JP2002356981A - Floor with anticorrosive coating layer with determinable degree of deterioration and method of constructing it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a floor with an anticorrosive cover layer whose degree of deterioration is determinable. SOLUTION: The floor is formed having at least two layers: an undercoat layer containing an indicator which discolors in the presence of strong acid, provided on a base; and an anticorrosive cover overcoat layer enabling the discoloring to be determined; or the floor is formed having at least three layers: an undercoat layer; an intermediate layer containing an indicator which discolors in the presence of strong acid; and an anticorrosive cover overcoat layer enabling the discoloring to be determined.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a floor having an anticorrosion coating layer whose deterioration degree can be determined, and a method for forming the floor.

[0002]

2. Description of the Related Art Generally, the degree of deterioration over time of an anticorrosion coating film applied to a concrete layer or the like is determined by the appearance change such as swelling or cracking of the anticorrosion coating layer. However, at the stage where the appearance change occurs, the deterioration has already spread to the concrete layer of the base.

[0003] Deterioration of the concrete layer and the like, for example, in factories and laboratories that use a strong acid such as sulfuric acid, the corrosion protection coating layer first deteriorates due to leakage of the strong acid used.
Reach the concrete layer. Upon reaching the concrete layer, the deterioration of the concrete layer progresses rapidly.

[0004] However, even if the anticorrosion coating layer deteriorates,
Initially, there is no major change in appearance, only the barrier properties of sulfuric acid and the like are reduced. Therefore, the swelling of the anticorrosion coating layer,
They are left until cracks occur. As a result, not only the deterioration of the anticorrosion coating layer, but also the deterioration of the concrete layer of the base material and the like, the time required for repair is long,
The costs are enormous.

[0005]

Means for Solving the Problems The present inventors have solved the problem that not only the deterioration of the anticorrosion coating layer but also the deterioration of the concrete layer and the like progresses, and the time required for repair is long and the cost is enormous. As a result of intensive studies to solve it,
The present invention has been completed.

That is, the present invention is directed to a degradation method having at least two layers: an undercoat layer provided on a substrate and containing an indicator that changes color with a strong acid and an anticorrosion coating top coat layer capable of determining the change in color. A floor having an anticorrosion coating layer of which degree can be determined (claim 1), provided on a substrate,
A floor having at least three anticorrosive coating layers whose deterioration degree can be determined, the floor having at least three layers: an undercoat layer, an intermediate layer containing an indicator that changes color with a strong acid, and an anticorrosive coating top coat layer capable of determining the color change. 2) The intermediate layer is an anticorrosion coating intermediate layer formed from an epoxy resin-based coating, a urethane resin-based coating, or a vinyl ester resin-based coating containing an indicator that changes color with a strong acid. The floor (Claim 3), the floor (Claim 4) having the anticorrosion coating layer according to Claim 1, 2 or 3, wherein the indicator discoloring with a strong acid is a pH indicator, the anticorrosion coating topcoat layer is an epoxy resin-based coating, The floor having the anticorrosion coating layer according to claim 1, 2, 3 or 4, which is formed from a urethane resin coating or a vinyl ester resin coating (claim 5), wherein the anticorrosion coating top coat is an epoxy resin coating Claim 1, which is formed from the paint which contains a phenol-modified hydrocarbon oligomers in charge,
The floor having the anticorrosion coating layer according to claim 2, 3, or 4, and an undercoat layer containing an indicator that changes color with a strong acid on the substrate, and at least the discoloration can be determined. A method of forming a floor having a corrosion-resistant coating layer capable of determining the degree of deterioration characterized by providing an overcoat layer (claim 7), an undercoat layer on a substrate,
Then, after providing an intermediate layer containing an indicator that changes color with a strong acid, a floor having an anticorrosion coating layer having at least three layers and having a deteriorating degree which can be determined is provided with an anticorrosion coating top coat layer capable of determining the discoloration. Wherein the intermediate layer is an anticorrosion-coated intermediate layer formed from an epoxy resin-based paint, a urethane resin-based paint or a vinyl ester resin-based paint containing an indicator that changes color with a strong acid. The method according to claim 9, wherein the indicator that changes color with a strong acid is a pH indicator (claim 1).
0), the method according to claim 7, 8, 9 or 10 (claim 11), wherein the anticorrosion coating top coat layer is formed from an epoxy resin-based paint, a urethane resin-based paint or a vinyl ester resin-based paint. The method according to claim 7, 8, 9 or 10, wherein the coating top coat layer is formed from a paint containing a phenol-modified hydrocarbon low polymer in an epoxy resin paint.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The floor of the present invention having an anticorrosion coating layer whose deterioration degree can be determined is provided by using an undercoat layer provided on a substrate and containing an indicator that changes color with a strong acid and its color change. A floor having at least two layers of an anticorrosive coating topcoat layer (the floor of the present invention 1) or an intermediate layer provided on a substrate and containing an undercoat layer and an indicator which discolors with a strong acid, and its discoloration is determined. A floor (floor according to the present invention 2) having an anticorrosion coating layer having at least three layers, which can be subjected to an anticorrosion coating and an anticorrosion coating layer capable of determining a degree of deterioration. In the case of the floor of the present invention 1, if necessary, an intermediate layer containing no indicator discoloring with a strong acid may be provided between the undercoat layer and the anticorrosion coating topcoat layer in order to obtain the thickness of the anticorrosion coating layer, A top coat layer may be provided on the anticorrosion coating top coat layer to improve the anticorrosion performance. Also,
In the case of the floor of the present invention 2, if necessary, a top coat layer may be provided on the anticorrosion coating top coat layer for improving the anticorrosion performance.

Examples of the substrate include floors of factories and laboratories using various chemicals formed from concrete, resin mortar, asphalt, polymer cement, and the like.

The anticorrosion coating top coat layer capable of determining discoloration is a layer used to improve the anticorrosion of the floor as a substrate, and is usually an epoxy resin-based paint, a vinyl ester resin-based paint, an acrylic It is formed from a resin paint, a urethane resin paint, a fluororesin paint, a silicone resin paint, or the like, but is not limited thereto. In addition, it is preferable to use a clear paint from the viewpoint that discoloration can be determined.

As the epoxy resin-based paint, any epoxy resin-based paint used for forming a coating film on a floor can be used, and there is no particular limitation.
Specific examples of the epoxy resin paint include, for example, 100 parts by weight of epoxy resin (hereinafter, referred to as parts).
Examples of the coating agent include 30 to 70 parts of a curing agent, and 40 to 60 parts of a curing agent.

As the epoxy resin, various epoxy resins conventionally used as anticorrosion paints for floors, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, bisphenol AD epoxy resin, biphenyl Epoxy resin, naphthalene epoxy resin, alicyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, heterocyclic epoxy resin, diaryl sulfone epoxy resin, hydroquinone epoxy resin and modified products thereof. can give. In addition, a reactive diluent can be used for adjusting the viscosity and the like. Among these, a polyfunctional epoxy resin is preferable in terms of increasing the crosslink density and improving chemical resistance, but a bifunctional epoxy resin is more preferable in terms of adjustment of viscosity and balance of mechanical strength such as abrasion resistance. preferable.

Examples of the curing agent include those conventionally used, such as amine-based curing agents (eg, aliphatic amine-based curing agents, aromatic amine-based curing agents, cyclic amine-based curing agents, and heterocyclic amine-based curing agents). Curing agent) and a polymercaptan-based curing agent. Of these,
Among the amine-based curing agents, aromatic amine-based curing agents and cyclic amine-based curing agents are preferable from the viewpoint of good chemical resistance and water resistance.

Specific examples of the aliphatic amine-based curing agent among the amine-based curing agents include, for example, triethylenetetramine (TETA) and diethylenetriamine (DET).
A), hexamethylenediamine (HMDA), diethylaminopropylamine (DEAPA), trimethylhexamethylenediamine (TMD), and modified products thereof.

Specific examples of the aromatic amine curing agent among the above amine curing agents include, for example, metaphenylenediamine (MPDA), diaminodiphenylmethane (DD)
M), diaminodiphenyl sulfone (DDS), and modified products thereof, for example, modified epoxy adducts obtained by reacting these with an epoxy compound such as a bisphenol A type epoxy resin. Of these,
The epoxy adduct-modified aromatic amine-based curing agent is preferable because it has both the adhesiveness and the sulfuric acid resistance of the coating film to be formed.

Specific examples of the cyclic amine-based curing agent among the amine-based curing agents include mensendiamine (MDA), isophoronediamine (IPDA), m-xylenediamine (MXDA), and modified products thereof. can give. Among these, m-xylene diamine (MXDA) or a Mannich modified product obtained by reacting m-xylene diamine with aldehydes or ketones such as formalin (formaldehyde) has improved adhesiveness and resistance to the wet surface of concrete. It is preferable since an anticorrosion coating film having both sulfuric acid properties can be formed.

As the urethane resin-based paint, any urethane resin-based paint used for forming a coating film on a floor can be used, and there is no particular limitation.
Specific examples of the urethane resin-based coating include, for example, a urethane resin coating which gives a high-hardness coating film using a curing system of a polyol and an isocyanate synthesized from an epoxy compound.

The vinyl ester resin-based paint includes:
Any vinyl ester resin-based paint used to form a coating film on the floor can be used, and there is no particular limitation. Specific examples of the vinyl ester resin-based paint include, for example, a curable resin composition similar to an unsaturated polyester resin composition, and are basically made of epoxy acrylate (a highly reactive acrylic double end at the terminal of the resin main chain). Is a radical polymerizable composition diluted with a copolymerizable monomer (usually, styrene, acrylic acid ester, or other reactive monomer), and is a composition for corrosion-resistant FRP or a composition for high-strength FRP. And those used as low shrinkage vinyl ester resin paints.

As the epoxy resin paint used for forming the anticorrosion coating top coat, an epoxy resin paint may be used as it is, but in order to further improve the deterioration resistance, a phenol-modified hydrocarbon is used. A polymer or the like may be contained.

The phenol-modified hydrocarbon low polymer contained in the epoxy resin paint or the like makes a coating film formed from the epoxy resin paint or the like hydrophobic (water repellent) and suppresses penetration of sulfuric acid and the like. And a non-reactive liquid diluent, for example. Since permeation of sulfuric acid or the like into the coating film formed from the epoxy resin-based paint can be suppressed, corrosion of the base by sulfuric acid or the like can be suppressed.

The phenol-modified hydrocarbon lower polymer is
For example, it is a mixture of a phenol copolymer and a C _{8 to} C ₁₀ aromatic hydrocarbon fraction polymer. Generally, commercially available products further include a C _{4 to} C ₅ hydrocarbon fraction or a C _{8 to} C ₁₀ aromatic compound. It contains hydrocarbon fractions and the like.

The general characteristics of the phenol-modified hydrocarbon low polymer (commercially available) include, for example, a viscosity (B-type rotational viscometer) of 1 to 10 P (25 ° C.) and 2 to 14 P (20 ° C.).
℃), specific gravity (20 ℃) 0.92-0.94, acid value 2
mgKOH / g, volatile matter (100 ° C, 2 hours, 1g
5/16% of sample / 16 cm ² ), flash point (Cleveland open type) of 120-160 ° C., epoxy resin (for example, Epicoat 815, 828, 834, 872)
-X-75, 1001, 1004, 1007, 100
9) / Phenol-modified hydrocarbon low polymer = 3/1 to 1 /
3 (weight ratio), very good compatibility with curing agents (e.g. Epicur 103, H-3, DX-124, Var
samid 115, 125) / phenol-modified hydrocarbon low polymer = 3/1 to 1/3 (weight ratio), very good compatibility, solvent (toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzyl alcohol) Butyl acetate) / phenol-modified hydrocarbon low polymer = 3/1 to 1/3 (weight ratio), but compatible with aliphatic alcohol (ethanol, butanol) /
When the phenol-modified hydrocarbon low polymer is 3/1 to 1/3 (weight ratio), it may not be compatible.

Specific examples of the phenol-modified hydrocarbon low-polymer (commercially available) include, for example, Toho Chemical Industry Co., Ltd.
TRE100 (viscosity (B-type rotational viscometer) 2P (25
° C), 3P (20 ° C), specific gravity (20 ° C) 0.93, acid value less than 2 mgKOH / g, volatile matter (100 ° C, 2 hours, 1 hour)
g sample / 16 cm ² ) 5%, flash point (Cleveland open type) 150 ° C), TRE200 (viscosity (B type rotational viscometer) 7P (25 ° C), 12P (20 ° C), specific gravity (2
0 ° C.) 0.92, acid value less than 2 mg KOH / g, volatile matter (100 ° C., 2 hours, 1 g sample / 16 cm ² ) 5
%, Flash point (Cleveland open type) 152 ℃), TR
E300 (viscosity (B-type rotational viscometer) 7P (25 ° C), 1
2P (20 ° C), specific gravity (20 ° C) 0.94, acid value 2mg
KOH / g, volatile content (100 ° C., 2 hours, 1 g sample / 16 cm ² ) 10%, flash point (Cleveland open type) 134 ° C.). These may be used alone or in combination of two or more. Among these, TRE200 is preferable from the viewpoint of low viscosity and low volatility.

The amount of the phenol-modified hydrocarbon low polymer to be added to the epoxy resin paint or the like is 100 parts of the epoxy resin paint (active ingredient) per 100 parts of the phenol-modified hydrocarbon low polymer (non-volatile content). 5 to 100 parts, more preferably 10 to 60 parts, is preferred. If the blending amount of the phenol-modified hydrocarbon low polymer is too small, the hydrophobicity of the formed coating film is reduced, and the dilution effect is reduced,
The anticorrosion coating topcoat tends not to have a sufficiently low viscosity, and if too much, the mechanical strength of the coating tends to decrease.

The anticorrosion coating top coat layer has a thickness of 0.1 mm.
A clear coating film having a thickness of 1 to 3 mm, more preferably 0.2 to 0.5 mm is preferable in that it has good anticorrosion coating properties and is easily judged by an indicator.

The undercoat layer according to the first aspect of the present invention is a layer originally used for improving the adhesion between the anticorrosive coating top coat and the substrate, for the adhesion on the wet surface of the substrate and for preventing pinholes. These are layers generally called a primer layer, an undercoat layer, and a base adjustment layer. In the present invention 1, the layer further contains an indicator that changes color with a strong acid such as a pH indicator. . As a result, the anticorrosion coating performance of the anticorrosion coating topcoat layer is reduced, and when, for example, sulfuric acid permeates to the undercoat layer, the indicator acts to inform that the substrate is becoming unfavorable. If the anticorrosion coating layer is repaired at this time, only the anticorrosion coating layer whose anticorrosion coating performance has been reduced before the substrate is damaged can be repaired. If a pH indicator is used as an indicator that changes color with a strong acid, and the color changes when sulfuric acid permeates to the substrate side, for example, the degree of deterioration of the anticorrosion coating layer can be confirmed with the naked eye.

As the undercoat layer, any commonly used undercoat layer can be used. For example, when the undercoat layer is a primer layer, specific examples include epoxy resin (water), epoxy resin (solvent), epoxy resin (solvent-free), urethane resin, and polyester resin (vinyl ester). Resin layer), polyurea resin type, acrylic resin type, silicone resin type, primer layer from fluororesin type, etc. Specific examples of the undercoat layer include epoxy resin type (water type), epoxy resin type (solvent type) ), Epoxy resin-based (solvent-free), urethane resin-based, polyester resin-based (including vinyl ester resin), polyurea resin-based, acrylic resin-based, silicone resin-based, and fluorine resin-based undercoat layers. . Of these, epoxy resin-based (water-based) or epoxy resin-based (solvent-free) is used as the base floor,
It is preferable from the viewpoints of adhesion to the overcoat layer and safety and health.

Specific examples of the pH indicator include, for example, methyl red, bromothymol blue, methanyl yellow, thymol blue, tropeolin 00, 2,6-dinitrophenol, methyl yellow, bromophenol blue, methyl orange, congo red, alizarin S,
Bromocresol green, 2,5-dinitrophenol, lacmoid, p-nitrophenol, chlorophenol red, bromocresol purple, phenol red, rosolic acid, neutral red, cresol red, phenolphthalein, o-cresolphthalein, thymol lid Rain, Alizarin Yellow GG, Tropeolin O, nitramine, 1,3,5-trinitrobenzene and the like. Among these, metanil yellow and thymol blue have a discoloration range (pH 1.2 to 2.2).
8) is preferable.

The pH indicator may be added to the undercoat layer as it is, but in the case of a pH indicator having a functional group, an immobilized pH indicator immobilized by covalent bonding to a carrier insoluble in the functional group-containing undercoat agent. It may be added as an indicator. By adding the pH indicator as an immobilized pH indicator, diffusion of the pH indicator from the undercoat layer and the like are less likely to occur, and the indicator performance is less likely to decrease with time. When the pH indicator diffuses into the anticorrosion coating topcoat layer, if sulfuric acid or the like penetrates into the portion of the anticorrosion coating topcoat layer where the pH indicator has diffused, the pH indicator discolors even if the sulfuric acid does not reach the undercoat layer. Begins,
Also, even if sulfuric acid or the like enters the undercoat layer, p
The difference in the color tone due to the discoloration of the H indicator is not vivid, and the determination is difficult.

Specific examples of the pH indicator having a functional group include, for example, methyl red, congo red, neutral red, methyl orange, bromophenol blue, bromocresol purple, bromothymol blue, phenol red, phenolphthalein, and cresol red. And so on. Among them, Congo Red and Neutral Red having an amino group as a functional group,
Methyl red having a carboxyl group is preferred because it can be easily immobilized on a carrier that is insoluble in the undercoat agent, and the immobilization does not inhibit the discoloration action as a pH indicator.

As the carrier insoluble in the undercoat agent having a functional group, various materials, for example, those made of resin or glass are known in the field of immobilized enzymes, and can be used. Since the carrier is added to the undercoat layer, the size of the carrier is preferably 以下 or less of the thickness of the undercoat layer, and the shape is preferably particulate.

The proportion of the pH indicator and the carrier insoluble in the undercoat agent having a functional group in the immobilized pH indicator is preferably such that the surface of the carrier is covered with the pH indicator. Since the surface area of the carrier varies depending on the particle size, it cannot be unconditionally limited.
Since the H indicator can be used as it is, it is preferable to use it so that the pH indicator is increased.

The method for producing the immobilized pH indicator and the like are described in JP-A-1-272965.

The amount of the pH indicator used is 0.005 to 5.0% by weight (hereinafter referred to as%) in the undercoat layer, and more preferably 0.01 to 0.1% (the amount of the active ingredient). It is preferable to use it in such a manner that the determination of discoloration and the influence on the resin properties are small. Further, in order to improve the dispersibility of the pH indicator, it is preferable to use the pH indicator after dissolving and dispersing it in a solvent such as methanol in advance.

The amount of the immobilized pH indicator used is as follows:
It is preferable to use 0.005 to 5.0%, more preferably 0.01 to 0.1%, in the undercoat layer, since the influence on the resin properties is small.

The amount and method of application of the undercoat layer and the anticorrosion coating top coat layer may be the same as those in the case where no indicator is added. Specifically, when the undercoat layer is a primer layer and an anticorrosion coating topcoat layer is applied thereon, the primer layer has an application amount of 0.1 to 0.4 kg / m ² ,
1.0 to 3.0 kg / m as the coating amount of the anticorrosion coating top coat layer
² was employed, for example, roller coating method primer layer, was coated with such brushing, spraying machine anticorrosion coating overcoat layer (hybrid cancer, cups cancer) preferably applied in such method.

As a preferred embodiment of the present invention 1, for example, 0.01 to 0.10 parts of a pH indicator (preferably methanyl yellow) per 100 parts (solid content) of a primer composition, preferably an epoxy primer composition. 0.1 to 0.4 k of the primer composition containing
After applying g / m ² , an anticorrosive coating overcoat layer, preferably an epoxy anticorrosive coating overcoat layer is applied at 1.0 to 3.0 kg / m ^2, and the discoloration state of the pH indicator due to aging is determined. By judging the deterioration state of the anticorrosion coating layer,
It can be repaired before the substrate deteriorates.

When an epoxy resin-based (water-based) primer layer is used, the use of an epoxy resin-based (solvent-free) one as the anticorrosion coating top coat layer is advantageous in terms of working environment and health and safety. Is preferred.

Further, the epoxy-based anticorrosion coating topcoat layer is formed, for example, by adding Mannich-modified metaxylenediamine curing agent 40 to 100 parts of bisphenol A type epoxy resin.
In the case where a coating composed of 100 parts of an epoxy resin-based coating containing 60 parts and 20 to 60 parts of a phenol-modified hydrocarbon low polymer is formed by applying 1.0 to 3.0 kg / m ² , especially the anticorrosive coating property is obtained. Becomes better.

If necessary, an intermediate layer containing no indicator discolored by a strong acid may be provided between the undercoat layer and the anticorrosion coating top coat layer in the present invention 1 in order to obtain the thickness of the anticorrosion coating layer. A top coat layer may be provided on the coating top coat layer to improve the anticorrosion performance.

The intermediate layer may be made of, for example, an epoxy resin (no solvent), a urethane resin, a polyester resin (including a vinyl ester resin), an acrylic resin, or the like, preferably an epoxy resin (no solvent). And a layer having a thickness of 0.1 to 1.0 mm formed from an object.

The intermediate layer is preferably a clear layer because it is necessary to be able to determine the discoloration of the indicator discolored by the strong acid contained in the undercoat layer.

Since the intermediate layer is a layer provided between the undercoat layer and the anticorrosion coating top coat layer, the intermediate layer has good compatibility (such as adhesiveness, chemical resistance and concrete cracking followability). For example, when the undercoat layer is an epoxy resin-based (solvent-free) and the anticorrosive coating top coat layer is an epoxy resin-based (solvent-free), an epoxy resin-based (solvent-free) is used from the viewpoint of adhesion and chemical resistance. It is preferred that

The top coat layer is formed of, for example, an epoxy resin (no solvent), urethane resin, acrylic resin, polyester resin (including vinyl ester resin), and has a thickness of 0.1 mm. 1-1.0m
m layer. This layer is also preferably a clear layer because it is necessary to be able to determine the discoloration of the indicator discolored by the strong acid contained in the undercoat layer.

According to the second aspect of the present invention, instead of the undercoat layer according to the first aspect of the present invention, an indicator which discolors with a strong acid is contained in the intermediate layer. Therefore, although the intermediate layer not containing the indicator is provided, the undercoat layer containing the indicator discolors faster than the case where the discoloration is caused by the strong acid, but the period from the discoloration until the strong acid reaches the base is the intermediate layer. And the period until repair of the anticorrosion coating layer can be lengthened. As a result, it becomes easier to repair the anticorrosion coating layer at a convenient time. Also, since it is only necessary to be able to determine the discoloration of the intermediate layer,
For example, a non-clear undercoat layer can be used.

The substrate, anticorrosive coating topcoat layer of the present invention 2,
The top coat layer used if necessary may be the same as that of the first embodiment. Also, the undercoat layer may be the same as that of the first embodiment except that the undercoat layer does not contain an indicator discolored by a strong acid and may contain a coloring agent or the like. further,
The intermediate layer may be the same as that of the first embodiment, except that the intermediate layer contains an indicator that changes color with a strong acid and may contain a coloring agent and the like.

In a preferred embodiment of the present invention 2, for example, a primer composition, preferably an epoxy-based primer composition, is applied to a substrate at 0.1 to 0.4 kg / m ² and then cured to a tack-free state. Preferably, an intermediate layer containing 0.01 to 0.1 part of a pH indicator (preferably methanyl yellow) per 100 parts (solid content) of the intermediate layer is applied to the primer layer in an amount of 0.5 to 3.0 kg / m ^2. And
Then, an anticorrosion coating top coat layer, preferably an epoxy anticorrosion coating top coat layer, is applied in an amount of 1.0 to 3.0 kg / m ² , and the deterioration state of the anticorrosion coating layer is determined by judging the discoloration state of the pH indicator over time. By making the determination, the base can be repaired before it deteriorates.

When an epoxy resin-based (water-based) primer layer is used, an epoxy resin-based (solvent-free) layer is used as the intermediate layer, and an epoxy resin-based (solvent-free) is used as the anticorrosion coating top coat layer. The use of (system) is preferred in terms of working environment and health and safety.

Further, the epoxy-based anticorrosion coating top coat is formed, for example, by using a Mannich-modified meta-xylene diamine curing agent 40 to 100 parts per 100 parts of bisphenol A type epoxy resin.
In the case where a coating composed of 100 parts of an epoxy resin-based coating containing 60 parts and 20 to 60 parts of a phenol-modified hydrocarbon low polymer is formed by applying 1.0 to 3.0 kg / m ² , especially the anticorrosive coating property is obtained. Becomes better.

[0049]

EXAMPLES Next, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

Example 1 Bisphenol A type epoxy resin (base material) 80 parts,
4-butanediol glycidyl ether (diluent) 20
Parts, epoxysilane (modifier, SL-A187 manufactured by Nippon Unicar Co., Ltd.), 1 part, metanil yellow (pH indicator)
A curing agent 50 composed of 101.05 parts of a main agent composed of 0.05 parts of a mixture and a Mannich-modified meta-xylene diamine (DS-4 manufactured by BITR Japan KK)
From there, a solventless epoxy primer was prepared.

Further, as a standard epoxy-based anticorrosive coating, 80 parts of a bisphenol A type epoxy resin,
A coating composition was prepared comprising 20 parts of 4-butanediol glycidyl ether and 50 parts of a Mannich-modified cyclic amine-based curing agent (Ancamine MCA manufactured by BITR Japan KK).

On a concrete substrate, the above-mentioned solvent-free epoxy primer (a mixture of a base agent and a curing agent containing an indicator) was applied at a rate of 0.2 kg / m ² , and cured until a tack-free state was reached. Coating top coat paint thickness 0.05-0.1mm, 0.1-0.3mm,
It was applied so as to have a thickness of 0.5 to 1.0 mm and 1.0 to 1.2 mm, and was cured by placing it in a thermostat at 20 ° C. for 7 days.

Two drops of a 50% sulfuric acid solution (approximately φ15 mm) were dropped on the formed coating film, and the state of discoloration was observed after being left for one week in an atmosphere of 40 ° C.

Table 1 shows the results.

Example 2 Instead of the standard epoxy anticorrosion coating topcoat used in Example 1, bisphenol A type epoxy resin 80 was used as an epoxy anticorrosion coating with improved sulfuric acid resistance.
Part, 20 parts of a phenol-modified hydrocarbon low polymer for improving sulfuric acid resistance (TRE200 manufactured by Toho Chemical Industry Co., Ltd., about 95% of non-volatile content), Mannich-modified cyclic amine-based curing agent (BITR) -The state of discoloration and discoloration by a 50% sulfuric acid solution was observed in the same manner as in Example 1 except that a coating consisting of 40 parts of Ankamin MCA manufactured by Japan KK was used.

Table 1 shows the results.

[0057]

[Table 1]

From the results shown in Table 1, it can be seen that by including a pH indicator in the primer layer, it is possible to determine whether sulfuric acid has permeated the anticorrosive coating top coat layer and reached the primer layer. In addition, it can be seen that the anticorrosion coating topcoat layer of Example 2 is less likely to transmit sulfuric acid than the anticorrosion coating topcoat layer of Example 1.

Example 3 Bisphenol A type epoxy resin (base material) 80 parts,
4-butanediol glycidyl ether (diluent) 20
Parts, epoxysilane (modifier, SL-A187 manufactured by Nippon Unicar Co., Ltd.) 1 part, thymol blue (pH indicator)
A curing agent 50 composed of 101.05 parts of a main agent composed of 0.05 parts of a mixture and a Mannich-modified meta-xylene diamine (DS-4 manufactured by BITR Japan KK)
From there, a solventless epoxy primer was prepared.

As a standard epoxy-based anticorrosive coating topcoat, 80 parts of bisphenol A type epoxy resin,
A paint was prepared comprising 20 parts of 6-hexanediol glycidyl ether and 50 parts of an epoxy-modified meta-xylene diamine-based curing agent (Fujicure FXK898B manufactured by Fuji Kasei Kogyo Co., Ltd.).

On a concrete substrate, 0.2 kg / m ^{2 of the} solvent-free epoxy primer (a mixture of a base agent and a curing agent containing an indicator) is applied, and after curing to a tack-free state, the epoxy-based anticorrosive coating is applied. Paint with a thickness of 0.05-0.1mm, 0.1-0.3mm, 0.5-
It was applied to 1.0 mm and 1.0 to 1.2 mm, and cured in the same manner as in Example 1. After that, two drops of a 50% sulfuric acid solution were dropped (about φ15 mm) on the formed coating film. hand,
After standing for one month in an atmosphere of 40 ° C., the degree of discoloration and discoloration was observed.

Table 2 shows the results.

Example 4 Instead of the standard epoxy anticorrosive coating topcoat used in Example 3, bisphenol A type epoxy resin 70 was used as an epoxy anticorrosive coating with improved sulfuric acid resistance.
Parts, 30 parts of a phenol-modified hydrocarbon low polymer (TRE200 manufactured by Toho Chemical Industry Co., Ltd., nonvolatile content: about 95%)
Except for using a paint consisting of 35 parts of a Mannich-modified cyclic amine-based curing agent (Ancamine MCA manufactured by BTR Japan Co., Ltd.), 50%
The degree of discoloration due to the sulfuric acid solution was observed.

Table 2 shows the results.

[0065]

[Table 2]

From the results shown in Table 2, it can be seen that by including a pH indicator in the primer layer, it is possible to determine whether or not sulfuric acid permeates the anticorrosion coating top coat layer and reaches the primer layer. In addition, it can be seen that the anticorrosion coating topcoat layer of Example 4 is more difficult to transmit sulfuric acid than the anticorrosion coating topcoat layer of Example 3.

Example 5 As a solvent-free epoxy primer, bisphenol A
80 parts of epoxy resin (base material), 20 parts of 1,4-butanediol glycidyl ether (diluent), epoxy silane (modifier, SL-A187 manufactured by Nippon Unicar Co., Ltd.)
A composition was prepared comprising 0.5 part of the base agent (100.5 parts) and 50 parts of Mannich-modified metaxylenediamine (DS-4, a curing agent manufactured by BTR Japan Co., Ltd.).

As a solvent-free epoxy-based intermediate layer paint, bisphenol A type epoxy resin (base material) 80 parts,
1,4-butanediol glycidyl ether (diluent)
20 parts, 100.05 parts of a main ingredient consisting of 0.05 parts of metanil yellow (pH indicator) and 50 parts of Mannich-modified metaxylenediamine (DS-4, a hardener), manufactured by BTR Japan Ltd. The following compositions were prepared.

Further, a bisphenol A type epoxy resin (base material) 8
0 parts, 100 parts of a main agent composed of 20 parts of 1,4-butanediol glycidyl ether (diluent), and 50 parts of a Mannich-modified cyclic amine-based curing agent (ancamine MCA manufactured by BTR Japan Ltd.) A clear solvent-free anticorrosion paint consisting of

On a concrete substrate, 0.2 kg / m ^{2 of the} solvent-free epoxy primer was applied, and after curing to a tack-free state, the paint for a solvent-free epoxy intermediate layer was applied to a thickness of 0.5 mm. Cured to the tack-free state. Then, the standard epoxy-based anticorrosion coating top coat is 0.5 mm thick as a standard thickness and 0.3 mm as a thinner.
It was applied to three types of thicknesses of 05 mm thick and 1.3 mm thicker, and cured under conditions of 20 ° C./7 days.

Two drops (about 15 mm) of a 50% sulfuric acid solution were dropped on the formed coating film, and the condition of the discoloration and discoloration was observed after leaving it for one week and one month in an atmosphere of 40 ° C.

Table 3 shows the results.

[0073]

[Table 3]

Example 6 The solvent-free epoxy primer, the solvent-free epoxy interlayer paint and the standard epoxy anti-corrosion coating top coat used in Example 5 were used.

On a concrete substrate, 0.2 kg / m ^{2 of the} solvent-free epoxy primer was applied, and after curing to a tack-free state, the paint for a solvent-free epoxy intermediate layer was applied to a thickness of 0.5 mm. Cured to the tack-free state. Then, the standard epoxy-based anticorrosive coating was applied to a standard thickness of 0.5 mm. Assuming that pinholes and cracks occurred in the anticorrosion coating top coat layer, test pieces having pinholes having a diameter of about 0.1 mm and cracks having a width of 0.1 mm were prepared.

Two drops of 50% sulfuric acid solution were respectively dropped onto the pinholes and cracks of the formed coating film (approximately φ15
mm), and after standing for one week and one month in an atmosphere of 40 ° C., the degree of discoloration was observed.

Table 4 shows the results.

[0078]

[Table 4]

From the results shown in Table 4, when there is a pinhole or a crack in the anticorrosion coating topcoat layer, it is possible to evaluate whether or not the anticorrosion coating topcoat layer has a defect because the intermediate layer is discolored. it can. The persistence after discoloration was also confirmed.

[0080]

According to the present invention, it is possible to determine whether or not the anticorrosion coating layer provided on the substrate has deteriorated.
Repairs can be made at appropriate times.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 D 5/08 5/08 7/12 7/12 131/00 131/00 161/04 161/04 163/00 163/00 175/04 175/04 201/00 201/00 (72) Inventor Yoshio Tanioka 236 Nakai, Tatsuno-cho, Tatsuno-shi, Hyogo Nagasechem Tex Corporation F-term (reference) 4D075 AE03 AE06 AE08 AE09 CA33 DB12 DC02 EA05 EB33 4J038 CF001 CG001 DA032 DB001 DD001 DG001 DL001 EA001 GA12 JA03 JA33 JA49 JB01 JB06 JB16 JB18 JB21 JB28 JB33 JC02 JC18 KA02 NA02 PC12 PB05

Claims (12)

[Claims] 1. Deterioration degree can be determined having at least two layers of an undercoat layer provided on a substrate and containing an indicator that changes color with a strong acid and an anticorrosive coating layer capable of determining the color change. Floor with a strong anticorrosive coating. 2. Deterioration degree having at least three layers of an undercoat layer, an intermediate layer containing an indicator discolored by a strong acid, and an anticorrosion coating top layer capable of judging discoloration provided on a substrate. A floor having an anticorrosion coating layer that can be determined. 3. The anticorrosion coating layer according to claim 2, wherein the intermediate layer is an anticorrosion coating intermediate layer formed of an epoxy resin-based coating, a urethane resin-based coating, or a vinyl ester resin-based coating containing an indicator that changes color with a strong acid. Floor with. 4. The floor having an anticorrosion coating according to claim 1, wherein the indicator discolored by a strong acid is a pH indicator. 5. The floor having an anticorrosion coating layer according to claim 1, wherein the anticorrosion coating top coat layer is formed from an epoxy resin-based coating, a urethane resin-based coating or a vinyl ester resin-based coating. 6. The anticorrosion coating layer according to claim 1, 2, 3 or 4, wherein the anticorrosion coating top coat layer is formed from a coating composition containing a phenol-modified hydrocarbon low polymer in an epoxy resin coating composition. floor. 7. A method for judging the degree of deterioration, wherein an undercoat layer containing an indicator discolored by a strong acid is provided on a substrate, and then an anticorrosive coating overcoat layer capable of determining at least the discoloration is provided. A method of forming a floor with a possible anticorrosion coating. 8. An at least three layers comprising an undercoat layer, an intermediate layer containing an indicator discolored by a strong acid, and an anticorrosion coating top layer capable of determining discoloration on a substrate. A method for forming a floor having an anticorrosion coating layer whose deterioration degree can be determined. 9. The method according to claim 8, wherein the intermediate layer is an anticorrosion coating intermediate layer formed of an epoxy resin-based coating, a urethane resin-based coating, or a vinyl ester resin-based coating containing an indicator that changes color with a strong acid. 10. The method according to claim 7, wherein the indicator that changes color with a strong acid is a pH indicator. 11. The method according to claim 7, wherein the anticorrosion coating top coat layer is formed from an epoxy resin-based paint, a urethane resin-based paint or a vinyl ester resin-based paint. 12. The method according to claim 7, 8, 9 or 10, wherein the anti-corrosion coating top coat layer is formed from a paint obtained by adding a phenol-modified hydrocarbon low polymer to an epoxy resin-based paint.