JPS5964667A - Corrosion-resistant material for use in coating tank - Google Patents

Abstract

PURPOSE:To provide a corrosion-resistant material compsn. for use in coating a tank, which has excellent resistance to water and impact, adhesion, mechanical characteristics, etc. and can be cured at room temp., by adding a vinyl monomer and a urethane prepolymer to a specified vinyl ester compd. CONSTITUTION:The titled compsn. is obtd. by adding 20-150pts.wt. vinyl monomer (A) such as styrene and 20-100pts.wt. urethane prepolymer (B) to 100pts.wt. vinyl ester compd. (C) having at least one free OH group per molecule obtd. by reacting an epoxy compd. having at least one epoxy group per molecule, such as diglycidyl ether, with a monobasic acid mainly composed of an unsaturated monobasic acid such as (meth)acrylic acid and in which the equivalent ratio of free OH group in compd. C to free NCO group in compd. B is in the range of 3.5 to 70.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anticorrosive composition for coating and protecting tanks for storing gasoline, light oil, kerosene (hereinafter abbreviated as Karin, etc.).

Conventionally, Arosphald and asphalt roofing have been used as anticorrosive materials for tank protection. but,
Asphalt and asphalt roofing have problems in terms of environmental hygiene when heated and melted in the coating process, cracks occur in the anti-corrosion coating, peeling occurs due to poor adhesion, and the anti-corrosion properties tend to deteriorate due to dissolution in oils such as gasoline. It had a fundamental flaw as an anti-corrosion coating for tanks.

The purpose of the present invention is to solve the problems of conventional anticorrosive materials for tank coatings, to have excellent gasoline resistance, water resistance, stalk impact resistance, adhesion, mechanical properties, etc. An object of the present invention is to provide a novel curable anticorrosion composition for tank coating.

That is, the present invention provides (1) one measurement of free hydroxyl groups in a molecule obtained by reacting an epoxy compound containing one or more epoxy groups in the molecule with a basic acid, mainly an unsaturated basic acid; (2) 20 to 150 parts by weight of a vinyl monomer and (3) 20 to 100 parts by weight of a urethane prepolymer to 100 parts by weight of a vinyl varnish/chill compound containing the vinyl ester. 41!F lfi that the M ratio between It hydroxyl in the compound and the M# isocyanate group in the urethane prepolymer is within the range of 3.5 to 70.
This is an anticorrosive composition for coating tanks.

The vinyl ester compound used in the coated anticorrosive composition of the present invention is an epoxy compound containing epoxyno, (inverted 1) in minutes, unsaturated, basic acid or unsaturated depending on psychic properties. Part of the basic acid is one or more basic acids selected from saturated basic acids, saturated polybasic acids, anhydrous saturated polybasic acids, unsaturated polybasic acids, and anhydrous unsaturated polybasic acids. It is a vinyl ester compound containing one or more free hydroxyl groups in the molecule obtained by reacting with a substituted compound.

This vinyl ester compound can be prepared by a conventional method, for example, by adding a polymerization inhibitor, a specific reaction catalyst, and, if necessary, a solvent to an epoxy compound containing an epoxy group in an inverted position and an unsaturated basic acid. It is produced by reacting with C.

Examples of the above-mentioned epoxy compounds include diglycidyl ethers and polycricidyl ethers such as noholac type epoxy resins, and of course, they are obtained by epoxidizing the intramolecular double bond with peracetic acid (hypolysyl compounds can also be used).

Examples of unsaturated base resistance include acrylic acid, meccrylic acid, crotonic acid, methyl maleate, propyl maleate, 2-ethyl maleate, methyl fumarate, propyl fumarate, butyl fumarate-1., 2-ethyl Examples include hexyl fumarate.

In order to obtain a vinyl ester compound suitable for the present invention, unsaturated -
The molar ratio of the basic acid is usually in the range of 0.1 to 1.9 mol, preferably 0.3 to 1.2 mol.

In addition, in the present invention, in addition to the above-mentioned unsaturated basic acid, a part of this acid may be used as a saturated polybasic acid such as acetic acid, propionic acid, isophthalic acid, and hydrochloric acid; maleic anhydride, fumaric acid, and citraconic acid. There is no problem in using it as a substitute with at least one unsaturated polybasic acid such as. In addition, other unsaturated polyesters such as ortho-, iso-, or bisphenol-based unsaturated polyesters may be used in combination as long as the characteristics of the present invention are not lost.

Examples of vinyl monomers used in the present invention include styrene, α-methylstyrene, p-chlorostyrene, vinyl acetate, bisallylcarpho-4-l., p-t-2-butylstyrene, vinyltoluene, divinylbenzene, 4-vinylcyclohexane, Methyl acrylic, chrysyl acrylate-1, glycidyl methacrylate,) realyl cyanurate, hydroxyethyl acrylate, hydroxymethyl methacrylate, hydroxypropyl methacrylate, ethylene glycol methacrylate-I, diethylene glycol acrylate, trimethylolpropane triacrylate, Examples include glycerin monoacrylate monomethacrylate, isocyanate group monohydroxyacrylate, and at least one of these various vinyl monomers can be used.

In the present invention, 20 to +50 parts by weight of vinyl monomer is added to 100 parts by weight of vinyl esterification 1) b.
Preferably 30 to 150 nail parts are used, and if the amount of Z0 hinyl mo/mer used is out of this range, vinyl ester compounds, vinyl monomers and urethane prepolymer can be used.
The mechanical properties and oil resistance of the cured product of the resin composition (hereinafter abbreviated as cured product) deteriorate.

The urethane prepolymer used in the present invention is produced by a conventional method, and is obtained by reacting diincyanate or polyisocyanate with polyester polyol or polyester polyol at a temperature of, for example, about 30 to 100°C. .

Examples of the diisocyanate include tetramethylene diisocyanate, tetramethylene diisocyanate,
Pentamethylene diisocyanate, octamethylene diisocyanate, dipropyl ether-3,3'-diisocyanate, synchro\xylmethane-4,4'-diincyate, ■, 4-cyclohexylene diisocyanate, xylylene isocyanate, Diphenylmethane-4,4'-cyisocyanate, metaphenylene diisocyanate, 2.6-1 lylene diisocyanate,
A typical example is 2,4-trilene isocyanate-1.

Examples of polyisocyanates include 1-methylbenzoyl-2,4,6-1-liisocyanate (1., naphthalene-1,3,7-'), biphenyl-2,4,4'-1 -diisocyanate, toluene-2,4,6-1-diisocyanate, and the like are representative. Moreover, as the polyester polyol, those produced by a conventional method from various dicarboxylic acids and polyols can be used. In addition, polyether polyols can be prepared using one method: ethylene oxide, propylene oxide, trimethylene oxide, butylene oxide, α-methyltrimethylene oxide, 3.
Those produced by ring-opening polymerization or copolymerization of cyclic ethers such as 3-methyltrimethylene oxide, tetrahydrofuran, dioxane, dioxamine, etc. can be used.

When producing the urethane prepolymer, the equivalent ratio (NGOloH) of the incyanate group in the diisocyanate-1 or polyinsyanate and the hydroxyl group in the polyester polyol or polyether polyol described in 1.
It is preferable to manufacture the urethane prepolymer so that the amount of the urethane prepolymer is usually 1.5 to 20, and the proportion of free isocyanate groups contained in the urethane prepolymer is preferably about 2 to 15% by weight. In addition, the average molecular weight of the polyester polyol or polyether polyol is usually 300 to 10,000, and especially 4
．． : The range of 1,000-7,000 is preferable.

The urethane prepolymer is used in an amount of 3.5 to 100 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the vinyl ester compound. If the amount of the urethane prepolymer is less than 3.5 parts by weight, the impact resistance, adhesion, and crack resistance of the cured product will decrease, while if it exceeds 100 parts by weight, the mechanical properties of the cured product will deteriorate. It is not suitable as it reduces oil resistance.

Free hydroxyl groups in the vinyl ester compound and M# in the urethane prepolymer in the anticorrosion composition of the present invention
The equivalent ratio of isocyanate groups (OH/NGO) is 3
．． A range of 5 to 70, preferably 5 to 60 is suitable and appropriate. If this equivalent ratio is less than 3.5, the oil bending properties and mechanical properties of the cured product will deteriorate, and if it exceeds 70, there will be an excess of MIlfl hydroxyl groups in the vinyl ester compound relative to the isocyanate groups of the urethane polymer. The cured product does not form an elastic polymer,
Impact resistant charm? f: Poor adhesion.

The anticorrosive composition of the present invention usually contains, for example, penyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, isobutyl ketone peroxide, cyclohexanoyl peroxide, lauryl peroxide, t-butyl peroxide, etc. curing catalysts and naphthenic metal salts such as salts of cobalt, manganese, iron, lead, etc., tertiary amines such as dimethylaniline, alcoholic acid such as sodium methylate, laurimer butane, N-methyl metatoluidine, etc. It is cured by using a curing accelerator. In this case, the amount of the curing catalyst added is in the range of 0.5 to 15 parts by weight based on 100 parts by weight of the vinyl ester compound and the vinyl ester compound.

In addition to these ingredients, the anticorrosive composition of the present invention also contains viscosity adjustment, 6I! For the purpose of improving the physical properties of i-oxides,
Various substances can be further added depending on the spirit.

Examples of these additives include diamines and polyols. Suitable diamines include, for example, ethylenediamine, tetraethylenecyamine, hexamethylenediamine, p-phenylenediamine, and 4,4'-methylene-bis(2-chloroaniline). ), 4,4'-diaminodiphenylmethane, and 3,3'-dichlorobenzidine. As the polyol, various known polyester polyols and polyether polyols can be added.

In addition, pigments such as titanium white, carbon black, and bay color; benzene, toluene, methyl ethyl ketone,
Solvents such as mineral spilint; polyethylene, polypropylene, nylon, calcium oxides, magnesium carbonate, halide sulfate, calcium sulfate, alumina, clay, kaolin, talc, silica gel, silica gel, mica powder, glass! @ Fillers such as fiber powder, asbestos powder, silica powder, etc.

It is also possible to add thixotropic substances such as colloidal silicic acid, castor oil derivatives, etc.

The cured product of the uninvented anticorrosive composition has high toughness and impact resistance due to intermolecular crosslinking between the free incyanate groups of the urethane prepolymer and the free hydroxyl groups in the vinyl ester compound through urethane bonds during the curing process. When a three-dimensional structure of an elastic body is formed, a cured product of a vinyl ester compound and a vinyl monomer is formed in order to form a highly rigid and kalin-resistant structure by polymerizing the terminal vinyl group of the vinyl ester compound and vinyl monomer. Also, it exhibits an excellent anticorrosion function that cannot be obtained with urethane resins.

The anticorrosion composition of the present invention can be used for waterproofing and rust prevention of gasoline storage tanks, roof waterproofing, basement waterproofing, interior and exterior waterproofing of subway structures, submarine tunnel/channel waterproofing, and the like.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Examples 1-11 and Comparative Examples 1 to 5 964 parts by weight of methacrylic acid, 2200 parts by weight of Epicor (82scrf) as a bisphenol A-based epoxy resin, manufactured by Yuka Seson Epoxy Co., Ltd., and 3.2 parts by weight of hydroquinone as a polymerization inhibitor. Trimethylbenzylammonium 8-fold M parts were added at 120°C as a reactor and a reaction catalyst.
The reaction was carried out for a period of time to obtain a bisphenol vinyl ester compound having an acid value of almost O. A bisphenol-based vinyl ester resin (vinyl ester compound hydroxyl value: 260 mgKOH/g) was prepared by adding 1 m of styrene in an amount shown in Table 1 to 100 parts by weight of this product.This bisphenol-based vinyl ester resin or Novolanc vinyl ester resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., product name: Nystar H8000, vinyl ester compound and droxyl value 260 mg KDH/g, vinyl ester compound: vinyl 1,000-ton weight ratio-too: 67)
0.5i part of cobalt naphthenate (containing 6% cobalt) was added to 100 parts by weight, and then urethane prepolymer (manufactured by Mitsui Toatsu Chemicals (Chichi), trade name: Hypren P-78) was added to 100 parts by weight.
0, M# incyanate content 7.5%), curing catalyst methyl ethyl ketone peroxide (manufactured by NOF Corporation,
A resin composition was prepared by uniformly mixing 55% concentration (trade name: Permec N) according to the blending ratio in Table 1. After curing this composition, test pieces were prepared for each test item,
Impact resistance, adhesion (flexibility), tensile strength, elongation rate, and gasoline resistance were measured and the results shown in Table 1 were obtained. Note that various evaluation items were measured according to the method described in f.

1) Impact resistance: Herashan cloth (JIS La2O2,) #? on a copper plate with a thickness of 8mm. Single layer thickness 1.
Create an 8mm sheet and make 24FF! The test piece was left at room temperature for f hours and then cured at 80°C for 113 hours.
A 2.75 kg iron ball was dropped onto the test piece, and the impact resistance was expressed as the height at which the test piece broke.

2) Tensile strength, elongation rate: Cut out a specimen with a length of 250 mm and a width of 20 mm from the same test piece as in 1.
It was measured based on the test method of IS At (008).

3) Flexibility: 250 m in length from the same test piece as in 1) above.
m, cut out a specimen with a width of 25 mm, and divide this specimen into 2
After soaking in water at 5°C for 15 minutes, remove the
Bend it 180 degrees around a mm rod for about 2 seconds and check whether there are any cracks on the surface of the bent part. It11 was determined.

4) Kallin resistance: diameter 501nI11. Thickness: 1mm
The test piece was molded into a disk, and this test piece was
After drying for 24 hours in a constant temperature bath at °C,
After soaking for a day, the sample was taken out and the weight change rate was measured.

Comparative Example 1 The same evaluation test as in Example 1 was carried out on the anticorrosive properties of conventional asphalt and asphalt roof ink.

1) Impact resistance: Apply epoxy primer (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: EP Primer) to a 6 mm thick steel plate, and after curing 1fj FISG34! A finished test piece was made with 3 layers of 35 kg of Al blown asphalt and asphalt roof ink to a thickness of 10 mm, and a 2.75 kg iron ball was dropped onto the test piece from a height of 100 cm to check for damage. Ta.

2) Tensile strength, elongation rate; length from the test piece in l) above 2
A specimen with a length of 50 m+n and a width of 20 mm was cut out and tested.

3) Flexibility: A specimen with a length of 250 mm and a width of 25 mm was cut out from the test piece of 1) above and tested.

4) #Callinity was tested in the same manner as in Example 1.

Claims (1)

[Claims] 1. (1) One amount of hydroxyl group separated by 'ML in the molecule obtained by reacting an epoxy compound containing one amount of epoxy group in the molecule with a basic acid, mainly an unsaturated basic acid. (2) 20 to 150 parts by weight of vinyl monomer and
(3) A resin composition in which 20 to 100 parts of a urethane prepolymer is added, and the NL releasing hydroxyl group in the vinyl ester compound and the M# isocyanate group in the urethane prepolymer are Equivalence ratio is 3.5
A composition for coating a tank with corrosion protection, characterized in that the composition has an anti-corrosion content in the range of 70 to 70.