JP2000063448A - Corrosionproof coating composition for steel product and corrosionproof coated steel structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve acid resistance, low volatility, endurance, economics, and workability of a corrosionproof coating composition for steel products by employing a composition comprising a non-styrene type vinyl ester resin containing a vinyl ester and a low volatile radical polymerizable monomer, a scaly inorganic filler and a radical curing accelerator. SOLUTION: A corrosionproof coating composition for steel products is obtained by reacting an epoxy resin with (meth)acrylic acid in 0.8-1.2 of an equivalent ratio of the epoxy resin to the (meth)acrylic acid at a temperature of 80-140 deg.C for 1-4 hr to prepare a vinyl ester, and blending 70-85 pts.wt. of a non-styrene type vinyl ester resin containing 40-90 pts.wt. of the resultant vinyl ester and a low volatile radical polymerizable monomer having a vapor pressure of 1 mmHg or below at 20 deg.C, 15-30 pts.wt. of a scaly inorganic filler and 0.5-2.0 pts.wt. of a radical curing accelerator. A corrosionproof coated steel structure is obtained by coating the non-styrene type vinyl ester resin on the surface of a steel product 1, curing the coating layer to prepare a primer layer 2 having a thickness of 0.02-1 mm, applying the corrosionproof coating composition onto the layer 2, and curing the composition to form a corrosionproof coating layer 3.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a steel anticorrosion coating structure. More specifically, bridges, breakwaters, piers, steel towers,
The present invention relates to an anticorrosion coating structure for steel structures in roof materials, wall materials, chimneys, flues and the like.

[0002]

2. Description of the Related Art Since steel materials are excellent in durability and economy, they are used for bridges, breakwaters, piers, steel towers, roof materials, wall materials, chimneys,
Alternatively, it is widely used as a structure such as a flue. These steel structures are usually exposed to erosion deterioration due to salt damage, acid rain damage, wind and water damage, and the like. In order to prevent this, it is often adopted to apply a coating material to the surface of the steel structure to prevent corrosion (for example, described in the Corrosion Resistance Handbook, published by the High Pressure Gas Safety Association, March 10, 1983 edition). That is, it is common to use plating anticorrosion, epoxy resin, tar epoxy resin, unsaturated polyester resin, vinyl ester resin and the like. However, these have the following problems.

That is, in plating anticorrosion, since the anticorrosion layer is thin and the steel material is likely to have an exposed portion due to post-processing, it is difficult to prevent deterioration of the steel material from the exposed portion. Epoxy resins and tar epoxy resins have a drawback in that the resin itself is poor in acid resistance, so that it is necessary to apply a thick coating material, and durability, economy, and workability are inferior. Further, the unsaturated polyester resin and the vinyl ester resin have good acid resistance, but they use a styrene monomer, and since they have a high volatility, they have a strong odor and have a problem to the environment.

[0004]

An object of the present invention is to provide a steel anticorrosion coating material composition having low volatility and excellent durability, economy and workability while maintaining the acid resistance originally possessed by vinyl ester resins. Is to provide. Another object of the present invention is to provide a steel anticorrosion coating structure that uses the anticorrosion coating material composition, has less volatile components during anticorrosion, and has excellent durability and adhesive strength with steel materials. It is to be.

[0005]

As a result of intensive studies to solve the above problems, the present inventors have found that the following steel material anticorrosion coating material composition and steel material anticorrosion coating structure using the same are effective. I found it. That is, the present invention provides [1] 70 to 85 parts by weight of a non-styrene type vinyl stell resin containing a vinyl ester and a low volatile radically polymerizable monomer, 15 to 30 parts by weight of a scale-like inorganic filler, and a radical curing accelerator 0 .5-
A steel material anticorrosion coating material composition comprising 2.0 parts by weight, and [2] the steel material according to [1] above with a primer layer formed by curing a non-styrene type vinyl ester resin on a steel material substrate. A steel anticorrosion coating structure comprising an anticorrosion coating layer obtained by curing an anticorrosion coating material composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. First, the terms used in this specification will be described. (1) Non-styrene type vinyl ester resin is a composition containing 40 to 90 parts by weight of vinyl ester and 60 to 10 parts by weight of a low-volatile radically polymerizable monomer. (2) The scaly inorganic filler is an inorganic filler having an aspect ratio of 10 or more and an average particle diameter of 100 to 300 μm, and preferably glass flakes. (3) The radical curing accelerator is not particularly limited as long as it has a function of causing a redox reaction with an organic peroxide and facilitating generation of radicals, but cobalt organic compounds such as cobalt naphthenate and cobalt octenoate. Examples thereof include acid salts, vanadium salts and aromatic tertiary amines.

(4) Epoxy resin is a commercially available epoxy resin having two or more glycidyl groups in one molecule, and Epicoat 828, 1001, manufactured by Yuka Shell Co.,
Examples thereof include bisphenol A type epoxy resins such as 1002 and 1004, bisphenol F type epoxy resins such as Epicoat 807, novolac type epoxy resins such as Epicoat 152 and 154, and cresol type epoxy resins. (5) Steel materials refer to so-called ordinary steel materials specified in JIS G3100-3600 series and so-called alloy steel materials specified in 4000-4900 series.

Next, the present invention will be specifically described. (1) Production of non-styrene type vinyl ester resin The non-styrene type vinyl ester resin in the present invention is
It comprises 40 to 90 parts by weight of vinyl ester and 60 to 10 parts by weight of a low-volatile radically polymerizable monomer. Here, the vinyl ester can be produced by heating and reacting the above-mentioned epoxy resin and acrylic acid / and / or methacrylic acid at 80 to 140 ° C. in a reactor equipped with a stirrer. Acrylic acid and / or methacrylic acid may be charged all at once from the beginning, or after the reaction temperature is reached, they may be added dropwise successively and continuously. During the reaction,
It is also possible to use a tertiary amine or a quaternary ammonium salt as a reaction catalyst for the glycidyl group and the carboxyl group.

Further, in order to prevent the gelation of the resin during the reaction, it is general to preliminarily charge a polymerization inhibitor into the reactor or blow dry air (oxygen). The ratio of reacting the glycidyl group contained in the epoxy resin with acrylic acid and / or methacrylic acid is an equivalent ratio of 0.
8 to 1.2 is preferable. Outside this range, the crosslink density after curing is low and the chemical resistance is poor, which is not preferable. The end point of the reaction is determined by measuring the acid value of the reaction product, but the reaction rate is 90%.
The reaction is generally completed as described above.

After completion of the reaction between the epoxy resin and acrylic acid and / or methacrylic acid, an organic acid anhydride having a hydroxyl group present in the vinyl ester molecule and an unsaturated group such as maleic anhydride or tetrahydrophthalic anhydride is added, The modified vinyl ester obtained by further heating reaction is also included in the vinyl ester of the present invention. At that time, with respect to the hydroxyl group present in the vinyl ester molecule, 0.1 to 0.1
1 to 4 at 60 to 120 ° C. with 1 equivalent of organic acid anhydride
Can react for hours. 40 to 90 parts by weight of the vinyl ester thus obtained can be dissolved in 60 to 10 parts by weight of the low-volatile radically polymerizable monomer to produce the non-styrene type vinyl ester resin of the present invention. When a vinyl ester is dissolved in a low-volatile radically polymerizable monomer, a quinone, a hydroquinone, or a phenol, which is a polymerization inhibitor, may be blended with the vinyl ester in advance and dissolved, as in a conventional method. .

The low-volatile radically polymerizable monomer is not particularly limited as long as it has a vapor pressure at 20 ° C. of 1 mmHg or less and has a radically polymerizable unsaturated group. Examples thereof include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate,
Dimethacrylates such as triethylene glycol dimethacrylate, trimethacrylates such as trimethylolpropane trimethacrylate, diallyl phthalates,
Examples thereof include allyl compounds such as trimethylolpropane diallyl ether and pentaerythritol triallyl ether. Moreover, these can be used individually or in mixture of 2 or more types in arbitrary ratios.

(2) Steel material anticorrosion coating material composition The steel material anticorrosion coating material composition comprises 70 to 85 parts by weight of a non-styrene type vinyl ester resin, 15 to 30 parts by weight of a scale-like inorganic filler and 0.5 to 0.5 of a radical curing accelerator. It can be produced by stirring and mixing 2.0 parts by weight with a stirrer or the like. At this time, in order to adjust the curing time as necessary,
Aromatic tertiary amines such as dimethylaniline, curing promoters such as N, N-dimethylacetoacetamide, acetylacetone and acetoacetate, quinones such as p-benzoquinone and toluquinone, hydroquinone, methylhydroquinone, p- It is also possible to blend a polymerization inhibitor such as hydroquinone such as t-butylcatechol. Further, in order to impart the brown modification, it is also possible to add a brown modifying agent such as fumed silica or a pigment for coloring. If the scale-like inorganic filler is less than 15 parts by weight, the corrosion resistance is inferior, which is not preferable, and if it exceeds 30 parts by weight, the workability is inferior, which is not preferable.

It is not preferable that the steel material anticorrosion coating material composition of the present invention is directly applied to the steel material substrate and cured, since the oxide film on the surface of the steel material and the insufficient adhesion between the steel material and the anticorrosion coating material result in poor durability. Therefore, it is common to apply solvent-type urethane resin or vinyl ester resin containing styrene as a primer on the surface of steel material, and to apply an anticorrosion coating layer on it as a primer. It does not fit the gist of the present invention of obtaining a corrosion protection coating structure using a volatile material.

In order to solve this, it is effective to use a primer layer as follows. That is, it is a method of forming an anticorrosion coating layer obtained by curing the above-described steel anticorrosion coating material composition via a primer layer obtained by curing a non-styrene type vinyl ester resin on a steel material substrate. When the primer layer is applied on the steel substrate, cobalt such as cobalt naphthenate (containing 5 to 10% by weight of cobalt) which is a curing accelerator, cobalt such as cobalt octenoate is used with respect to 100 parts by weight of the non-styrene type vinyl ester resin. The surface of the steel material is mixed with 0.5 to 2 parts by weight of an organic salt and 0.3 to 3 parts by weight of an organic peroxide such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide, which are hardeners. Apply it on the surface with a brush, roller, sprayer, etc. and harden it before use. Both the curing accelerator and the curing agent can be freely adjusted and used within this range depending on the temperature at the time of construction, but if both are less than this range, curing failure tends to occur, which is not preferable. The thickness of the primer layer is preferably 0.02 to 0.1 mm. Thickness is 0.02mm
If it is less than 0.1 mm, the adhesive strength between the layers is poor, and if it is more than 0.1 mm, it is inferior in economic efficiency and workability, both of which are not preferable.

When the anticorrosion coating layer is applied on the primer layer, 100 parts by weight of the steel anticorrosion coating material composition is a curing agent such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide. 0.3 to 3 parts by weight of organic peroxide are mixed, and a brush, roller,
Apply by spraying machine, etc. and harden before use. The thickness of the anticorrosion coating layer is preferably 0.3 to 2 mm. If the thickness is less than 0.3 mm, the acid resistance is poor, and if it is more than 2.0 mm, the economical efficiency and the workability are poor, both of which are not preferable.

[0016]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Reference Examples, Comparative Examples and Examples, but the scope of the present invention is not limited by the following description. In the following, "part" indicates a weight basis unless otherwise specified.

Example 1 Production of Non-Styrene Type Vinyl Ester Resin and Steel Anticorrosion Coating Composition Using the Same Epicap 828 (Oilized) in a 2 liter four-necked flask equipped with a stirrer, condenser, thermometer, and air inlet tube. (Shell Co.) 494 g and Epicoat 834 94 g were charged, and while blowing 10 liters of dry air per minute, 12
The temperature was raised to 0 ° C. After heating, the polymerization inhibitor 2,5-
0.8 g of di-t-butyl-4-methylphenol was added, and 258 g of methacrylic acid was added dropwise over 2 hours. The acid value was measured every hour after 3 hours from the end of the dropping, and after confirming that the acid value was 15 mgKOH / g or less, the reaction was terminated. After the reaction was completed, 0.2 g of hydroquinone (polymerization inhibitor) was added. This was cooled to 100 ° C., 223 g of ethylene glycol dimethacrylate and 223 g of trimethylolpropane diallyl ether were added and dissolved, and then cooled to room temperature to obtain a non-styrene type vinyl ester resin.

This was thoroughly mixed at the following ratio for 30 minutes with a mixer equipped with a stirring blade to obtain a steel anticorrosion coating material composition. Non-styrene type vinyl ester resin 100 parts Glass flakes (average particle size 140 μm) 25 parts 6% Cobalt naphthenate 1 part Aerosil 200 (Nippon Aerosil Co., Ltd.) 4 parts Inorganic pigment 2 parts

Example 2 Production of Non-Styrene-Type Modified Vinyl Ester Resin and Steel Anticorrosion Coating Material Composition Using the Same Epicap 828 is placed in a two-liter four-necked flask equipped with a stirrer, condenser, thermometer, and air inlet tube. 53
Charged 2g and 49g of Epicote 834, 10 per minute
The temperature was raised to 120 ° C. while blowing liters of dry air. After the temperature was raised, 0.8 g of 2,5-di-t-butyl-4-methylphenol as a polymerization inhibitor was added, and 258 g of methacrylic acid was added dropwise over 2 hours. The acid value is measured every hour from the time when 3 hours have passed since the end of the dropping.
After confirming that the amount was 5 mgKOH / g or less, the reaction was terminated. After completion of the reaction, 144 g of maleic anhydride was charged and reacted at 120 ° C. for 2 hours. After completion of the reaction, 0.2 g of hydroquinone was added and cooled to 100 ° C., 324 g of ethylene glycol dimethacrylate and 324 g of trimethylolpropane diallyl ether were added and dissolved, and then cooled to room temperature to obtain a non-styrene type vinyl ester resin.

This was thoroughly mixed at the following ratio for 30 minutes with a mixer equipped with a stirring blade to obtain a steel material anticorrosion coating material composition. Non-styrene type vinyl ester resin 100 parts Glass flakes (average particle size 140 μm) 25 parts 6% Cobalt naphthenate 1 part Aerosil 200 (Nippon Aerosil Co., Ltd.) 4 parts Inorganic pigment 2 parts

Comparative Example 1 Production of a commonly used styrene type vinyl ester resin and an anticorrosion coating material composition using the same Epicap 828 was placed in a two-liter four-necked flask equipped with a stirrer, a condenser, a thermometer, and an air inlet tube. 44
2g, 84g of Epicote 834 were charged and 1 minute per minute under stirring
The temperature was raised to 130 ° C. while blowing 0 liter of dry air. After heating, hydroquinone (polymerization inhibitor) 0.3
g and trimethylbenzylammonium chloride 2 g were added, and 172 g of methacrylic acid was added dropwise over 2 hours. After 3 hours had passed since the end of the dropping, the measurement of the acid value was started every hour, and after confirming that the acid value was 10 mgKOH / g or less, it was cooled to 100 ° C. To this, 450 g of styrene was added and dissolved, and then cooled to room temperature to obtain a styrene type vinyl ester resin.

This was thoroughly mixed with a mixer equipped with a stirring blade at the following ratio for 30 minutes to obtain a steel material anticorrosion coating material composition, which was used in the test examples. Styrene type vinyl ester resin 100 parts Glass flakes (average particle size 140 μm) 25 parts 6% Cobalt naphthenate 1 part Aerosil 200 (Nippon Aerosil Co., Ltd.) 4 parts Inorganic pigment 2 parts

Comparative Example 2 Preparation of a commonly used epoxy resin steel anticorrosion coating material composition A steel anticorrosion coating material composition was obtained by thoroughly mixing with a paint shaker at the following ratio for 60 minutes, and used in the following test examples. Epicoat 828 100 parts Aerosil 200 4 parts Glass flakes (average particle size 140 μm) 25 parts Butyl glycidyl ether 10 parts Titanium white (Sakai Chemical Co. R-5N) 5 parts Pigment (Dainippon Ink and Chemicals Co. PC-5830) 1 part

Test Example 1 Volatility test of steel material anticorrosion coating material composition The steel material anticorrosion coating material composition obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was added to a glass petri dish having a diameter of 90 mm at 30 g.
Samples were collected and the accumulated volatilization amount was measured every 10 minutes for 60 minutes in a constant temperature water bath at 37 ° C. The results are shown in Table 1 (Table 1).

Test Example 2 Acid resistance test of steel anticorrosion coating material composition produced from non-styrene type vinyl ester resin (method of preparing test piece) 1 according to JIS K5410
Blasting a 50 × 70 × 3.2 mm steel plate, JI
It was pretreated in accordance with SK5400 and stored in a constant temperature and humidity chamber at a temperature of 20 ± 1 ° C. and a humidity of 65 ± 5% to obtain a material to be used for the test. As the primer layer, 100 parts of the non-styrene type vinyl ester resin produced in Example 1 was mixed with 1 part of 6% cobalt naphthenate and 1 part of 55% methyl ethyl ketone peroxide so that the thickness became 0.05 mm. The above material was applied with a brush.

Example 1 after the primer layer was dry to the touch
5 to 100 parts of the steel material anticorrosion coating material composition manufactured in
Add 1 part of 5% methyl ethyl ketone peroxide,
It was applied with a brush so that the thickness would be 0.6 mm to obtain a test piece, which was used for evaluation after curing. (Evaluation method) After the application of the steel anticorrosion coating material composition was completed, it was aged in a constant temperature and humidity chamber for 7 days and then used for the test. Ie 1
It was immersed in a 0% aqueous solution of sulfuric acid for 1, 2, 3, 4, 5, 6 months, the surface condition was visually observed, and the weight change was measured. The results of the acid resistance test are shown in Table 2 (Table 2).

Test Example 3 Acid resistance test of steel material anticorrosion coating material composition produced from non-styrene type modified vinyl ester resin The non-styrene type vinyl ester resin produced in Example 1 and the same were applied to the primer layer and the steel material anticorrosion coating layer. The same as Test Example 2 except that the non-styrene modified vinyl ester resin produced in Example 2 and the steel anticorrosion coating material composition using the same were used instead of using the steel anticorrosion coating material compositions used, respectively. A test piece was prepared by the method of 1. and evaluated. The results are shown in Table 2 (Table 2).

Test Example 4 Acid resistance test of steel material anticorrosion coating material composition using styrene type vinyl ester resin which is commonly used The primer layer and the steel material anticorrosion coating layer were mixed with the non-styrene type vinyl ester resin produced in Example 1. Similar to Test Example 2 except that the styrene-type vinyl ester resin produced in Comparative Example 1 and the steel anticorrosion coating material composition using the same are used instead of the steel anticorrosion coating material composition using the same. A test piece was prepared and evaluated by the method. The results are shown in Table 2.
It shows in (Table 2).

Test Example 5 Acid resistance test of steel anticorrosive coating composition using a commonly used epoxy resin A non-styrene resin used in Example 1 was used as a primer layer and a steel anticorrosive coating layer. Instead of using each of the steel anticorrosion coating compositions, the epoxy resin used in Comparative Example 2 was used as the primer layer, and as the steel anticorrosion coating layer, 100 parts of the steel anticorrosion coating composition produced using the same was used. A test piece was prepared and evaluated in the same manner as in Test Example 2 except that 25 parts of Epicure-138 (Yukaka Shell Co., Ltd.), which is an amine curing agent, was mixed and cured. The results are shown in Table 2 (Table 2).

Test Example 6 Adhesive Strength Test Using Primer Layer The adhesive strength between the steel base material and the steel anticorrosive coating structure was evaluated by the following method. (Preparation of test piece) 70 × in accordance with JIS K5410
A 70 × 4 mm steel plate was pretreated according to JIS K5400. A test material was prepared in the same manner as in Test Example 2. (Evaluation method) A non-styrene type vinyl ester resin produced in Example 1 was used to apply a primer layer to the above test material, and the steel material anticorrosive coating composition of Example 1 was used to apply a steel anticorrosive coating layer. After completion, after curing for 7 days in a constant temperature and constant humidity chamber, a tensile tester shown in JIS K5400.8.7 was used to perform a test according to JIS K5400.8.7 to measure the adhesive strength. The results are shown in Table 3 (Table 3).

Test Example 7 Adhesion Strength Test without Primer Layer The test piece was evaluated in the same manner as in Test Example 6 except that the anticorrosion coating layer was applied directly to the steel material base and cured. The results are shown in Table 3 (Table 3).

[0032]

[Table 1] The steel anticorrosion coating material composition using a commonly used styrene type vinyl ester resin as in Comparative Example 1 has a large volatilization amount and a strong odor, whereas the non-styrene type vinyl ester resin of the present invention is used. The steel material anticorrosion coating material composition has a very small volatilization amount and a small odor.

[0033]

[Table 2] As shown in Test Examples 2 and 3, the steel anticorrosion coating material composition using the non-styrene type vinyl ester resin of the present invention has good acid resistance as well as the steel anticorrosion coating material composition using the styrene type vinyl ester resin. Had. On the other hand, as shown in Test Example 5, the steel anticorrosion coating material composition using an epoxy resin was inferior in acid resistance.

[0034]

[Table 3] The steel anticorrosion coating structure of the present invention shown in Test Example 6 having a primer layer has a higher adhesive strength than that of the structure shown in Test Example 7 having no primer layer. Therefore, the steel anticorrosion coating structure of the present invention exhibits good durability.

[0035]

EFFECT OF THE INVENTION The steel material anticorrosion coating material composition of the present invention has low volatility, durability, and durability during corrosion protection while maintaining good chemical resistance such as acid resistance originally possessed by vinyl ester resin. Excellent economy. Further, the steel anticorrosion coating structure comprising the steel anticorrosion coating composition of the present invention has excellent durability, weather resistance, chemical resistance and high adhesive strength.

[Brief description of drawings]

FIG. 1 is a cross-sectional view illustrating a steel material anticorrosion coating structure of the present invention.

[Explanation of symbols]

1; Steel base 2; primer layer 3; Steel material anticorrosion coating layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Takashi Iiyama, inventor             1900 Togo, Mobara-shi, Chiba Mitsui Chemicals, Inc.             In the company (72) Inventor Junzo Kobori             1900 Togo, Mobara-shi, Chiba Mitsui Chemicals, Inc.             In the company (72) Inventor Eio Nagasaki             18-1, Sakae-chome, Naka-ku, Nagoya-shi, Aichi             Within CRM Co., Ltd. (72) Inventor Nobuo Chikauchi             18-1, Sakae-chome, Naka-ku, Nagoya-shi, Aichi             Within CRM Co., Ltd. (72) Inventor Masafumi Nozaki             18-1, Sakae-chome, Naka-ku, Nagoya-shi, Aichi             Within CRM Co., Ltd. (72) Inventor Shigeki Maeda             18-1, Sakae-chome, Naka-ku, Nagoya-shi, Aichi             Within CRM Co., Ltd. F-term (reference) 4J002 CD051 CD061 CD071 CD201                       DL007 EE038 EG048 EH028                       EH076 EH146 EK049 EK069                       EK079 EN078 EP018 FA017                       FD017 FD090 FD149 FD158                       GH01 HA05                 4J027 AC03 AC06 AE02 AE03 AE04                       AJ08 BA17 BA20 BA22 BA23                       BA26 CA19 CA36 CB03 CB07                       CB08 CC01 CD08                 4J038 CF011 CG141 CH051 CH061                       KA04 KA08 KA20 NA03 PA07                       PC02                 4K062 AA01 BA17 BB06 BC11 BC13                       BC21 FA08 FA12 FA16 GA01                       GA03

Claims (2)

[Claims] 1. 70 to 85 parts by weight of a non-styrene type vinyl ester resin containing vinyl ester and a low-volatile radically polymerizable monomer, 15 to 30 parts by weight of a scale-like inorganic filler, and a radical curing accelerator of 0.5. A steel material anticorrosion coating material composition comprising about 2.0 parts by weight. 2. A steel material substrate, via a primer layer formed by curing a non-styrene type vinyl ester resin,
A steel anticorrosive coating structure comprising an anticorrosive coating layer obtained by curing the steel anticorrosive coating composition according to claim 1.