned properties, it is possible to significantly improve the gelation rate of the coating film and, by extension, the air-drying properties. Said bifunctional bisphenol A in the present invention
Type epoxy resin (hereinafter simply referred to as epoxy resin) is a compound having the following structural formula. In this formula, n is usually appropriately selected from the range of 0 to 3. In addition, the epoxy equivalent of the epoxy resin is approximately
It ranges from 100 to 500, preferably about 180 to 300.
In the above range, if the epoxy equivalent is less than about 100, the glass transition temperature will be too low and the drying rate will tend to decrease. On the other hand, if it is about 500 or more, the functional group equivalents of allyl ether groups and (meth)acryloxy groups become too low when producing the unsaturated polyester of the present invention, and the curing rate decreases, which is also not preferred. The allyl ether group-containing unsaturated polyester used in the present invention must contain a free carboxyl group in its molecule, and the carboxyl group participates in the reaction with the epoxy group in the epoxy resin. Such unsaturated polyesters can be produced by any method. Generally, an allyl group-containing unsaturated polyester in which at least one free carboxyl group remains in the molecule is prepared by condensing polybasic acids, polyhydric alcohols, and polyhydric alcohol allyl ethers. As the polybasic acid, unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid, cistraconic acid, and anhydrides thereof are used, and if necessary, phthalic acid, isophthalic acid, terephthalic acid, and hettic acid are used. Saturated polybasic acids such as , adipic acid, sebacic acid, succinic acid, azelaic acid, and anhydrides thereof can also be used in combination. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylene glycol, triethylene glycol, trimethylolethane, trimethylolpropane, dihydroxypentadiene, pentaerythritol, diglycerin, ditrimethylolpropane, and the like. Examples of polyhydric alcohol allyl ethers include glycerin monoallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, trimethylolethane monoallyl ether, trimethylolethane diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether,
Pentaerythritol triallyl ether, 1,
Examples include 2,6-hexanetriol monoallyl ether, 1,2,6-hexanetriol diallyl ether, sorbitan monoallyl ether, and sorbitan diallyl ether. However, these compounds are merely examples, and the present invention is not limited to these compounds. Furthermore, the allyl ether group-containing unsaturated polyester is not necessarily limited to the above-mentioned composition, but may contain a polybasic acid, preferably an unsaturated polycarboxylic acid such as maleic anhydride or fumaric acid, and at least one polyester in the molecule. Even low-molecular compounds such as partially esterified products with polyhydric alcohol allyl ether having a hydroxyl group can be used. The desired epoxy resin-modified unsaturated polyester can be obtained by reacting the allyl ether group-containing unsaturated polyester with an epoxy resin. Specifically, for example, an allyl group-containing unsaturated polyester is prepared in advance, and an epoxy resin is mixed therein and reacted. In addition, during the reaction of polybasic acid, polyhydric alcohol, and polyhydric alcohol allyl ether, which are the raw materials for the unsaturated polyester, to produce an allyl ether group-containing unsaturated polyester in the system, an epoxy resin is further mixed with this. hand,
Methods such as continuing the reaction may also be taken as appropriate. During this reaction, a small amount of 2-hydroxyethylvalatluidine, 2-methylimidazole, trimethylbenzylammonium chloride, etc. is added as a catalyst. The reaction temperature ranges from 50 to 90°C, preferably from 60 to 70°C. In the present invention, by reacting the allyl ether group-containing unsaturated polyester with the epoxy resin as described above, a bisphenol skeleton, allyl ether group, maleic anhydride, etc. can be added to the unsaturated polyester of the present invention. There will be an unsaturated acid double bond based on the unsaturated polybasic acid. However, due to the presence of these three components, the performance of conventional air-drying paints is not reduced, and
Corrosion resistance, coating hardness, etc. can be significantly improved. In the above epoxy resin-modified unsaturated polyester, the epoxy resin component is
The purpose can be sufficiently achieved if the content is 20 to 80% by weight, but the anticorrosion property is more preferably exhibited in the range of 50 to 70% by weight. If the epoxy resin component is less than 20% by weight, the hardness of the coating film tends to decrease. On the other hand, if you use more than 80% by weight,
The viscosity becomes too high, which poses a practical problem. Further, the allyl ether group is selected from a range of 5 to 20% by weight based on the total polymer. In the present invention, in addition to the allyl ether group-containing unsaturated polyester, when (meth)acrylic acid is further bonded to the epoxy group in the epoxy resin, the coating film is improved compared to when the allyl ether group-containing unsaturated polyester is used alone. In other words, an epoxy resin-modified unsaturated polyester with excellent air-drying properties is obtained. As for the reaction, the carboxyl group in the molecule of (meth)acrylic acid also reacts with the epoxy group in the epoxy resin and bonds to it. In the present invention, in order to bond an allyl ether group-containing unsaturated polyester and (meth)acrylic acid with an epoxy resin, the allyl ether group-containing unsaturated polyester is usually first produced by the various methods described above, and then, A method is used in which an epoxy resin and (meth)acrylic acid are reacted at a temperature of 70 to 110°C. Further examples include a method in which an epoxy resin and an allyl ether group-containing unsaturated polyester; or a method in which an epoxy resin and (meth)acrylic acid are first reacted; and then the remaining one component is reacted. However, the present invention is not limited to these methods. In the above, it is desirable that (meth)acrylic acid be present in an amount of 5 to 50% by weight based on the total polymer.
The molecular weight of the epoxy resin-modified unsaturated polyester of the present invention thus obtained is about 1000 to
A range of 3000, more preferably about 1500 to 2500 is suitable. In the above, when the molecular weight becomes 1000 or less,
The coating viscosity is too low and the curing speed decreases. Also about
If it is more than 3,000, the viscosity is too high, and the desired coating viscosity cannot be achieved unless a large amount of styrene or the like is used, resulting in a decrease in the curing rate, which is similarly undesirable. In the present invention, the polymerizable monomers used together with the epoxy resin-modified unsaturated polyester include styrene, vinyltoluene, chlorostyrene, α-methylstyrene, divinylbenzene,
(meth)acrylic acid ester, glycidyl methacrylate, vinyl acetate, diallyl phthalate,
Triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tung oil, linseed oil, soybean oil,
Examples include cottonseed oil, safflower oil, and coconut oil. The polymerizable monomer is added after producing the epoxy resin-modified unsaturated polyester so that the solid content is about 45 to 65% by weight, as described above. Furthermore, if necessary, it may be used as a reactive diluent for adjusting the viscosity of the composition. Next, the glass flakes used in the anticorrosive lining composition of the present invention are extremely thin glassy flat particles with an average thickness of 0.5 to 10 μm and an average size of about 100 to 400 μm. The glass flakes are laminated in many layers parallel to the material within the coating, and have the effect of increasing the strength of the resin and at the same time preventing the permeation and penetration of external vapors, moisture, and other environmental agents. In general, the thinner the glass flakes and the larger the diameter, the greater the inhibition effect, and this tendency becomes more pronounced in severe corrosive environments. In the present invention, the mixing ratio of the epoxy resin-modified unsaturated polyester resin and glass flakes is 10 to 70 parts by weight of glass flakes per 100 parts by weight of resin.
A range of parts by weight (particularly preferably 20 to 60 parts by weight) is suitable from the viewpoint of corrosion resistance and physical properties. If the amount of glass flakes is less than 10 parts by weight in the above mixing ratio, the desired corrosion resistance cannot be obtained. On the other hand, if it exceeds 70 parts by weight, the flexibility of the film decreases and it becomes brittle, both of which are not preferred. On the other hand, the flat metal pigment used in the present invention is preferably one that is stable in the resin. for example,
Examples include flat lead powder, flat lead alloy powder, flat zinc powder, flat stainless steel powder, flat aluminum powder, and flat copper alloy powder. Particularly preferred is a flat metal rust-preventing pigment represented by a flat lead powder and/or a flat zinc powder that exhibits rust-preventive properties against metals. The flat metal pigment preferably has an average length of about 30 to 300 microns, preferably 50 to 250 microns, and a thickness of about 3 to 10 microns, preferably about 4 to 7 microns. In the length range of the flat metal pigment, if it is smaller than 30 μm, the pigment will not be flat, so that almost no effect of suppressing the permeation of corrosive ions in the coating film can be expected. On the other hand, if the length of the flat metal pigment exceeds the above 300μ, it will not line up parallel to the substrate due to the viscous resistance of the resin in the coating film, and in addition, the strength of the pigment itself will weaken.
During paint manufacturing (kneading) or painting, pigments tend to bend and therefore lose their flat shape, making it difficult to achieve the various effects aimed at by the present invention. Furthermore, metal pigments longer than 300μ tend to clog the spray tip when spray painting.
This is not preferable because it significantly reduces painting workability. In the present invention, the flat metal pigment is used in an amount of 10 to 150 parts by weight (particularly preferably 15 to 90 parts by weight) based on 100 parts by weight of the resin (component (a)). In the above mixing ratio, if the flat metal pigment is less than 10 parts by weight, the toughness, flexibility, and rust prevention properties of the film will deteriorate, which is undesirable. On the other hand, if it exceeds 150 parts by weight, the film becomes brittle, which is not preferable in either case. The present invention eliminates various drawbacks of conventional resin linings through the synergistic effect of the three components: (a) the epoxy resin-modified unsaturated polyester resin, (b) glass flakes, and (c) flat metal pigment, and, among other things, A coating film with excellent corrosion resistance, adhesion, and weather resistance can be obtained. That is, in addition to the effect of suppressing the permeation of corrosive ions by laminating glass flakes and flat metal pigments, the corrosive ions are made to react with the flat metal pigments before reaching the metal base, making them harmless. The anticorrosion properties of the film can be significantly improved. The permeation suppressing effect and trapping effect of the corrosive ions are due to the flat shape of the pigment. Furthermore, by using a flat metal pigment, the malleability of the metal is added to the film, and the flexibility of the film is improved. This effect plays a major role in improving the lack of physical properties, especially in thick films. The composition of the present invention having the above-mentioned structure is used in combination with a curing agent, a curing accelerator, etc. in a conventional manner. As the curing agent, ketone peroxide, hydroperoxide, peroxy ester, etc. are preferably used. Methyl ethyl ketone peroxide is suitable as the ketone peroxide. In addition, as hydroperoxide,
Examples include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, 2,5-dimethyl-2,5-dihydroperoxyhexane, and in particular cumene hydroperoxide, Preference is given to using t-butyl hydroperoxide. These are 1
It can be used as a species or a mixture of two or more. Furthermore, the peroxy esters include t-butyl peroxy phthalate, t-butyl peroxybenzoate, t-butyl peroxylaurate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy bivalate, Examples include t-butyl peroxyacetate and t-butyl peroxyisobutyrate. Particularly preferred is t-butyl peroxyphthalate and t-butyl peroxylaurate. These may be used alone or as a mixture of two or more. In the present invention, cobalt octylate, cobalt naphthenate, manganese naphthenate, etc. are used as the curing accelerator. In the present invention, a polymerization inhibitor may also be used in combination to adjust pot life. Such polymerization inhibitors include p-benzoquinone, naphthoquinone, phenanthraquinone, 2,5-diphenyl-
p-benzoquinone, hydroquinone, p-t-butylcatechol, 2,5-di-t-butylhydroquinone, mono-t-butylhydroquinone,
Examples include 2,5-di-t-amylhydroquinone. Furthermore, it is possible to add coloring pigments, extender pigments, suspending agents, dispersants, diluents, other flat pigments, etc. to the composition of the present invention, if necessary. The composition of the present invention thus obtained is applied onto a steel material by a conventional method such as brushing, roller, air spraying, etc. to a film thickness of about 2 mm or less, preferably 300 μ or more, and then dried at room temperature or by heating. be done. The coating film obtained after drying naturally has excellent properties such as strength and corrosion resistance. If necessary, a top coat of chlorinated rubber, alkyd resin, epoxy resin, urethane resin, acrylic resin, or a top coat of unsaturated polyester resin and glass flakes may be applied to the coating film obtained from the composition of the present invention. May be applied. It has thus been found that the coating film obtained from the composition of the present invention exhibits excellent adhesion to these top coatings. The details of the present invention will be explained below using Examples and Comparative Examples. Example 1 Formulation 1 (Main ingredient) Part by weight Epoxy resin-modified unsaturated polyester resin A 40 Organic bentonite [Bentone #34: trade name manufactured by National Red Co., Ltd.] 2.0 Styrene 32.5 Cobalt naphthenate (contains 6% metallic cobalt)
0.5 Glass flakes [CCF-150: manufactured by Nippon Sheet Glass Co., Ltd. Product name: average size 150-200μ, thickness 3-5μ] 15 Flat lead powder [manufactured by Fukuda Metals Co., Ltd.: average length 150-200μ
μ, thickness 4 to 6 μ] 10 100.0 (Curing agent) Methyl ethyl ketone peroxide 1.0 The epoxy resin-modified unsaturated polyester resin A was obtained as follows; 0.45 mol of glycerin monoallyl ether, anhydrous maleic 1.0 mol of acid and 0.5 mol of ethylene glycol were charged and reacted for 6 hours at a temperature of 180°C to obtain an allyl ether group-containing unsaturated polyester. To this, 0.5 mole of bisphenol A diglycidyl ether was added as an epoxy resin component, and
0.3% amount of 2-hydroxy paratoluidine was added and reacted at 90°C for 1 hour. Compared to this, 2.5% of the total system
After adding methanol and reacting for an additional hour,
After depressurizing at 10 mmHg for 30 minutes, styrene was added to give a solid content of 60%, acid value of 18 mgKOH/g, and viscosity.
An epoxy resin-modified unsaturated polyester resin of 3000 cps and an epoxy resin component content of 60% based on the total polymer was obtained. Resin A was prepared by adding 0.03% of hydroquinone as a polymerization inhibitor to this resin. (Preparation of test piece) The epoxy resin-modified unsaturated polyester resin A and organic bentonite were mixed and kneaded with a roller, then other components were added and stirred with a disper to prepare a base material. 150×50×1.6mm mild steel plate (JIS-G
-3141) by sandblasting to completely remove black scales, rust, and oil, and then apply a paint containing the main ingredient of Formulation 1 with a curing agent added to it by air spraying to reduce the dry film thickness.
It was coated to a thickness of 500±50μ, dried for 7 days, and then subjected to a comparative test. Example 2 Blend 2 (Main ingredient) Part by weight Epoxy resin modified unsaturated polyester resin B 40 Organic bentonite (same as Example 1) 2.0 Styrene 9.5 Cobalt naphthenate (same as Example 1) 0.5 Glass flakes (same as Example 1) 8 Flat lead alloy powder [manufactured by Toyo Kinzoku Powder Co., Ltd.: Cu addition amount
0.1%, average length 30-80μ, thickness 4-6μ]
40 100.0 (Curing agent) Methyl ethyl ketone peroxide 0.4 Cumene hydroperoxide 0.4 The epoxy resin-modified unsaturated polyester resin B was obtained as follows. Diarylpentaerythritol 0.45 mol, fumaric anhydride 0.8 mol, phthalic anhydride 0.2 mol, temperature
0.5 mol of acrylic acid was added to the allyl ether group-containing polyester obtained by reacting at 60°C for 2 hours.
0.5 mol of bisphenol A diglycidyl ether and 2-hydroxyethyl para-toluidine in an amount of 0.3% based on the total system were charged at once and heated at 90°C for 10
Allowed time to react. Then, cool to 60℃, add 2% methanol to the whole system, react for another 1 hour, and reduce to 10mmHg.
After vacuum treatment for 30 minutes, styrene was added to modify the epoxy resin with a solid content of 60%, an acid value of 13 mgKOH/g, a viscosity of 2000 cps, and a content of epoxy resin component and acrylic component of the total polymer of 10% and 50%, respectively. An unsaturated polyester resin was obtained. Epoxy resin-modified unsaturated polyester resin B was obtained by adding 0.03% of hydroquinone to this. (Preparation of test piece) A paint was prepared in the same manner as in Example 1, and a test piece was prepared and subjected to a comparative test. Example 3 Blend 3 (Main ingredient) Epoxy resin modified unsaturated polyester resin C 35 Organic bentonite (same as Example 1) 3.0 Styrene 16.5 Cobalt naphthenate (same as Example 1) 0.5 Glass flakes (same as Example 1) 15 Flat zinc powder [manufactured by Sakai Chemical Industry Co., Ltd.: average length 50~
60μ, thickness 6-7μ] 30 100.0 (Curing agent) Methyl ethyl ketone peroxide 0.7 The epoxy resin-modified unsaturated polyester resin C was obtained as follows; Diallylpentaerythritol 0.45 mol, maleic anhydride Methacrylic acid was added to the allyl ether group-containing polyester obtained by reacting 1.0 mol and 0.3 mol of ethylene glycol at a temperature of 60°C for 2 hours.
0.5 mol of bisphenol A diglycidyl ether, and 0.3% of 2-hydroxyethyl para-toluidine based on the total system were charged in bulk.
The reaction was carried out at 90°C for 10 hours. Then, cool to 60℃, add 2% methanol to the whole system, and let the reaction continue for 1 hour.
After depressurizing at 10 mmHg for 30 minutes, styrene was added and the solid content was 60%, acid value 17 mgKOH/g, viscosity
An epoxy resin-modified unsaturated polyester resin of 3500 cps and a content of epoxy resin component and acrylic component of the total polymer of 45% and 17%, respectively, was obtained.
Epoxy resin-modified unsaturated polyester resin C was obtained by adding 0.03% of hydroquinone to this. (Preparation of test piece) A paint was prepared in the same manner as in Example 1, and a test piece was prepared and subjected to a comparative test. Example 4 Blend 4 (Main ingredient) Part by weight Epoxy resin modified unsaturated polyester resin D 40 Organic bentonite (same as Example 1) 1.0 Styrene 28.5 Cobalt naphthenate (same as Example 1) 0.5 Glass flakes (same as Example 1) ) 15 Flat lead alloy powder [manufactured by Toyo Kinzoku Powder Co., Ltd.: Sb addition amount
1.0%, average length 30-80μ, thickness 4-6μ]
20 100.0 (Curing agent) Methyl ethyl ketone peroxide 0.4 t-butyl peroxyphthalate 0.6 The epoxy resin-modified unsaturated polyester resin D was obtained as follows. To the allyl ether group-containing unsaturated polyester obtained by reacting 0.45 mol of diallyl pentaerythritol and 1.0 mol of maleic anhydride at a temperature of 60°C for 2 hours, 0.5 mol of acrylic acid, 0.5 mol of bisphenol A diglycidyl ether, and 2-hydroxyethyl para-toluidine was added in an amount of 0.3% to the entire system and reacted at 90°C for 10 hours. Then cool to 60℃ and add 2% methanol to the whole system.
After further reaction for 1 hour and vacuum treatment at 10 mmHg for 30 minutes, styrene was added and the solid content was 60%, the acid value was 13 mg KOH/g, the viscosity was 2500 cps, and the content of the epoxy resin component and acrylic component was 50% each based on the total polymer. %, 15% epoxy resin modified unsaturated polyester resin was obtained. Hydroquinone 0.03 to this
% was added as the resin D. (Preparation of Sample) The formulation 4 was made into a paint in the same manner as in Example 1, and a test piece was prepared and subjected to a comparative test. Comparative Example 1 Blend 5 (Main ingredient) Part by weight Isophthalic acid-based unsaturated polyester resin [Rigorak 150HR: trade name manufactured by Showa Kobunshi Co., Ltd.] 45 Organic bentonite (same as Example 1) 2.5 Styrene 26.7 Cobalt naphthenate (Example) 1) 0.8 Glass flakes (same as Example 1) 25 100.0 (Curing agent) Methyl ethyl ketone peroxide 0.6 Formulation 5 was made into a paint in the same manner as in Example 1,
A test piece was prepared and subjected to a comparative test. Comparative Example 2 (Main ingredient) Part by weight Isophthalic acid-based unsaturated polyester resin (same as Comparative Example 1) 30 Organic bentonite (same as Example 1) 2.0 Styrene 37.5 Cobalt naphthenate (same as Example 1) 0.5 Glass flakes (same as Example 1) Same as Example 1) 10 Zinc powder (average particle size 5μ) 20 100.0 (Curing agent) Methyl ethyl ketone peroxide 0.5 The composition with the above formulation was made into a paint in the same manner as in Example 1, and a test piece was prepared for a comparative test. provided. Comparative Example 3 (Main ingredient) Isophthalic acid-based unsaturated polyester resin (same as Comparative Example 1) 40 Organic bentonite (same as Example 1) 2.0 Styrene 32.5 Cobalt naphthenate (same as Example 1) 0.5 Glass flakes (Same as Example 1) ) 15 Flat lead powder (manufactured by Fukuda Metal Co., Ltd.: average length 150-200
μ, thickness 4 to 6 μ] 10 100.0 (Curing agent) Methyl ethyl ketone peroxide 0.5 The composition with the above formulation was made into a paint in the same manner as in Example 1, and a test piece was prepared and subjected to a comparative test.

【table】

[Table] It is clear from the above comparison test table that the coating obtained from the composition of the present invention not only has much better rust prevention properties than the coating obtained from the conventional lining composition. It showed excellent performance in terms of adhesion, impact resistance, weather resistance, and chemical resistance. These are obtained as a result of the synergistic effect of epoxy resin-modified unsaturated polyester resin, glass flakes and flat metal pigments.

Claims (1)

[Scope of Claims] 1. An epoxy resin-modified unsaturated polyester resin in which an unsaturated polyester having an allyl ether group and a carboxyl group is bonded to an epoxy group in a bifunctional bisphenol A type epoxy resin.
An anticorrosive lining composition comprising: 100 parts by weight of glass flakes, 10 to 70 parts by weight, and 10 to 150 parts by weight of flat metal pigment. 2. The anticorrosive lining composition according to claim 1, wherein the flat metal pigment is at least one type of flat metal rust preventive pigment selected from lead powder and zinc powder. 3. Claim 1, wherein the unsaturated polyester having an allyl ether group and a carboxyl group is a partial esterification product of an unsaturated polybasic acid or its anhydride and a polyhydric alcohol allyl ether having one hydroxyl group. The anticorrosive lining composition described. 4. The anticorrosive lining composition according to claim 3, wherein the unsaturated polybasic acid or anhydride thereof of the unsaturated polyester is maleic anhydride. 5 Epoxy resin-modified unsaturated polyester resin in which acrylic acid or methacrylic acid is combined with an unsaturated polyester having an allyl ether group and a carboxyl group in the epoxy group in a bifunctional bisphenol A type epoxy resin...100 parts by weight Glass flakes... An anticorrosive lining composition comprising 10 to 70 parts by weight of a flat metal pigment and 10 to 150 parts by weight. 6. The anticorrosive lining composition according to claim 5, wherein the flat metal pigment is at least one type of flat metal rust preventive pigment selected from lead powder and zinc powder. 7. Claim 5, wherein the unsaturated polyester having an allyl ether group and a carboxyl group is a partial esterification product of an unsaturated polybasic acid or its anhydride and a polyhydric alcohol allyl ether having one hydroxyl group. anti-corrosion lining composition. 8. The anticorrosive lining composition according to claim 7, wherein the unsaturated polybasic acid or anhydride thereof of the unsaturated polyester is maleic anhydride.