JP2808087B2 - Deterioration inhibitor and method for preventing deterioration of concrete structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is used for water treatment facilities such as revetment blocks, cooling introduction waterways, aquaculture tanks, steel pipes for water supply and sewerage, water storage tanks, etc., and is used to prevent oxidative deterioration of concrete or microorganisms. The present invention relates to a deterioration preventing agent or a method for preventing deterioration.

[0002]

2. Description of the Related Art In recent years, in water treatment facilities such as water supply and sewerage, corrosion and deterioration of concrete have become a problem.
It has been found that the main cause of these factors is sewage treatment facilities, which are mainly caused by hydrogen sulfide generated by the action of anaerobic sulfate-reducing bacteria in sewage and sewage sludge. In water purification plants and fish and fish farms, many are caused by organic acids generated by metabolites of water algae and crustaceans due to their generation and attachment. In view of this situation, the following has been proposed by the Japan Sewage Works Agency as measures to prevent corrosion and deterioration of concrete. A method of preventing the generation of hydrogen sulfide itself by preventing sewage decay. A method to prevent the generated sulfide from diffusing into the atmosphere. A method for suppressing the production of sulfur-oxidizing bacteria that produces sulfuric acid based on hydrogen sulfide. A method to prevent the adhesion of water algae and crustaceans. A method of painting or lining anticorrosive paints on concrete or iron surfaces.

[0003] In the above method, since the sewage contains sludge, it is impossible to completely remove the sludge, and a satisfactory effect has not been obtained. The method is
There is immobilization of hydrogen sulfide by adding a chemical agent such as an oxidizing agent (hydrogen peroxide). However, this method is economically problematic because the chemical is expensive and requires special care in handling. In the above method, a method of absorbing and exhausting air in a facility to dilute hydrogen sulfide is known, but hydrogen sulfide gas is one of eight substances that are odorous specified by the Odor Control Law. Therefore, there is a problem of pollution, and if the working environment is 10 ppm or more, there is a problem of health, and if the concentration is further increased, there is a danger of poisoning and explosion, so that implementation is difficult.

In the method (1), as a means for preventing adhesion of algae and crustaceans, a paint is known in which a toxic agent such as phosphate is mixed into concrete or the like and applied to, for example, the bottom of a ship to gradually elute toxic substances. However, in recent years, its use has been refrained from the viewpoint of preventing marine pollution. As a method, epoxy resin or polyester resin is used as a paint, but it is difficult to provide both acid resistance and alkali resistance, and pinholes and cracks occur in concrete structures and iron, and adhesion strength is low. There is a problem that the effect of preventing corrosion is insufficient due to insufficient. In addition, when used for lining the inner surface of a settling tank, FRP, flake lining, and sheet lining are known, but their workability is poor. (For example, it is necessary to construct concrete structures with high temperature, high humidity environment or high water content.) In addition, there is an economical problem because the construction is expensive.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and, when applied to a concrete structure, has good adhesiveness over a long period of time and has a sufficient antioxidant effect even in a corrosive environment due to oxidation. An object of the present invention is to provide a coating agent and a coated product that are not easily affected by microorganisms, algae, crustaceans, shellfish, and the like.

[0006]

SUMMARY OF THE INVENTION The invention of the present application has been made from such a viewpoint. The invention of claim 1 comprises at least a fluorine resin, copper / titanium / nickel powder, uncured Portland cement or mortar. And water dispersed in water. The invention according to claim 2 is characterized in that the mixing ratio of the fluororesin and the copper / titanium / nickel powder is 1: 3 by weight. ~ 3: 1
The invention according to claim 3 further comprises a silane-based water repellent in addition to the deterioration inhibitor for concrete structures according to claim 1 or 2.
At least one of a water-soluble polymer and a surfactant
It is an agent for preventing deterioration of concrete structures by adding and blending seeds. Further, the invention according to claim 4 applies at least a fluorine resin, copper / titanium / nickel powder, and an uncured Portland cement or mortar to a concrete structure deterioration preventive agent dispersed in water on the surface of the concrete structure. A method for preventing the deterioration of a concrete structure, characterized in that the mixture is cured by curing. The invention according to claim 5 is a method in which the mixing ratio of the fluorine resin and the copper / titanium / nickel powder is 1: 3 to 3: A method for preventing deterioration of a concrete structure according to claim 4, wherein the silane-based water repellent is further added to the deterioration inhibitor according to claim 4 or 5.
At least one of a water-soluble polymer and a surfactant
This is a method for preventing the deterioration of a concrete structure, which comprises applying an agent for preventing deterioration of a concrete structure to which a seed is added and blending, onto the surface of the concrete structure and curing the agent.

[0007] The fluororesin used in the practice of the present invention is not particularly limited, but it can be easily used in the form of an emulsion with water in general. For example, Lumiflon (trade name of Asahi Glass Co., Ltd.) Polymer), Zaffle (difluoroethylene polymer) from Daikin, Floren (polyvinylidene fluoride) from ISR, and the like are applicable. The copper / titanium / nickel powder may be added individually or simultaneously, and may have an oxide film in a natural state as well as an intermetallic compound, or may further comprise a complex. These powders having a particle diameter of 2 to 0.01 mm can be applied.

When the fluororesin is applied to a concrete structure, it forms a net-like bond in the above composition and has corrosion resistance, and the copper, titanium and nickel powders are present on the surface to be coated due to the coexistence of these three components. It was confirmed that the appearance was good, there was no adhesion of organisms, and there was no change in the oxidation state. In particular, it is desirable that the mixing ratio of the fluororesin to the copper / titanium / nickel powder be 1: 3 to 3: 1 in terms of the anticorrosion effect after coating and curing. Other silane-based water repellents,
At least one of a water-soluble polymer and a surfactant
Adding and blending seeds is a common means of concrete, but silane-based water repellents enhance water resistance after curing, and water-soluble polymers improve workability, water retention, resistance to bleeding, There are various surfactants (AE agents) such as anionic, cationic and amphoteric surfactants.
Since it has a bubble effect, it should be used after careful consideration for its addition. Other portland cement or mortar components used are other than cement, for example, sand has a particle size of 0.1.
A material having a size of about 5 to 1.2 mm is used, but fine stones and siliceous materials can also be used. The amount of the cement and the various compounding agents is preferably from 70 to 80 parts by weight based on 10 to 30 parts by weight of the fluororesin from the viewpoints of workability and curability of the coating film. On the other hand, water uses a water-dispersed paint as a fluororesin, but in fact, a considerable amount of water is required to add various compounding agents in addition to cement and apply it uniformly to concrete. It is the same as that of a normal mortar that an appropriate amount may be added to such an extent that mixed coating is easy.

[0009]

According to the present invention, since the composition has the composition described above, the cement is firmly bonded to the concrete structure by hardening of the cement, and the structure is protected by the strong mesh-like film of fluororesin. . In addition, copper, titanium and nickel powders gradually elute from the coating film into water and produce copper, titanium and nickel metal ions, which react with sulfide ions generated in the water to become insoluble. The generation of metal oxides and the generation of organisms and bacteria can be prevented or suppressed, for example, the production of toxic sulfides can be prevented by sterilization with the metal ions. In addition, the fluororesin used at the same time is hardly soluble in water, and gives the cement film a strong water and soil resistance.

In practicing the present invention, 10 to 30 parts by weight of a fluororesin and 10 to 30 parts of copper, titanium and nickel powders
30 parts by weight with Portland cement or mortar material and mixed with water to disperse, and paint harden on the concrete surface. In this case, it is preferable that the fluororesin be dispersed in water to form an emulsion as described above. The reason that the ratio of the fluororesin to the copper / titanium / nickel powder is 1: 3 to 3: 1 by weight as described above is that the fluororesin is less than 1 part by weight and the copper / titanium / nickel powder is more than 3 parts by weight. And dispersibility of metal powder in water is poor,
When applied to concrete, the adhesiveness is poor, handling becomes difficult, and the coating film is liable to crack, and the sterilization effect is excessive, so that the cost is increased and the practical effect is small. . Conversely, if the fluororesin is more than 3 parts by weight and the copper / titanium / nickel powder is less than 1 part by weight, the formation of intermetallic bonds between the metals is too small and the amount of free ions is small, resulting in an insufficient sterilization effect. , The desired anticorrosion effect cannot be obtained. The composition ratio of each metal in the copper / titanium / nickel powder is not particularly limited. However, even if any one of them is missing, the bactericidal effect or the anticorrosion effect as intended in the present invention cannot be obtained. Copper, titanium, nickel powder in a predetermined amount, it is easy to obtain a dispersed coating film,
At room temperature, each metal is easily bonded, and light and robust copper / nickel combination, copper / titanium combination, or copper / titanium combination
Construct a titanium-nickel combination to form a stable corrosion resistant coating.

Fluororesins are inherently chemically stable,
The addition of a water-soluble polymer allows the presence of air or water between the particles without lowering the water resistance itself, so that the curing of curable components such as cement and mortar to be mixed at the same time is accelerated, And the anti-corrosion function can be enhanced by the cooperative coating of the fluororesin and the water-soluble polymer. That is, in the composition of the present invention, the reason why copper / titanium / nickel powder is used is that the metal oxide is easily obtained by being easily liberated into water in water, and the coating film has an anticorrosive effect, The object is to prevent the adhesion of crustaceans and the deterioration of concrete caused by hydrogen sulfide generated by the action of anaerobic sulfate-reducing bacteria. This is a remarkable difference in that conventionally all of these effects could not be expected by the sterilization action of only copper or copper oxide.

[0012]

EXAMPLES Examples of the present invention and comparative examples will be described below. In the following, parts are parts by weight. Example 1 Copper / titanium / nickel powder (5: 2.5: 2.5) 20 parts Fluororesin 15 parts was added to an appropriate amount of water to form an emulsion composition, to which cement, silica sand, and silane-based water spouting The composition, the styrene-based water-soluble polymer, and the surfactant were added in a total amount of 65 parts by weight together with an appropriate amount of water to obtain a composition of the present invention, which was applied to the surface of concrete.

EXAMPLE 2 15 parts of copper / titanium / nickel powder (15: 5: 5) 15 parts of a fluororesin was added to an appropriate amount of water to form an emulsion composition, to which a cement, a silicate and an acrylic water-soluble composition were added. A total of 50 parts by weight of the polymer was added together with an appropriate amount of water to obtain a composition of the present invention, which was applied to the surface of concrete.

Example 3 10 parts of copper / titanium / nickel powder (5: 2.5: 2.5) 15 parts of a fluororesin were added to an appropriate amount of water to form an emulsion composition, to which cement and silica sand were added. A total of 55 parts by weight was added together with an appropriate amount of water to obtain a composition of the present invention, which was applied to the surface of concrete.

Comparative Example 1 Epoxy resin 15 parts Portland cement 50 parts Silica sand 35 parts was added to a polymer water of Comparative Example by adding an appropriate amount of water.
This was applied to the concrete surface.

Comparative Example 2 As a comparative example, a polyester resin paint was applied to the surface of concrete.

Comparative Example 3 An ordinary cement prepared by adding an appropriate amount of water to 30 parts of Portland cement and 70 parts of silica sand was used as a comparative example, and this was applied to the surface of concrete.

COMPARATIVE EXAMPLE 4 10 parts of copper powder and 15 parts of epoxy resin were added to a proper amount of water to form an emulsion composition, and a total of 55 parts by weight of cement and silica sand were added together with a proper amount of water. A composition was obtained and applied to the concrete surface.

Comparative Example 5 A concrete to which nothing was applied as in the prior art was used as a comparative sample.

Each sample of the above Examples and Comparative Examples was subjected to a comparative test by the following method. Comparative Test Each of the formulations shown in the above Examples and Comparative Examples was applied to a concrete block, dried, and then immersed in an aeration tank and a final sedimentation tank of a water treatment plant for 18 months to attach the organisms and concrete. Was observed for oxidation (neutralization). The results are as shown in Table 1 for the aeration tank and Table 2 for the final sedimentation tank. In the measurement, the following test method was used.評 価 Evaluation of appearance of coating film; O Adherence of living things; Observation by visual evaluation and observation by electron microscope O Oxidation (neutralization) state: The test method was measured by X-ray diffraction analysis and differential thermal analysis using a test piece sliced.

[0021]

[Table 1]

[0022]

[Table 2]

Example 11 An emulsion composition was prepared by adding 20 parts of copper / nickel / titanium powder (1: 1: 1) to 15 parts of a fluororesin and adding an appropriate amount of water to the emulsion composition, and then adding 50 parts of Portland cement and 15 parts of silica sand. An appropriate amount of water was added to obtain a composition of the present invention.

Example 12 15 parts of copper / titanium / nickel powder (15: 15: 5) 20 parts of a fluororesin was added to an appropriate amount of water to form an emulsion composition, which was then used as Portland cement, silica sand, and silane water generating agent. Was added to 65 parts and an appropriate amount of water to obtain a composition of the present invention.

Example 13 15 parts of copper / titanium / nickel powder (10: 5: 5) 15 parts of a fluororesin were added with an appropriate amount of water to form an emulsion paint, which was then made into Portland cement, silicate, acrylic water-soluble 60 parts of activator was added to the composition of the present invention.

Comparative Example 11 An appropriate amount of water was added to 15 parts of an epoxy resin, 50 parts of Portland cement, and 35 parts of silica sand to prepare a comparative polymer cement.

Comparative Example 12 A polyester resin paint was used as a comparative sample.

Comparative Example 13 A comparative cement was prepared by adding an appropriate amount of water to 15 parts of Portland cement and 70 parts of silica sand.

Comparative Example 14 A comparative sample was prepared by adding a surfactant and an appropriate amount of water to 15 parts of copper powder, 15 parts of epoxy resin, and 50 parts of Portland cement.

Comparative Example 15 A concrete to which nothing was applied as in the prior art was used as a comparative sample.

Comparative Test Each of the formulations shown in the above Examples and Comparative Examples was applied to a concrete block to a thickness of 1 mm, dried and then immersed in a final sedimentation tank of a sewage treatment plant for 6 months. The oxidation (neutralization state) of the concrete was observed. The results are shown in Table 3 for the final settling tank. In the measurement, the following test method was used.評 価 Evaluation of appearance of coating film; O Adherence of living things; Observation by visual evaluation and observation by electron microscope O Oxidation (neutralization) state: The test method was measured by X-ray diffraction analysis and differential thermal analysis using a test piece sliced.

[0032]

[Table 3]

[0033]

According to the present invention, the preferred effects of copper, titanium and nickel powders and fluororesins provide strong adhesion when applied to the surface of a cement structure and contact with water such as pools and seawall concrete. Neutralizing acid groups such as sulphate bacteria, which are likely to occur in a contaminated state, in order to eliminate toxicity and prevent the attachment and propagation of organisms for a long period of time, and prevent concrete deterioration. it can.

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Claims (6)

(57) [Claims] (1) at least a fluorine resin, copper, titanium,
An agent for preventing deterioration of a concrete structure, wherein nickel powder and uncured Portland cement or mortar are dispersed in water. 2. The compounding ratio of the fluororesin to the copper / titanium / nickel powder is 1: 3 to 3: 1 by weight.
An agent for preventing deterioration of the concrete structure according to the above. 3. The concrete structure according to claim 1, wherein at least one of a silane-based water repellent, a water-soluble polymer, and a surfactant is further added and blended as a deterioration inhibitor. Deterioration inhibitor. 4. At least a fluorine resin, copper, titanium,
A method for preventing deterioration of a concrete structure, which comprises applying a hardening agent for a concrete structure in which nickel powder and uncured Portland cement or mortar are dispersed in water to the surface of the concrete structure and hardening the same. . 5. The compounding ratio of the fluororesin to the copper / titanium / nickel powder is 1: 3 to 3: 1 by weight.
A method for preventing deterioration of a concrete structure, comprising applying the agent for preventing deterioration of a concrete structure according to any one of the preceding claims to the surface of the concrete structure and curing the same. 6. A concrete structure further comprising at least one of a silane-based water repellent, a water-soluble polymer, and a surfactant. The method for preventing deterioration of a concrete structure according to claim 4 or 5, wherein the method is applied to the surface of the object and cured.