JP2000063449A - Corrosionproof coating composition for slate and corrosionproof coated slate structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve acid resistance, low volatility, economy, weather resistance and adherence to a slate material of a corrosionproof coating composition 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 a slate is obtained by reacting an epoxy resin with (meth)acrylic acid 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 60-10 pts.wt. of 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 having an aspect ratio of at least 10 and an average particle size of 100-300 μm, and 0.5-2.0 pts.wt. of a radical curing accelerator. A corrosionproof coated structure of slate is obtained by forming a slate conditioning layer 2 onto a slate 1, providing a primer layer 3 containing 70-95 pts.wt. of the non-styrene type vinyl ester resin and 5-30 pts.wt. of a solvent-free type urethane resin on the conditioning layer and forming a corrosionproof coating layer 4 comprising the corrosionproof coating composition on the primer layer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a slate anticorrosion coating structure. More specifically, the present invention relates to an anticorrosion coating structure for a slate structure such as a roof material and a wall material.

[0002]

2. Description of the Related Art Slate materials are widely used as roofing materials, wall materials, etc. because of their excellent durability and economy. These roofing materials or wall materials are usually exposed to erosion deterioration due to salt damage, acid rain, ultraviolet rays, storm and flood damage and the like. In order to prevent this, it is often adopted to apply a coating material to the surface of the slate material to prevent corrosion. Conventionally, acrylic resin, epoxy resin, vinyl ester resin, or the like is generally used as the coating material. However, these have the following problems.

That is, a coating material using an acrylic resin has a strong odor because it contains a so-called thinner, which is a highly volatile organic solvent. Since the epoxy resin contains no organic solvent, it hardly causes an odor problem, but is generally poor in acid resistance and weather resistance. Further, the vinyl ester resin not only has a low weather resistance but also uses a styrene monomer, and since it has a high volatility, it has a strong odor and has a problem for the environment.

[0004]

An object of the present invention is to provide an anticorrosion coating material composition for a slate material, which has low volatility and is excellent in economical efficiency and weather resistance while retaining the acid resistance originally possessed by the vinyl ester resin. It is to be. Another object of the present invention is to use the slate anticorrosion coating material composition,
An object of the present invention is to provide a slate anticorrosion coating structure which is excellent in durability, weather resistance, adhesion to a slate material, and the like.

[0005]

As a result of earnest studies to solve the above problems, the present inventors have found that the following slate anticorrosion coating material composition and slate 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 A slate anticorrosive coating material composition comprising 0.5 to 2.0 parts by weight, and

[2] A slate comprising an anticorrosion coating layer obtained by curing the slate anticorrosion coating material composition described in [1] on the slate substrate provided with the substrate conditioning layer (I) via the primer layer (III). It is an anticorrosion coating structure, and [3] The primer layer (III) is obtained by curing 70 to 95 parts by weight of a non-styrene type vinyl ester resin and 5 to 30 parts by weight of a solventless urethane resin. A slate comprising a slate anticorrosion coating structure, and [4] a slate comprising an anticorrosion coating layer (IV) obtained by curing the slate anticorrosion coating material composition according to [1] by applying a substrate adjusting layer (II) [5] The base material adjusting layer (II) is an anticorrosion coating structure, and 100 to 300 parts by weight of the aggregate and 100% by weight of the solventless urethane resin relative to 100 parts by weight of the non-styrene type vinyl ester resin.
The slate anticorrosion coating structure according to [4], wherein 30 to 30 parts by weight are cured.

[0007]

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) What is an acrylic resin? Acrylic acid and / or its ester, methacrylic acid and / or its ester, and a monomer having a number average molecular weight of 10,000 to 100,000 are polymerized with toluene and ethyl acetate. , Dissolved in a solvent such as methyl ethyl ketone. (5) Epoxy resin has 2 glycidyl groups in one molecule.
Epoxy coat 828, 1001, 1002, 1 of Yuka Shell Co., Ltd.
Examples thereof include bisphenol A type epoxy resin such as 004, bisphenol F type epoxy resin such as Epicoat 807, novolac type epoxy resin such as Epicoat 152 and 154, cresol type epoxy resin and the like.

(6) The matrix adjusting layer (I) means a latex- or emulsified water-dispersed epoxy resin, acrylic resin, urethane resin, SBR, NBR which is generally used for polymer cement. Cement 150-300 for 100 parts by weight of vinyl acetate resin
It is obtained by mixing parts by weight, directly applying it on a slate using a brush, a roller, a trowel, etc. and curing it. (7) Aggregates include natural aggregates such as sand, gravel, crushed stone, crushed sand, silica sand, crushed slag and slag, as well as calcium carbonate powder,
It is a known and commonly used filler such as aluminum hydroxide, barium sulfate, alumina powder, talc, clay, cold water stone, silica powder and glass powder.

(8) Solventless urethane resin may be any known urethane resin as long as it does not contain a so-called solvent. For example, toluidine diisocyanate, hexamethylene diisocyanate, 4,
A urethane resin obtained by reacting diisocyanates such as 4-diphenylmethylene diisocyanate with 1,4-butanediol, polypropylene glycol, polyethylene glycol, or a urethane resin obtained by subjecting diisocyanates and water to a burette reaction. is there.

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 of 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 the acid value of the reaction product, but the reaction is generally completed when the reaction rate is 90% or more.

After the reaction of the epoxy resin with acrylic acid and / or methacrylic acid is completed, 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.

Vinyl ester 4 thus obtained
0 to 90 parts by weight of low vapor pressure radically polymerizable monomer 60 to
It can be dissolved in 10 parts by weight 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) Slate anticorrosion coating material composition The slate anticorrosion coating material composition comprises 70 to 85 parts by weight of a non-styrene type vinyl ester resin and 15 to 3 of scale-like inorganic filler.
It can be produced by stirring and mixing 0 part by weight and 0.3 to 2.0 parts by weight of a radical curing accelerator with a stirrer or the like. In this case, aromatic tertiary amines such as dimethylaniline, N, N, etc. are used to adjust the curing time as needed.
-A hardening accelerator such as dimethylacetoacetamide, acetylacetone, acetoacetic acid ester, p-benzoquinone,
It is also possible to add a polymerization inhibitor such as quinones such as toluquinone, hydroquinone, methylhydroquinone, hydroquinones such as pt-butylcatechol. Further, in order to impart the brown modification, it is possible to blend a brown modifying agent such as fumed silica or a pigment.

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.

When the slate anticorrosion coating material composition of the present invention is applied directly to the slate substrate and cured, the water content in the slate inhibits the curing of the slate anticorrosion coating material composition, resulting in low adhesive strength. And is inferior in durability, which is not preferable. For that, on the foundation adjustment layer,
It is common to apply solvent-type urethane resin or styrene-containing vinyl ester resin as a primer, and then apply an anticorrosion coating layer on top of it, but using these resins uses low-volatile materials. It does not fit the present invention of obtaining an anticorrosion coating structure.

There are two methods to solve this. That is, the substrate conditioning layer (I) and primer layer described below
There are a method (3-i) using (III) and a method (3-ii) using the substrate adjusting layer (II). (3-i) Method using base adjustment layer (I) and primer layer (III) 70-95 parts by weight of non-styrene type vinyl ester resin and solvent-free urethane are applied to the slate base material on which the base adjustment layer (I) has been applied. An anticorrosion coating layer (IV) obtained by curing the above slate anticorrosion coating material composition via a primer layer (III) obtained by curing a resin composition comprising 5 to 30 parts by weight of a resin.
Is a method of forming. This will be described.

In order to reinforce and smooth the surface of the slate, it is necessary to first apply the green body adjusting layer (I). The materials and construction method used here are as described in the explanation of terms (6). The thickness of the base material adjusting layer (I) is preferably 0.5 to 3.0 mm. When the thickness is less than 0.5 mm, the durability is poor due to the insufficient strength of the slate surface, and when it exceeds 3.0 mm, the economy and the workability are poor, and both are not preferable. The primer layer (III) is applied to improve the adhesive strength between the base material conditioning layer (I) and the anticorrosion coating layer (IV). The primer layer (III) is applied after the base material adjustment layer (I) is sufficiently cured. The primer layer (III) is a non-styrene type vinyl ester resin 10
The solvent-free urethane resin is mixed in an amount of 5 to 30 parts by weight with respect to 0 parts by weight and cured. If the amount is less than 5 parts by weight, the adhesive strength to the slate when water is absorbed decreases, which is not preferable, and if the amount exceeds 30 parts by weight, the physical strength of the substrate adjusting layer (I) decreases, which is not preferable.

When the primer layer (III) is applied on the substrate adjusting layer (I), the non-styrene type vinyl ester resin 10
Cobalt naphthenate (containing 5 to 10% by weight of cobalt) and octene, which are curing accelerators, per 100 parts by weight of a resin composition in which 5 to 30 parts by weight of a solventless urethane resin is mixed with 0 parts by weight. 0.5 to 2 parts by weight of a cobalt organic salt such as cobalt acid and a curing agent, methyl ethyl ketone peroxide, cyclohexanone peroxide,
Mix 0.3 to 3 parts by weight of organic peroxides such as methyl acetoacetate peroxide and acetylacetone peroxide, apply the base adjustment layer (I), and apply with a brush, roller, sprayer, etc. to cure. . 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. Primer layer (III)
The thickness is preferably 0.02 to 0.1 mm. The thickness is 0.
If it is less than 02 mm, the adhesive strength between the layers will be poor, and if it is more than 0.1 mm, it will be inferior in economic efficiency and workability, both of which are not preferable.

When the anticorrosion coating layer (IV) is applied on the primer layer (III), 100 parts by weight of the slate anticorrosion coating material composition is used as a curing agent for methyl ethyl ketone peroxide, cyclohexanone peroxide and methyl acetoacetate peroxide. 0.3 to 3 parts by weight of an organic peroxide such as oxide or acetylacetone peroxide is mixed, and the mixture is applied with a brush, roller, sprayer or the like and cured. The thickness of the anticorrosion coating layer (IV) 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 mm, the economical efficiency and the workability are poor, both of which are not preferable.

(3-ii) Method using the substrate adjusting layer (II) Non-styrene type vinyl ester resin 1 on the slate substrate
A base material adjusting layer (II) obtained by curing a resin composition consisting of 100 to 300 parts by weight of an aggregate and 5 to 30 parts by weight of a solventless urethane resin is applied to 00 parts by weight, and the above slate corrosion protection is applied thereon. Anticorrosion coating layer by curing the coating composition (IV)
A method of forming the will be described below.

The base adjusting layer (II) is obtained by curing a base adjusting agent consisting of 100 to 300 parts by weight of aggregate and 5 to 30 parts by weight of solventless urethane resin to 100 parts by weight of non-styrene type vinyl ester resin. To be If the amount of the aggregate is less than 100 parts by weight, the composition after mixing is unlikely to be in the form of cement and the workability is apt to occur. On the other hand, if the amount is more than 300 parts by weight, the physical strength of the green body adjusting layer (II) is lowered, which is not preferable. If the amount of the solventless urethane resin is less than 5 parts by weight, the adhesive strength to the slate particularly when absorbing water is lowered, which is not preferable. If the amount is more than 30 parts by weight, the base adjusting layer (I
It is not preferable because the physical strength of I) decreases. When applying the substrate conditioning layer (II), 0.5 to 2 parts by weight of a cobalt organic salt such as cobalt naphthenate or cobalt octenoate, which is a curing accelerator, and 100 parts by weight of the substrate conditioning agent and the curing agent. 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 is sequentially mixed with a stirrer or the like, and a spatula, a brush, and a brush are directly applied on the slate base material. It is applied and cured by using a roller or the like. The thickness of the base adjustment layer (II) is 0.
5 to 3.0 mm is preferable. If the thickness is less than 0.5 mm, the durability is poor due to insufficient strength of the slate surface, and 3.0 m
If it exceeds m, both economical efficiency and workability are deteriorated, which is not preferable.

One of the slate anticorrosion coating structures referred to in the present invention can be obtained by curing the anticorrosion coating layer (IV) on the base material adjusting layer (II) thus formed. Anticorrosion coating layer (I
When V) is applied and applied on the substrate adjusting layer (II), methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, which is a curing agent, is added to 100 parts by weight of the slate anticorrosive coating material composition. 0.3 to 3 parts by weight of an organic peroxide such as oxide is mixed, and the mixture is applied with a brush, roller, sprayer or the like and cured. The thickness of the anticorrosion coating layer (IV) is preferably 0.3 to 2.0 mm. If the thickness of the anticorrosion coating layer (IV) is less than 0.3 mm, it is not preferable because it is inferior in acid resistance, and if it is more than 2.0 mm, it is not preferable because it is inferior in economic efficiency and workability.

[0026]

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 slate anticorrosive coating composition using the same Epicap 828 was put in a 2-liter four-necked flask equipped with a stirrer, a condenser, a thermometer and an air inlet tube.
0 g was charged and the temperature was raised to 120 ° C. while blowing 10 liters of dry air per minute. After heating, the polymerization inhibitor 2,5-di-t-butyl-4-methylphenol 0.8
g 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 is 100 ℃
Cool to ethylene glycol dimethacrylate 22
3 g, trimethylolpropane diallyl ether 223
g was added and dissolved, and then cooled to room temperature to obtain a non-styrene type vinyl ester resin.

This was thoroughly mixed with a paint shaker at the following ratio for 60 minutes to obtain a slate anticorrosive coating material composition, which was subjected to the following test examples. Non-styrene type vinyl ester resin 100 parts 6% Cobalt naphthenate 1 part Fumed silica (Aerosil 200, Nippon Aerosil Co., Ltd.) 4 parts Titanium white (R-5N, Sakai Chemical Co., Ltd.) 5 parts Pigment (PC-5830, Dainippon Ink and Chemicals Co., Ltd.) ) Part 1

Example 2 Production of non-styrene type modified vinyl ester resin and slate anticorrosion coating material composition using the same Epicap 828 was placed in a two-liter four-necked flask equipped with a stirrer, condenser, thermometer, and air inlet tube. 57
0 g was charged and the temperature was raised to 120 ° C. while blowing 10 liters of dry air per minute. After heating, the polymerization inhibitor 2,5-di-t-butyl-4-methylphenol 0.8
g 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 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 the mixture was cooled to 100 ° C., ethylene glycol dimethacrylate 324
g, trimethylolpropane diallyl ether 324g
Was added and dissolved, and then cooled to room temperature to obtain a non-styrene type modified vinyl ester resin.

This was thoroughly mixed with a paint shaker at the following ratio for 60 minutes to obtain a slate anticorrosive coating material composition,
The following test examples were used. Non-styrene type modified vinyl ester resin 100 parts 6% cobalt naphthenate 1 part Fumed silica (Aerosil 200, Nippon Aerosil Co., Ltd.) 4 parts Titanium white (R-5N, Sakai Chemical Co., Ltd.) 5 parts Pigment (Dainippon Ink and Chemicals, Inc. PC- 5830) Part 1

Comparative Example 1 Production of a commonly used styrene type vinyl ester resin and a slate anticorrosive coating material composition using the same Styrene-type 2 ester four-necked flask equipped with a stirrer, a condenser, a thermometer, and an air inlet tube was epicoated. 828 to 51
The temperature was raised to 130 ° C. while blowing 0 liter of dry air while stirring and charging 0 g of the air. After heating, 0.3 g of hydroquinone (polymerization inhibitor) and 2 g of trimethylbenzylammonium chloride were added, and methacrylic acid 172 was added.
g was added dropwise over 2 hours. After 3 hours have passed since the end of the dropping, the measurement of the acid value was started every hour, and 10 mg was measured.
After confirming that the content became KOH / g or less, it was cooled to 100 ° C. 450g of styrene was added to this and dissolved,
After cooling to room temperature, a styrene type vinyl ester resin was obtained.

This was thoroughly mixed with a paint shaker at the following ratio for 60 minutes to obtain a slate anticorrosion coating material composition,
The following test examples were used. Styrene type vinyl ester resin 100 parts 6% cobalt naphthenate 1 part Fumed silica (Aerosil 200, Nippon Aerosil Co., Ltd.) 4 parts Titanium white (R-5N, Sakai Chemical Co., Ltd.) 5 parts Pigment (PC-5830, Dainippon Ink and Chemicals Co., Ltd.) 1 copy

Comparative Example 2 Production of a commonly used epoxy resin slate anticorrosion coating material composition A slate 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 Fumed silica (Aerosil 200, Nippon Aerosil Co., Ltd.) 4 parts Butyl glycidyl ether 10 parts Titanium white (R-5N, Sakai Chemical Co., Ltd.) 5 parts Pigment (PC-5830, Dainippon Ink and Chemicals Co., Ltd.) 1 part

Comparative Example 3 Production of a commonly used acrylic resin slate anticorrosion coating composition 2 equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube
A liter four-necked flask was sealed with nitrogen gas, 700 g of toluene was charged, and the temperature was raised to 95 ° C. 407 g of methyl methacrylate, 140 g of styrene monomer, 67 g of ethyl acrylate, and 86-n-butyl acrylate.
A monomer composition in which 15 g of tertiary-butyl peroctoate as a polymerization catalyst was dissolved was added dropwise to g over 2 hours, and after completion of the reaction, the reaction was further performed at 100 ° C. for 3 hours to obtain an acrylic coating resin.

This was thoroughly mixed with a paint shaker at the following ratio for 60 minutes to obtain a slate anticorrosion coating material composition,
The following test examples were used. Acrylic paint resin 100 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 slate anticorrosion coating material compositions The slate anticorrosion coating material compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were each placed in a glass petri dish having a diameter of 90 mm.
Collect 0g and adjust the accumulated volatile amount to 10 in a 37 ° C water bath.
It was measured every minute for 60 minutes. The results are shown in Table 1 (Table 1).

Test Example 2 Acid resistance test of slate anticorrosion coating material composition using non-styrene type vinyl ester resin (method of preparing test piece) 2 in accordance with JIS K5410
20x220x10mm asbestos cement perlite board was pre-treated according to JIS K5400, and temperature was 20 ± 1.
The material was stored in a constant temperature and humidity room at a temperature of 73 ° C. and a humidity of 73 ± 5% and used as a material for the test. As the substrate adjusting layer (I), 100 parts of a polymer for a commercially available epoxy polymer cement and 300 parts of cement mortar are mixed, and after sufficiently stirring, applied on the asbestos-cement pearlite plate to have a thickness of 0.5 mm. Was flattened with a metal spatula and cured for 24 hours.

As the primer layer (III), 100 parts of the non-styrene type vinyl ester resin produced in Example 1 was added,
Solventless urethane resin 10 parts, 6% cobalt naphthenate 1 part and 55% methyl ethyl ketone peroxide 1
Parts were mixed and applied with a brush so that the thickness would be 0.05 mm. After the primer layer (III) was dried by touch, 1 part of 55% methyl ethyl ketone peroxide was mixed with 100 parts of the slate anticorrosive coating material composition prepared in Example 1 to give a thickness of 0.6 mm. A test piece was obtained by coating with a brush and was used for evaluation after curing.

(Evaluation Method) The test pieces were evaluated as follows. After the application of the slate anticorrosion coating material composition was completed, it was cured in a constant temperature and humidity chamber for 7 days and then used for the test. That is,
It was immersed in a 10% sulfuric acid aqueous solution for 1, 2, 3, 4, 5, 6 months, and 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 slate anticorrosion coating material composition using non-styrene type modified vinyl ester resin Primer layer (III) and anticorrosion coating layer with non-styrene type vinyl ester resin produced in Example 1 Instead of using each of the slate anticorrosion coating material compositions using it,
Test pieces were prepared and evaluated in the same manner as in Test Example 2 except that the non-styrene type modified vinyl ester resin produced in Example 2 and the slate anticorrosive coating material composition using the same were used. The results are shown in Table 2 (Table 2).

Test Example 4 Acid Resistance Test of Slate Anticorrosion Coating Material Composition Using Conventionally Used Styrene Vinyl Ester Resin The non-styrene vinyl ester produced in Example 1 was used as the primer layer (III) and the anticorrosion coating layer. Instead of using a resin and a slate anticorrosion coating material composition using the resin, respectively,
Test pieces were prepared and evaluated in the same manner as in Test Example 2 except that the styrene-type vinyl ester resin produced in Comparative Example 1 and the slate anticorrosive coating material composition using the same were used. The results are shown in Table 2 (Table 2).

Test Example 5 Acid resistance test of slate anticorrosion coating material composition using a commonly used epoxy resin The primer layer (III) and the anticorrosion coating layer were prepared by using the non-styrene type vinyl ester resin produced in Example 1 and the same. Instead of using each slate anticorrosion coating material composition using
The epoxy resin used in Comparative Example 2 was used as the primer layer (III), and in the anticorrosion coating layer, 100 parts of the slate anticorrosion coating material composition produced in Comparative Example 2 was used as the amine curing agent Epicure-138 (Oilized). Shell Co.) 25 parts blended,
A test piece was prepared in the same manner as in Test Example 2 except that it was cured.
evaluated. The results are shown in Table 2 (Table 2).

Test Example 6 Acid resistance test of slate anticorrosion coating material composition using commonly used acrylic resin The primer layer (III) and the slate anticorrosion coating layer were subjected to Example 1
Instead of using the non-styrene type vinyl ester resin produced in and the slate anticorrosive coating material composition using the same,
The same method as in Test Example 2 except that the acrylic resin used in Comparative Example 3 was used as the primer layer (III), and the slate anticorrosive coating material composition using the same as the anticorrosion coating layer was applied and dried to a thickness of 80 μm. The test piece was prepared and evaluated. The results are shown in Table 2 (Table 2).

Test Example 7 Adhesion of the base material adjusting layer (I), the primer layer (III) using the non-styrene type vinyl ester resin produced in Example 1 and the slate anticorrosion coating structure using the slate anticorrosion coating material composition Strength Test The adhesive force between the slate substrate and the slate anticorrosion coating structure was evaluated by the following method. At this time, the slate substrate was used in a standard state and a wet state.

(Preparation of test piece) Standard state: 220 × 22 according to JIS K5410
A 0 × 10 mm slate plate was pretreated according to JIS K5400. A test piece was prepared by the same method as in Test Example 2. Wet condition: Before applying the base conditioning material, the test piece is 20 ±
Test Example 2 except that the surface was wiped with a clean cloth after being immersed in distilled water at 1 ° C. for 24 hours, and the substrate conditioning layer (I) was immediately applied.
A test piece was prepared in the same manner as in.

(Evaluation method) After the application of the anticorrosion coating layer (IV) is completed,
After curing in a constant temperature and constant humidity chamber for 7 days, a test was conducted with a Kenken type tensile tester according to JIS A6916 to measure the adhesive strength. The results are shown in Table 3 (Table 3).

Test Example 8 Adhesive strength test of the base material adjusting layer (II) using the non-styrene type vinyl ester resin produced in Example 1 and the anticorrosion coating structure using the slate anticorrosive coating material composition ) And the primer layer (III) instead of
As the substrate adjusting layer (II), 100 parts of the non-styrene type vinyl ester resin produced in Example 1, 10 parts of the solventless urethane resin, 1 part of 6% cobalt naphthenate and 250 of No. 9 silica sand.
Parts were mixed, 1 part of 55% methyl ethyl ketone peroxide was blended and applied, the surface was finished flat with a metal spatula to a thickness of 0.5 mm, and after curing for 24 hours, it was manufactured in Example 1. Test pieces were prepared and evaluated in the same manner as in Test Example 7 except that the slate anticorrosive coating material composition was applied.
The results are shown in Table 3 (Table 3).

Test Example 9 Primer layer in Test Example 7
Adhesive strength test without (III) When a test piece was prepared, it was evaluated in the same manner as in Test Example 7 except that the anticorrosion coating layer (IV) was directly applied onto the substrate conditioning layer (I) and cured. . The results are shown in Table 3 (Table 3).

Test Example 10 Adhesive strength test when solvent-free type urethane resin is not blended in the substrate conditioning layer (II) of Test Example 8 In solvent-free urethane resin is not blended in the substrate conditioning layer (II) in Test Example 8. Other than the above, test pieces were prepared and evaluated in the same manner as in Test Example 8. The results are shown in Table 3 (Table 3).

Test Example 11 A test piece prepared by the same method as in Test Example 2 was used to JIS.
Conduct an outdoor exposure test for 1 year according to A1410, and
Months, 6 months and 12 months at the end of the test were measured for gloss and discoloration. Gloss is JIS K5400,
It was based on the specular gloss (incident angle 60 °). The degree of discoloration is JIS
Lab with non-exposed test piece (0 months) according to Z8730
The color difference (ΔE) was measured. The respective measurement results are shown in Table 4 (Table 4).

Test Example 12 A test piece prepared by the same method as in Test Example 3 was used to JIS.
Conduct an outdoor exposure test for 1 year according to A1410, and
Months, 6 months and 12 months at the end of the test were measured for gloss and discoloration. The measurement of glossiness and discoloration was in accordance with Test Example 11. The measurement results are shown in Table 4 (Table 4).

Test Example 13 A test piece prepared by the same method as in Test Example 4 was used to JIS.
Conduct an outdoor exposure test for 1 year according to A1410, and
Months, 6 months and 12 months at the end of the test were measured for gloss and discoloration. The measurement of glossiness and discoloration was in accordance with Test Example 11. The measurement results are shown in Table 4 (Table 4).

Test Example 14 Using a test piece prepared by the same method as Test Example 5, JIS was used.
Conduct an outdoor exposure test for 1 year according to A1410, and
Months, 6 months and 12 months at the end of the test were measured for gloss and discoloration. The measurement of glossiness and discoloration was in accordance with Test Example 11. The measurement results are shown in Table 4 (Table 4).

Test Example 15 A test piece prepared by the same method as in Test Example 6 was used to JIS.
Conduct an outdoor exposure test for 1 year according to A1410, and
Months, 6 months and 12 months at the end of the test were measured for gloss and discoloration. The measurement of glossiness and discoloration was in accordance with Test Example 11. The measurement results are shown in Table 4 (Table 4).

[0055]

[Table 1] The slate anticorrosive coating material composition using the commonly used styrene type vinyl ester resin of Comparative Example 1 and the acrylic resin of Comparative Example 3 both have a large volatilization amount and a strong odor, whereas the non-styrene of the present invention The slate anticorrosion coating material composition using the vinyl ester resin has a small volatilization amount and a small odor.

[0056]

[Table 2] As shown in Test Examples 2 and 3, the slate anticorrosion coating material composition using the non-styrene type vinyl ester resin of the present invention is as good as the slate anticorrosion coating material composition using the styrene type vinyl ester resin. Has acid resistance. On the other hand, as shown in Test Examples 5 and 6, the slate anticorrosion coating material composition using an epoxy resin and an acrylic resin is inferior in acid resistance.

[0057]

[Table 3] Test Examples 7 and 8 were 100% slate fracture in which the adhesive strength between the slate base material and the slate anticorrosion coating structure was strong. On the other hand, in Test Examples 9 and 10, the adhesive strength was weak and peeling occurred at the interface between the substrate adjusting layer and the anticorrosion coating layer. Therefore, the slate anticorrosion coating structure of the present invention exhibits good durability.

[0058]

[Table 4] As shown in Test Examples 11 and 12, the slate anticorrosion coating material composition using the non-styrene type vinyl ester resin of the present invention has good weather resistance as in the case of the slate anticorrosion coating material composition using acrylic resin. Have.

[0059]

The slate anticorrosion coating material composition of the present invention comprises:
Excellent low volatility, economy and weather resistance while maintaining good chemical resistance such as acid resistance that vinyl ester resin originally has. Further, the slate anticorrosion coating structure using the slate anticorrosion coating material composition of the present invention has excellent durability, weather resistance, and strong adhesive strength to the slate matrix.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a slate anticorrosion coating structure of the present invention having a primer layer.

FIG. 2 is a cross-sectional view of a slate anticorrosion coating structure of the present invention having no primer layer.

[Explanation of symbols]

1; Slate substrate 2; Substrate adjustment layer (I) 3; Primer layer (III) 4; Slate anticorrosion coating layer (IV) 5; Substrate adjustment layer (II)

   ─────────────────────────────────────────────────── ─── 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 CD201 CK042 CK052 DA097                       DE147 DE237 DG047 DJ007                       DJ017 DJ037 DJ047 DL007                       EE038 EG108 EH028 EH076                       EH146 EK069 EK079 EN028                       EN058 FD017 FD090 FD149                       FD158 GH01 GH02 GL00                       HA05                 4J027 AC03 AC06 AE02 AE03 AE07                       AJ08 BA17 BA20 BA22 BA23                       BA26 CA10 CA19 CA36 CB03                       CB07 CB08 CC01 CD08                 4J038 DB371 DG002 FA012 FA251                       KA04 KA08 KA20 NA03 PA07                       PB05

Claims (5)

[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. ~ 2.0 parts by weight of a slate anticorrosion coating material composition. 2. From the anticorrosion coating layer (IV) obtained by curing the slate anticorrosion coating material composition according to claim 1 on the slate substrate provided with the substrate conditioning layer (I) via the primer layer (III). Slate anticorrosion coating structure. 3. The primer layer (III) is formed by curing 70 to 95 parts by weight of a non-styrene type vinyl ester resin and 5 to 30 parts by weight of a solventless urethane resin.
The slate anticorrosion coating structure described. 4. A slate anticorrosion coating structure comprising an anticorrosion coating layer (IV) obtained by applying a substrate conditioning layer (II) to a slate substrate and curing the slate anticorrosion coating material composition according to claim 1. 5. The base adjusting layer (II) comprises 100 to 30 parts by weight of an aggregate based on 100 parts by weight of a non-styrene type vinyl ester resin.
The slate anticorrosion coating structure according to claim 4, which is obtained by curing 0 parts by weight and 5 to 30 parts by weight of a solventless urethane resin.