JPH10316462A - Deterioration preventing agent for concrete or mortar and method for preventing deterioration of concrete or mortar - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deterioration preventing agent for concrete or mortar effective for preventing the deterioration of a concrete construction such as a sewage facility by sulfuric acid generated by the action of sulfur-oxidizing bacteria and provide a method for preventing the deterioration of concrete or mortar by using the preventing agent. SOLUTION: The deterioration of concrete or mortar can be prevented by making a concrete or mortar include a deterioration preventing agent containing a metallophthalocyanine expressed by the formula MXn Pc (M is a metal atom; X is oxygen atom, a halogen atom or hydroxyl group; Pc is phthalocyanine skeleton; (n) is an integer of 1-5) or its derivative as an active component in concrete or mortar, thereby causing bacteriostatic and/or bactericidal effect on sulfur-oxidizing bacteria. The deterioration of concrete or mortar can be prevented effectively over a long period by this process without polluting water and the process is especially effective for preventing the deterioration of concrete construction of sewage facility, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agent for preventing deterioration of concrete or mortar, which is characterized by preventing and / or sterilizing sulfur-oxidizing bacteria, and a method of preventing deterioration of concrete or mortar using the same. More specifically, the present invention relates to a concrete or mortar deterioration preventing agent suitably used for concrete structures or mortar structures such as sewerage facilities, and a method of preventing concrete or mortar deterioration.

[0002]

2. Description of the Related Art In recent years, in sewerage facilities in Japan,
There have been many reports of deterioration of concrete structures. Moreover, these degradations are not limited to Japan, the United States, Egypt, South Africa,
It has also been reported in Australia and elsewhere. Since the construction of sewerage facilities and other facilities is very expensive, it is important to take appropriate measures to prevent concrete deterioration in order for these facilities to function effectively over a long period of time. is there.

It is known that two types of microorganisms are involved in the deterioration cycle of concrete, namely, sulfate-reducing bacteria and sulfur-oxidizing bacteria such as Thiobacillus. In the degradation process of concrete by these microorganisms, first, sulfate present in the sewage (usually, the sulfate concentration in the sewage is in the range of 20 to 40 mg / L) is converted by sulfate reducing bacteria under anaerobic conditions. It is reduced to generate hydrogen sulfide. Next, the hydrogen sulfide is adsorbed by the water adhering to the concrete wall surface, and is oxidized by the sulfur-oxidizing bacteria under aerobic conditions to produce sulfuric acid.
The calcium contained in the concrete is changed into calcium sulfate (gypsum) by the generated sulfuric acid, thereby making the concrete brittle (deteriorated).

[0004] Of the above two types of microorganisms, sulfur oxidizing bacteria are considered to be the main cause of concrete deterioration, and various prevention methods for preventing the change of hydrogen sulfide to sulfuric acid by sulfur oxidizing bacteria are considered. Has been proposed. As one of them, a method for reducing the concentration of hydrogen sulfide, which is a substrate of sulfur-oxidizing bacteria, is described. For example, air and oxygen are injected into sewage to volatilize and oxidize hydrogen sulfide before it is adsorbed on the water on the concrete wall, and at the same time suppress the action of anaerobic sulphate-reducing bacteria to reduce hydrogen sulfide. There is known a method for reducing the occurrence of phenomena. Among these, the air injection method of injecting air into sewage is a relatively simple method, but may disturb the gas-liquid equilibrium of hydrogen sulfide and cause more hydrogen sulfide to diffuse into the air. Further, the oxygen injection method of injecting oxygen into sewage can more effectively oxidize hydrogen sulfide, but has a disadvantage of increasing cost. Separately, a method is known in which a large amount of a metal salt such as chlorine, hydrogen peroxide, potassium permanganate, or iron, zinc, lead, or copper is added to sewage to capture hydrogen sulfide in the sewage. I have. In addition, Japanese Patent Application Laid-Open
No. 70561 discloses a method of adding a water-soluble quinone derivative to sewage to oxidize hydrogen sulfide, and at the same time, suppressing the action of sulfate-reducing bacteria to prevent concrete deterioration. However, these methods are not effective because the added substances are washed away in the sewage, and have a problem in economics.

Further, a method is known in which an antibacterial agent, which is an organic compound, is mixed into concrete to kill sulfur-oxidizing bacteria and prevent deterioration of the concrete. However, these antimicrobial agents can cause pinholes and cracks in the concrete, which can reduce the durability of the concrete.
At present, the use of Na-PCP (sodium pentachlorophenol) having a strong antibacterial effect is prohibited.

It is known that the growth of sulfur-oxidizing bacteria is inhibited by various metal ions, and metals such as copper, nickel, tin, lead and the like which are hardly soluble in water and soluble in sulfuric acid are used. Japanese Patent Laid-Open No. 4-149 discloses a method for preventing the deterioration of concrete by adding a metal oxide of the formula (1) to concrete.
No. 053. In this method, metal ions are eluted from the metal and / or metal oxide by the sulfuric acid generated by the sulfur oxidizing bacteria, thereby preventing and / or sterilizing the sulfur oxidizing bacteria. However, this method uses a metal and / or metal oxide having high solubility in sulfuric acid, and thus has a drawback such as an increase in the amount of metal used in order to prevent concrete deterioration over a long period of time. doing. In addition, since heavy metal ions such as nickel, tin, and lead are eluted into the sewage, there is a possibility of water pollution by these.

[0007] Further, JP-A-6-16460 and JP-A-6-16461 show a method for preventing deterioration by adding concrete to a metal complex such as nickelocene and nickel dimethylglyoxime. However, these metal complexes have carcinogenicity and have a problem in safety.

Some methods using a material resistant to sulfuric acid have been proposed as a method for preventing concrete deterioration. For example, JP-A-63-16072 and JP-A-2-265708 disclose a method of protecting concrete by lining with an epoxy resin or polyester resin, and JP-A-1-55493 discloses a method of protecting concrete. A method for protecting concrete by lining materials is shown. However, these methods have the disadvantage that the construction cost is high and the life is short because the lining is peeled off through the pinhole. Therefore, in order to maintain the effect of preventing deterioration, periodic repainting is necessary, and every time the operation of the sewerage facility or the like must be stopped for a long time.

It is also known to use slag cement or the like having a high sulfate content to obtain concrete having excellent acid resistance and sulfate resistance. However, this slag cement is poor in strength and is obtained. Concrete cannot completely prevent deterioration due to sulfuric acid.

[0010]

SUMMARY OF THE INVENTION The present invention relates to a concrete or mortar deterioration inhibitor which can effectively and effectively prevent the deterioration of concrete or mortar, and a concrete or mortar using the same. The purpose is to provide a method for preventing deterioration.

[0011]

That is, the present invention provides a deterioration inhibitor for concrete or mortar, comprising a metal phthalocyanine represented by the following general formula (1) or a derivative thereof as an active ingredient. MX _n Pc (1) (wherein, M is a metal atom, X is an oxygen atom, a halogen atom or a hydroxyl group, Pc is a phthalocyanine skeleton, n represents 1 to 5
Are respectively shown. )

Further, the present invention provides the above-mentioned deterioration inhibitor for concrete or mortar, wherein the valence of the metal atom is 3 to 7.

Further, the present invention provides that the metal atom is at least one selected from the group consisting of titanium, vanadium, chromium, molybdenum, tungsten, manganese, aluminum, gallium, indium, silicon, germanium, and tin. The present invention provides the above-mentioned deterioration inhibitor for concrete or mortar.

Further, the present invention provides a method for preventing deterioration of concrete or mortar, which comprises adding the above-mentioned deterioration inhibitor to concrete or mortar.

When the deterioration inhibitor of the present invention is used in concrete or mortar, the cycle of concrete deterioration can be cut by preventing and / or sterilizing sulfur-oxidizing bacteria that are present in sewage or the like and propagate. Thus, it is possible to effectively prevent concrete and the like from being deteriorated for a long period of time.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The deterioration inhibitor for concrete or mortar of the present invention contains a metal phthalocyanine represented by the following general formula (1) or a derivative thereof as an active ingredient. MX _n Pc (1) (wherein, M is a metal atom, X is an oxygen atom, a halogen atom or a hydroxyl group, Pc is a phthalocyanine skeleton, n represents 1 to 5
Are respectively shown. The metal phthalocyanine represented by the general formula (1) has a metal atom represented by M coordinated to a phthalocyanine skeleton Pc having no substituent, and further has an oxygen atom represented by X in the axial direction, fluorine, and chlorine. , Bromine, a compound in which 1 to 5 halogen atoms or hydroxyl groups such as iodine are coordinated,
The derivative is a compound having a substituent atom or a substituent other than a hydrogen atom on the benzene ring in the metal phthalocyanine molecule. In the present invention, it is desirable to use a metal phthalocyanine or a derivative thereof that does not dissolve in water.

In the present invention, in order for the metal phthalocyanine to have the structure represented by the general formula (1), the valence of the metal atom must be 3 to 7. In the present invention, any metal atom can be used as long as it is a metal atom capable of taking such a valence, but in particular, titanium, vanadium, chromium, molybdenum, tungsten,
Desirably, it is at least one of manganese, aluminum, gallium, indium, silicon, germanium, and tin. The metal phthalocyanine having such a metal atom can be easily coordinated with an oxygen atom in the cells of a sulfur-oxidizing bacterium, and is considered to effectively suppress the oxidation of a sulfur compound to sulfuric acid.

Specific examples of the substituent or substituent other than the hydrogen atom of the metal phthalocyanine derivative include the following. That is, halogen atoms such as fluorine, chlorine, bromine and iodine, methyl group, ethyl group, propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group , Trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, 1,
3-cyclohexadienyl group, 2-cyclopentene-1
A substituted or unsubstituted alkyl group such as -yl group, 2,4-cyclopentadiene-1-ylenyl group, methoxy group, ethoxy group, propoxy group, n-butoxy group, se
substituted or unsubstituted alkoxy groups such as c-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, stearyloxy group, trifluoromethoxy group, etc., methylthio group, ethylthio group, propylthio group, butylthio group, sec- Substituted or unsubstituted thioalkoxy groups such as butylthio group, tert-butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nitro group, cyano group, carbonyl group, carboxyl group, ester group, hydroxyl group, sulfonic acid group Carbocyclic aromatic amino groups such as vinyl group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, dipropylamino group, dibutylamino group and other alkyl group-substituted amino groups, diphenylamino group and ditolylamino group , Bis (acetooxy Methyl) amino group, bis (aceto-oxyethyl) amino group, bis (aceto oxy propyl) amino group, bis (aceto oxy butyl) amino group,
Mono- or di-substituted amino group such as dibenzylamino group, phenoxy group, p-tert-butylphenoxy group, 3-
Substituted or unsubstituted aryloxy group such as fluorophenoxy group, substituted or unsubstituted arylthio group such as phenylthio group and 3-fluorophenylthio group, phenyl group, biphenyl group, triphenyl group, tetraphenyl group, 3-nitro Phenyl group, 4-methylthiophenyl group, 3,5-dicyanophenyl group, o-, m-, and p
-Tolyl, xylyl, o-, m-, and p-cumenyl, mesityl, pentalenyl, indenyl, naphthyl, azulenyl, heptalenyl, acenaphthylenyl, phenalenyl, fluorenyl, anthryl, anthraquinonyl Group, 3-methylanthryl group,
Phenanthryl group, triphenylene group, pyrenyl group, chrysenyl group, 2-ethyl-1-chrysenyl group, picenyl group, perylenyl group, 6-chloroperylenyl group, pentaphenyl group, pentacenyl group, tetraphenylene group, hexaphenyl group, hexacenyl group, It is a substituted or unsubstituted aromatic ring group such as a rubicenyl group, a colonenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an ovarenyl group, and the like.

In the present invention, as the metal phthalocyanine derivative, 1 to 8 hydrogen atoms of the benzene ring in the above-mentioned metal phthalocyanine molecule may be a halogen atom, an alkyl group having 1 to 6 carbon atoms, a nitro group or a cyano group. , A derivative substituted with a hydroxyl group or a sulfonic acid group.
These metal phthalocyanines or derivatives thereof may be used alone or in combination of two or more.

In the present invention, the metal phthalocyanine or its derivative is preferably in the form of a fine powder so that it can be easily and uniformly mixed with concrete or mortar. The average particle size of the fine powder of metal phthalocyanine or a derivative thereof is preferably 0.001 μm to 1 mm, more preferably 0.01 μm to 0.1 mm.

The deterioration inhibitor for concrete or mortar of the present invention can contain a known admixture for concrete or mortar, in addition to metal phthalocyanine or a derivative thereof. Examples of such an admixture include AE agents and water reducing agents used for improving workability such as fluidity, high-performance AE water reducing agents, and thickeners used for preventing material separation. it can. As AE agent / water reducing agent, high performance AE water reducing agent, naphthalene type,
Polycarboxylic acid-based, melamine-based, aminosulfonic acid-based polymers and the like, and as the thickener, starch, guar gum, methylcellulose, carboxymethylcellulose, xanthan gum, polysaccharides such as curdlan and derivatives thereof, Synthetic polymers such as polyacrylamide, sodium polyacrylate, and polyvinyl alcohol are exemplified. When the concrete or mortar deterioration inhibitor of the present invention contains the above-mentioned admixture, the amount of the metal phthalocyanine or a derivative thereof added to the admixture depends on the amount of the admixture added to the concrete or mortar. It is preferably from 5 to 500 parts by weight, more preferably from 10 to 100 parts by weight, based on 100 parts by weight of the admixture.

When the deterioration inhibitor for concrete or mortar of the present invention contains the above-mentioned admixture, the metal phthalocyanine or a derivative thereof is preferably dispersed in the admixture. In order to disperse the metal phthalocyanine or its derivative in the admixture, various known pulverizers or dispersers can be used. Specifically, a three-roll mill, a two-roll mill, a ball mill, an attritor, a sand mill, a co-ball mill, a basket mill, and a ball mill, which are dispersed by an impact force caused by collision with media such as glass beads, zirconia beads, and menor balls, are used.
A vibrating mill, a paint conditioner, and a device such as a disperser, a homogenizer, and Clearmix (R) that disperse by a rotating blade that generates shear stress, cavitation, collision force, potential core, and the like can be used. Further, a kneader, an extruder, a jet mill, an ultrasonic disperser, and the like can be used.

In the deterioration inhibitor for concrete or mortar of the present invention, the amount of metal phthalocyanine or a derivative thereof is preferably 0.001 to 30 parts by weight based on 100 parts by weight of cement component in concrete or mortar. , 0.01 to 5 parts by weight. When the amount of the metal phthalocyanine or its derivative is less than 0.001 part by weight, it is difficult to maintain the antibacterial and / or bactericidal effect against sulfur-oxidizing bacteria for a long time. On the other hand, if it exceeds 30 parts by weight, further improvement in the antibacterial and / or bactericidal effect against sulfur-oxidizing bacteria cannot be expected, and the cost is undesirably increased. In addition, the strength of the concrete or mortar is significantly reduced.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(Examples 1 to 24) Metal phthalocyanine or a derivative thereof shown in Table 1 having an average particle diameter of 1.0 µm was added to a concrete composition comprising 100 parts by weight of cement, 200 parts by weight of sand, and 50 parts by weight of water. 2.
5 parts by weight were added and kneaded well using a concrete mixer. This was put in a mold, molded, and cured for 28 days (24 hours in a moisture box, 27 days in water) to obtain a concrete specimen.

(Examples 25 to 48) To a mortar composition consisting of 120 parts by weight of cement and 80 parts by weight of water, 3.0 parts each of the metal phthalocyanine or its derivative shown in Table 1 having an average particle diameter of 1.0 μm was used. And kneaded well using a mortar mixer. This was put in a mold, molded, and cured for 28 days (24 hours in a moisture box, 27 days in water) to obtain a mortar specimen.

(Examples 49 to 57) Admixture (water reducing agent) for concrete containing a melamine polymer as a main component 100
50 parts by weight of each of the metal phthalocyanines or derivatives thereof shown in Table 1 having an average particle size of 1.0 μm was added to parts by weight, and dispersed by using a vibration mill. Cement 10
0 parts by weight, 200 parts by weight of sand, 3 parts by weight of the admixture in which the above-mentioned metal phthalocyanine was dispersed, and 40 parts by weight of water were mixed and thoroughly kneaded using a concrete mixer. This was put in a mold, molded, and cured for 28 days (24 hours in a moisture box, 27 days in water) to obtain a concrete specimen.

Table 1 Example Phthalocyanine Compound Example ─────────────────────────── 1,25 TiOPc 2,26 VOPc 3,27 CrOPc 4,28 CrO ₂ Pc 5,29,49 MoOPc 6,30,50 MoO ₂ Pc 7,31,51 WOPc 8,32,52 WO ₂ Pc 9,33 MnOPc 10,34 AlClPc 11,35 Al (OH) Pc 12,36 SiCl ₂ Pc 13,37 Si ( OH) ₂ Pc 14,38 SnCl ₂ Pc 15,39 MoOPc-Cl ₄ 16,40 MoOPc- (t-Bu) ₄ 17,41 MoOPc- (CN) ₄ 18,42 MoOPc- (NO ₂ ) ₄ 19,43 MoOPc- _{CN) 8 20,44,53 WOPc-Cl 4} 21,45,54 WOPc- (t-Bu) 4 22,46,55 WOPc- (CN) 4 23,47,56 WOPc- (NO 2) 4 24, 48,57 WOPc- (CN) ₈ ────────────────────────────────── * TiOPc, VOPc, CrOPc, CrO ₂ Pc,
MoOPc, MoO ₂ Pc, WOPc, WO ₂ Pc, M
nOPc, AlClPc, Al (OH) Pc, SiCl
₂ Pc, Si (OH) ₂ Pc and SnCl ₂ Pc are the same as those in the aforementioned general formula (1), wherein the metal atom M is titanium, vanadium, chromium, molybdenum, tungsten, manganese,
X represents a metal phthalocyanine in which aluminum, silicon, and tin are each an oxygen atom, a chlorine atom, or a hydroxyl group. In addition, Cl, t-Bu, CN, and NO ₂ are each a substituent atom or a substituent having a chlorine atom, a tert-butyl group,
It represents a cyano group and a nitro group.

Comparative Example 1 A concrete specimen was obtained by performing the same operation as in Example 1 except that no metal phthalocyanine or its derivative was added.

Comparative Example 2 The same operation as in Example 1 was carried out except that an organic nitrogen sulfur-based antibacterial agent ("Fine Sand A-3" manufactured by Tokyo Fine Chemical Co., Ltd.) was added instead of the metal phthalocyanine or its derivative. To obtain a concrete specimen.

Comparative Example 3 A mortar specimen was obtained in the same manner as in Example 25 except that no metal phthalocyanine or its derivative was added.

Comparative Example 4 The same operation as in Example 25 was performed, except that an organic nitrogen sulfur-based antibacterial agent ("Fine Sand A-3" manufactured by Tokyo Fine Chemical Co., Ltd.) was added instead of the metal phthalocyanine or its derivative. Thus, a mortar specimen was obtained.

The specimens obtained in Examples and Comparative Examples were exposed to the inside of a sludge facility wall of a sewage treatment plant, and exposed to sludge for 9 months to determine the adhesion of sulfur-oxidizing bacteria and the gypsum formation of the specimen. Was evaluated as follows. The results are shown in Table 2.

(Adhesion of Sulfur-Oxidizing Bacteria) The surface of the specimen was washed with 50 ml of sterilized tap water (sterilized in an autoclave for 20 minutes) using a tooth brush, and the washed solution was ultrasonically crushed. Diluted. This is a solid ONM medium solidified with gellan gum with the addition of yeast extract (Imai, Kazumi, Katagiri, "Biochemical research on sulfur bacteria (Part 2)
About the growth conditions of fungi ", Fermentation Engineering, 42, 762
, 1964), and the resulting colonies were counted at a culture temperature of 30 ° C. for 11 days. From this value, the number of sulfur-oxidizing bacteria per ml of the washing solution (cell / ml)
Was determined, and the state of adhesion of sulfur-oxidizing bacteria was evaluated based on the following evaluation criteria.

(Gypsum state) 10 g of the surface of the specimen was sampled, and the amount of calcium sulfate was measured using an X-ray diffractometer. From this value, the ratio (%) of calcium on the surface of the specimen that changed to calcium sulfate, which is a corrosion product due to sulfuric acid, was determined, and the gypsum state of the specimen was evaluated based on the following evaluation criteria.

Evaluation Criteria for Sulfur-Oxidizing Bacteria Adhesion Evaluation 1:10 ⁶ cell / ml or more Evaluation 2:10 ⁴ to 10 ⁶ cell / ml Evaluation 3:10 ² to 10 ⁴ cell / ml Evaluation 4:10 ² cell / ml Less than 5 ml Evaluation 5: No adhesion was observed at all

Evaluation Criteria for the Gypsum State of the Specimen Evaluation 1: 80% or more Evaluation 2: 50 to 80% Evaluation 3: 30 to 50% Evaluation 4: 1 to 30% Evaluation 5: No gypsum was recognized at all

Table 2 Example and Comparative Example Sulfur-oxidizing bacteria adhered Gypsum status ────────────────────────────────── Example 1 Evaluation 4 Evaluation 4 Example 2 Evaluation 4 Evaluation 4 Example 3 Evaluation 5 Evaluation 5 Example 4 Evaluation 4 Evaluation 5 Example 5 Evaluation 5 Evaluation 5 Example 6 Evaluation 4 Evaluation 5 Example 7 Evaluation 5 Evaluation 5 Example 8 Evaluation 4 Evaluation 5 Example 9 Evaluation 4 Evaluation 5 Example 10 Evaluation 4 Evaluation 5 Example 11 Evaluation 4 Evaluation 5 Example 12 Evaluation 4 Evaluation 4 Example 13 Evaluation 4 Evaluation 4 Example 14 Evaluation 4 Evaluation 5 Example 15 Evaluation 5 Evaluation 5 Example 16 Evaluation 5 Evaluation 5 Execution Example 17 Evaluation 5 Evaluation 5 Example 18 Evaluation 5 Evaluation 5 Example 19 Evaluation 5 Evaluation Example 20 Evaluation 5 Evaluation 5 Example 21 Evaluation 5 Evaluation 5 Example 22 Evaluation 5 Evaluation 5 Example 23 Evaluation 5 Evaluation 5 Example 24 Evaluation 5 Evaluation 5 Example 25 Evaluation 4 Evaluation 4 Example 26 Evaluation 4 Evaluation 4 Evaluation Example 27 Evaluation 5 Evaluation 5 Example 28 Evaluation 4 Evaluation 5 Example 29 Evaluation 5 Evaluation 5 Example 30 Evaluation 4 Evaluation 5 Example 31 Evaluation 5 Evaluation 5 Example 32 Evaluation 4 Evaluation 5 Example 33 Evaluation 4 Evaluation 5 Example 34 Evaluation 4 Evaluation 5 Example 35 Evaluation 4 Evaluation 5 Example 36 Evaluation 4 Evaluation 4 Example 37 Evaluation 4 Evaluation 4 Example 38 Evaluation 4 Evaluation 5 Example 39 Evaluation 5 Evaluation 5 Example 40 Evaluation 5 Evaluation 5 Example 41 Evaluation 5 Evaluation 5 Example 42 Evaluation 5 Evaluation 5 Example 43 Evaluation 5 Evaluation 5 Example 44 Evaluation 5 Evaluation 5 Example 45 Evaluation 5 Evaluation 5 Example 5 6 Evaluation 5 Evaluation 5 Example 47 Evaluation 5 Evaluation 5 Example 48 Evaluation 5 Evaluation 5 Example 49 Evaluation 5 Evaluation 5 Example 50 Evaluation 4 Evaluation 5 Example 51 Evaluation 5 Evaluation 5 Example 52 Evaluation 4 Evaluation 5 Example 53 Evaluation 5 Evaluation 5 Example 54 Evaluation 5 Evaluation 5 Example 55 Evaluation 5 Evaluation 5 Example 56 Evaluation 5 Evaluation 5 Example 57 Evaluation 5 Evaluation 5 Comparative example 1 Evaluation 1 Evaluation 1 Comparative example 2 Evaluation 1 Evaluation 1 Comparative example 3 Evaluation 1 Evaluation 1 Comparative Example 4 Evaluation 1 Evaluation 2

The specimen containing the metal phthalocyanine or the derivative thereof according to the present invention was evaluated as 4 to 5 in both the adhesion state of the sulfur-oxidizing bacteria and the gypsum state, but the specimen containing no metal phthalocyanine or the derivative thereof, and In the specimen containing the organic nitrogen sulfur-based antibacterial agent instead of the metal phthalocyanine or its derivative, adhesion of sulfur-oxidizing bacteria was remarkable, and the surface became gypsum and deteriorated.
From this, it was recognized that the metal phthalocyanine or its derivative of the present invention was effective in preventing deterioration of concrete or mortar.

[0040]

EFFECTS OF THE INVENTION Some enzymes involved in sulfur redox such as sulfide oxidase and sulfadioxidase are present in the body of sulfur-oxidizing bacteria present in sewage and soil and causing deterioration of concrete or mortar. Exist and sulfuric acid is generated by these interactions (Koizumi, “Physiological ecology and biotechnology of sulfur-oxidizing bacteria”, Water and wastewater, 31
Vol. 307, 1989). Also, sulfur oxidizing bacteria
It has an ecological feature that a solid substance such as sulfur particles can be used as a substrate. For this reason, metal phthalocyanine or its derivative contained in concrete or mortar is also easily taken into the cells of sulfur-oxidizing bacteria. The metal phthalocyanine or a derivative thereof incorporated into the sulfur-oxidizing bacteria can inhibit and / or sterilize the sulfur-oxidizing bacteria by inhibiting an enzymatic reaction in the sulfur-oxidizing bacteria. In addition, since the deterioration inhibitor of the present invention does not elute components in sulfuric acid, unlike the above-described deterioration inhibitor containing a metal and / or a metal oxide, a small amount of metal phthalocyanine or a derivative thereof is used for concrete or concrete. The effect of preventing the deterioration of the mortar can be maintained for a long time, and the water quality is not contaminated by the eluted metal ions. Furthermore, the metal phthalocyanine or its derivative is more easily dispersed in the polymer component contained in the concrete or mortar admixture than the above-mentioned metal or metal oxide, so that the metal phthalocyanine or its derivative is contained in the admixture. It is possible to prepare concrete or mortar in which metal phthalocyanine or a derivative thereof is uniformly dispersed without aggregation and precipitation. Therefore, the deterioration preventing agent for concrete or mortar of the present invention and the method for preventing deterioration of concrete or mortar can prevent deterioration of concrete or mortar over a long period of time without contaminating water quality. Or, it is used for a wide range of uses, such as structures of sewage facilities where mortar is used.

Claims (4)

[Claims] 1. A deterioration inhibitor for concrete or mortar, comprising a metal phthalocyanine represented by the following general formula (1) or a derivative thereof as an active ingredient. MX _n Pc (1) (wherein, M is a metal atom, X is an oxygen atom, a halogen atom or a hydroxyl group, Pc is a phthalocyanine skeleton, n represents 1 to 5
Are respectively shown. ) 2. The deterioration inhibitor for concrete or mortar according to claim 1, wherein the valence of the metal atom is 3 to 7. 3. The method according to claim 1, wherein the metal atom is at least one selected from the group consisting of titanium, vanadium, chromium, molybdenum, tungsten, manganese, aluminum, gallium, indium, silicon, germanium, and tin. The deterioration inhibitor for concrete or mortar according to claim 1. 4. The concrete or mortar according to claim 1
3. A method for preventing deterioration of concrete or mortar, characterized by including the deterioration preventing agent according to any one of the above (3).