JP2000204295A - Sulfur oxidizing bacteria growth inhibitor-containing paint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make formable a film which effectively inhibits degradation of coated matter by sulfur oxidizing bacteria by blending a paint component containing a nickel phthalocyanine (derivative) powder, a tungstate and a resin. SOLUTION: Nickel phthalocyanine (derivative) powder (0.001-5 pts.wt.) with a particle diameter of 0.01-100 μm and 0.001-5 pts.wt. of a tungstate, based on 100 pts.wt. of a resin in a paint component, are blended in a weight ratio of the nickel phthalocyanine (derivative) powder to the tungstate of 1:(0.1-10) to a paint component containing a resin selected from epoxy resin-based solventless lining paints, vinyl ester resin-based solventless lining paints, liquid epoxy resin-containing paints, water-based acrylic resin emulsion-containing paints, water-based polyester resin emulsion-containing paints, water-based polyurethane resin-containing paints and the like to obtain a sulfur oxidizing bacteria growth inhibitor-containing paint. The paint is coated on a material to be coated in a thickness of 0.01-2.0 mm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a sulfur-oxidizing bacteria growth inhibitor which inhibits the growth of sulfur-oxidizing bacteria such as Thiobacillus thiooxydans and the like, and can prevent the deterioration of a coated material by such sulfur-oxidizing bacteria. Regarding paint.

[0002]

2. Description of the Related Art It is known that sulfur-oxidizing bacteria belonging to the genus Thiobacillus, which generally exist in soil and water and oxidize sulfur compounds and assimilate carbon dioxide, oxidize hydrogen sulfide to produce sulfuric acid. . Depending on the type, this bacterium exists not only in the water but also in the air and the surface of the structure adjacent to the water where the sulfur-oxidizing bacteria inhabit, and degrades various structures. As a method of preventing such deterioration of the structure,
Conventionally, various proposals have been made. Conventionally, as a technique using a growth inhibitor of sulfur-oxidizing bacteria, a method of including a specific metal or metal oxide insoluble in water such as nickel and soluble in sulfuric acid in a structure such as concrete (Japanese Unexamined Patent Publication No.
No. 149053) has been proposed and implemented. In this method, the specific metal completely prevents the sulfur oxidizing bacteria's sulfur oxidizing activity, respiratory activity and carbon dioxide fixing activity in the vicinity of neutrality, and can sufficiently prevent the deterioration of the cement structure by the sulfur oxidizing bacteria. Is the way. However, when such a metal is blended in the paint, the desired effect cannot be obtained. In addition to the above-mentioned nickel and the like, studies have been made on metals having an inhibitory activity against Thiobacillus genus sulfur-oxidizing bacteria. For example, molybdenum, ammonium molybdate, or a mixture of ammonium molybdate and tungsten is used in Thiobacillus novels (Thiobacillus novel).
lus), but it is known that tungsten alone inhibits growth (Journal of Bacterio
153, No. 2, (1983) William M. et al. “Sulfite
Oxidase Activity in Thiobacillusnovellus "p.941-94
Four). On the other hand, it is also known that molybdenum (Mo ⁴⁺ ), which is known to activate the growth of Thiobacillus novels, inhibits the growth of Thiobacillus thiooxidans (Thiobacillus thiooxidans). Chmical
Abstracts, Volume 95, Issue 1 (July 6, 1981) p127 (1081
a)). By the way, nickel phthalocyanine powder is an analog of copper phthalocyanine which is known to be incorporated into paint as an organic pigment.However, a coating film containing this nickel phthalocyanine powder widely inhibits the growth of sulfur-oxidizing bacteria. Is not known.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a paint containing a sulfur-oxidizing bacteria growth inhibitor, which can form a coating film capable of effectively inhibiting the deterioration of a substrate by sulfur-oxidizing bacteria. .

[0004]

According to the present invention, there is provided a method for growing a sulfur-oxidizing bacterium, comprising a nickel phthalocyanine powder and / or a nickel phthalocyanine derivative powder, a tungstate, and a paint component containing a resin. An inhibitor-containing coating is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The paint of the present invention is applied to a metal such as an iron plate or the like; concrete, mortar, resin molded product or the like to form a coating film, whereby the material to be coated is thiobacillus thiooxidans, thiobacillus novels, or the like. Effectively inhibits its degradation by sulfur-oxidizing bacteria. The paint of the present invention contains nickel phthalocyanine powder and / or nickel phthalocyanine derivative powder, a tungstate, and a paint component containing a resin as essential components. The contained nickel phthalocyanine powder and / or nickel phthalocyanine derivative powder and the tungstate act as active ingredients of the sulfur-oxidizing bacterial growth inhibitor. This growth inhibitor has little inhibitory activity against, for example, gram-negative bacteria Escherichia coli and gram-positive bacteria S. aureus, etc., and also kills sulfur-oxidizing bacteria such as thiobacillus thiooxydans. Shows little effect.

The nickel phthalocyanine powder is a powder of a compound in which a nickel atom is coordinated to a phthalocyanine skeleton having no substituent. This nickel phthalocyanine powder is water-insoluble and is substantially water-insoluble in acids.

The nickel phthalocyanine derivative powder is a powder of a compound having a substituent atom or a substituent other than a hydrogen atom on the benzene ring of a nickel phthalocyanine skeleton molecule, and is usually insoluble in water and almost free of acids. The compound does not dissolve. As a substituent atom or a substituent of the nickel phthalocyanine derivative, a halogen atom such as fluorine, chlorine, bromine, and iodine; a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, and a ter
t-butyl group, pentyl group, hexyl group, heptyl group,
Octyl, stearyl, trichloromethyl, cyclopropyl, 1,3-cyclohexadienyl, 2-
Substituted or unsubstituted alkyl groups such as cyclopenten-1-yl group and 2,4-cyclopentadiene-1-ylenyl group; methoxy group, ethoxy group, propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group Substituted or unsubstituted alkoxy groups such as pentyloxy group, hexyloxy group, stearyloxy group, and trifluoromethoxy group; methylthio group, ethylthio group, propylthio group, butylthio group, sec-butylthio group, te
substituted or unsubstituted thioalkoxy groups such as rt-butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group; nitro group, cyano group, carbonyl group, ester group, hydroxyl group, sulfonic acid group, vinyl group, methylamino Alkyl-substituted amino groups such as groups, dimethylamino groups, ethylamino groups, diethylamino groups, dipropylamino groups, dibutylamino groups; carbocyclic aromatic amino groups such as diphenylamino groups and ditolylamino groups;
Bis (acetooxymethyl) amino group, bis (acetooxyethyl) amino group, bis (acetooxypropyl)
Mono- or di-substituted amino groups such as amino group, bis (acetooxybutyl) amino group and dibenzylamino group; substituted or unsubstituted aryloxy groups such as phenoxy group, p-tert-butylphenoxy group and 3-fluorophenoxy group A substituted or unsubstituted arylthio group such as a phenylthio group and a 3-fluorophenylthio group; a phenyl group,
Biphenyl group, triphenyl group, tetraphenyl group, 3
-Nitrophenyl group, 4-methylthiophenyl group, 3,
5-dicyanophenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, o-cumenyl group, m-
Cumenyl, p-cumenyl, mesityl, pentalenyl, indenyl, naphthyl, azulenyl, heptalenyl, acenaphthylenyl, phenalenyl, fluorenyl, anthryl, anthraquinonyl, 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, rubicenyl group, colonenyl group, trinaphthenyl group, heptaphenyl group, heptaenyl group, pyranthenyl group Or an unsubstituted aromatic ring group such as a valenyl group.

[0008] The particle size of the nickel phthalocyanine powder and / or the nickel phthalocyanine derivative powder is not particularly limited as long as the particle size can be dispersed in the paint. Preferably,
The range of 0.01 to 100 μm is preferred. Since the nickel phthalocyanine powder and / or the nickel phthalocyanine derivative powder exhibit a growth inhibitory activity against sulfur oxidizing bacteria particularly in an environment near neutrality, the compounding ratio is 100 parts by weight of a resin in a coating component described later. Against
0.001 to 5 parts by weight is preferred.

As the tungstate, for example,
Examples include calcium tungstate (CaWO4) and sodium tungstate (Na2WO4, Na2WO9). Such a tungstate can be uniformly dispersed or dissolved in a coating material, and is acidic,
Under acidity of H4 or less, it shows growth inhibitory activity against sulfur oxidizing bacteria such as Thiobacillus thiooxydans.
The compounding ratio of the tungstate is preferably 0.001 to 5 parts by weight based on 100 parts by weight of the resin in the coating component described later.

In the paint of the present invention, the mixing ratio of the nickel phthalocyanine powder and / or the nickel phthalocyanine derivative powder and the tungstate is preferably 1: 0.1 to 10 by weight.

The paint component used in the paint of the present invention contains a usual paint resin. As such a paint component,
For example, epoxy resin-based solventless lining paint, vinyl ester resin-based solventless lining paint, liquid epoxy resin-containing paint, water-based acrylic resin emulsion-containing paint,
Examples include a water-based polyester resin emulsion-containing paint and a water-based polyurethane resin-containing paint, and commercially available products can also be used.

The above-mentioned paint components can contain components other than the resins usually used in paints. For example, various solvents, pigments, inorganic components, dispersants, surfactants, various additives and the like may be blended. These mixing ratios can be appropriately selected according to the type of the paint. In addition, other sulfur-oxidizing bacteria growth inhibitors can be blended as long as the purpose of the paint of the present invention is not impaired.

In order to prepare the coating material of the present invention, for example, the nickel phthalocyanine powder and / or the nickel phthalocyanine derivative powder and the tungstate are mixed with each other.
It can be obtained by uniformly mixing the above-mentioned coating components with a dispersion mixer such as a sand mill, an attritor, a ball mill or the like; a mixer having a shearing stress such as a three-roll, two-roll, homomixer, kneader or the like. The coating material of the present invention can be formed into a coating film by a method of applying it to a metal such as an iron plate; a coating material such as concrete, mortar, and a resin molded product and drying and curing the coating material in the same manner as a usual coating material.
The thickness of the coating film is not particularly limited, but is usually 0.01 to
2.0 mm.

[0014]

The paint of the present invention has nickel phthalocyanine powder and / or nickel phthalocyanine derivative powder and tungstate dispersed and dissolved in the paint components as active ingredients of the sulfur-oxidizing bacterial growth inhibitor. It is possible to form a coating film having a sulfur-oxidizing bacterium growth inhibitory action on the surface of the object to be coated on the object to be coated, and to effectively prevent the object to be coated from being deteriorated by the sulfur-oxidizing bacteria.

[0015]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

EXAMPLE 1 Epoxy resin-based solventless lining paint (Nippon CRM Co., Ltd.)
Made, brand name "NK Flake EP-CT base agent", resin amount 6
(4% by weight), 98.5 parts by weight, 1 part by weight of nickel phthalocyanine powder having an average particle size of 2 μm and 0.5 part by weight of calcium tungstate having an average particle size of 3 μm were mixed. The mixture was sufficiently dispersed and kneaded using a three-roll mill until the average particle size of the dispersed particles became 1 μm or less. Then
A dedicated curing agent having a trade name of “NK Flake EP-CT main agent” is mixed with the obtained kneaded material so that the amount of the main agent and the amount of the curing agent in the kneaded material are 4: 1 by weight, and the paint is obtained. Prepared. The obtained paint was applied to a 5 × 5 cm iron plate to form a coating film having a thickness of 0.5 mm. The iron plate having the obtained coating film was exposed to sewage having an average hydrogen sulfide concentration of 80 ppm where Thiobacillus thiooxydans grows for one week,
One week later, the pH of the coating film surface was measured using universal test paper (Advantech Toyo Co., Ltd.). Table 1 shows the results
Shown in

Comparative Example 1 Instead of nickel phthalocyanine powder, the average particle size was 20
A coating material was prepared in the same manner as in Example 1 except that a μm nickel powder was used and a tungsten oxide powder having an average particle size of 10 μm was used instead of calcium tungstate. In addition,
The average particle size of the dispersed particles at the time of dispersion kneading was limited to 15 μm. The obtained paint was applied to an iron plate in the same manner as in Example 1,
After forming the coating film, an exposure test was performed. Table 1 shows the results.

Example 2 Vinyl ester resin-based solventless lining paint (Nihon CR
M Co., Ltd., trade name "N242B Topcoat Topcoat", resin content 70% by weight) 97.0 parts by weight, 2.0 parts by weight of a nickel phthalocyanine powder having an average particle size of 2 µm and an average particle size of 3 µm
and 1.0 part by weight of calcium tungstate. The mixture was sufficiently dispersed and kneaded using a three-roll mill until the average particle size of the dispersed particles became 1 μm or less.
Next, a dedicated curing agent having a trade name of “N242B top coat main agent” was mixed with the obtained kneaded material so that the amount of the main agent and the amount of the curing agent in the kneaded material became 100: 3 by weight ratio, and the paint was obtained. Prepared. The obtained coating material was applied to an iron plate in the same manner as in Example 1 to form a coating film, and an exposure test was performed. Table 1 shows the results.

Comparative Example 2 Instead of nickel phthalocyanine powder, the average particle size was 20
A coating material was prepared in the same manner as in Example 2 except that a nickel powder of μm was used and a tungsten oxide powder having an average particle size of 10 μm was used instead of calcium tungstate. In addition,
The average particle size of the dispersed particles at the time of dispersion kneading was limited to 15 μm. The obtained paint was applied to an iron plate in the same manner as in Example 1,
After forming the coating film, an exposure test was performed. Table 1 shows the results.

Example 3 70.0 parts by weight of a liquid epoxy resin (trade name "Epicoat 819" manufactured by Yuka Shell Epoxy Co., Ltd.) was added to an average particle size of 2
20.0 parts by weight of a nickel phthalocyanine powder of 2 μm and 10.0 parts by weight of calcium tungstate were mixed.
The mixture was sufficiently dispersed and kneaded using a three-roll mill until the average particle size of the dispersed particles became 1 μm or less. The obtained kneaded material is used as an epoxy resin-based solventless lining paint.
(Nippon CRM Co., Ltd., product name "NK Flake EP-CT
Epoxy resin-based solvent-free lining paint: kneaded material in a weight ratio of 9: 1 to the main agent and the resin amount of 64% by weight), and then trade name "NK Flake EP-CT"
The exclusive curing agent of the "main agent" was mixed so that the amount of the main agent to be contained and the amount of the curing agent to be added were 4: 1 by weight to prepare a coating material. The obtained coating material was applied to an iron plate in the same manner as in Example 1 to form a coating film, and an exposure test was performed. Table 1 shows the results.

Comparative Example 3 Instead of nickel phthalocyanine powder, the average particle size was 20
A coating material was prepared in the same manner as in Example 3 except that a μm nickel powder was used and a tungsten oxide powder having an average particle size of 10 μm was used instead of calcium tungstate. In addition,
The average particle size of the dispersed particles at the time of dispersion kneading was limited to 15 μm. The obtained paint was applied to an iron plate in the same manner as in Example 1,
After forming the coating film, an exposure test was performed. Table 1 shows the results.

Example 4 30.0 parts by weight of a liquid epoxy resin (trade name "Epicoat 815" manufactured by Yuka Shell Epoxy Co., Ltd.) was mixed with a reactive epoxy resin diluent (Nagase Kasei Kogyo Co., Ltd., trade name " Denacol EX-127 ") 25.0 parts by weight, average particle size 2 μm
Was mixed with 30.0 parts by weight of nickel phthalocyanine powder and 15.0 parts by weight of calcium tungstate having an average particle size of 3 μm. The mixture was sufficiently dispersed and kneaded using a three-roll mill until the average particle size of the dispersed particles became 1 μm or less. The obtained kneaded material is mixed with an epoxy resin-based solvent-free lining paint (manufactured by Nippon CRM Co., Ltd., trade name "NK Flake EP-CT main agent", resin content 64% by weight) in a weight ratio of an epoxy resin-based solvent-free lining. Paint: 2 kneaded materials
The mixture is mixed so as to have a ratio of 9: 1. Then, a dedicated hardener having a trade name of “NK flake EP-CT main agent” is added so that the amount of the main agent contained and the amount of the hardener to be added become 4: 1 by weight. To prepare a paint. The obtained coating material was applied to an iron plate in the same manner as in Example 1 to form a coating film, and an exposure test was performed. Table 1 shows the results.

Comparative Example 4 Instead of nickel phthalocyanine powder, the average particle size was 20
A coating material was prepared in the same manner as in Example 4, except that a nickel powder of μm was used and a tungsten oxide powder having an average particle size of 10 μm was used instead of calcium tungstate. In addition,
The average particle size of the dispersed particles at the time of dispersion kneading was limited to 15 μm. The obtained paint was applied to an iron plate in the same manner as in Example 1,
After forming the coating film, an exposure test was performed. Table 1 shows the results.

Example 5 Dispersant (Naphthalenesulfonic acid condensate sodium salt) 1
0.0 parts by weight, 20.0 parts by weight of a nickel phthalocyanine powder having an average particle diameter of 2 μm, 10.0 parts by weight of calcium tungstate 3 μm in average particle diameter, and 60 parts by weight of water were mixed. The mixture was sufficiently dispersed and kneaded using a sand mill filled with glass beads having a diameter of 1 mm until the average particle size of the dispersed particles became 1 μm or less. The obtained kneaded material is mixed with an aqueous acrylic resin emulsion (Mitsubishi Rayon Co., Ltd.)
Product name "Dianal LX-433", resin amount 60
Weight%) 1000 parts by weight and an aqueous acrylic resin emulsion (manufactured by Mitsubishi Rayon Co., Ltd., trade name "Dianal LX
-100 ", resin amount 47% by weight) and 500 parts by weight to prepare a coating material. The obtained paint was applied to a 5 × 5 cm piece of concrete to form a coating film having a thickness of 0.03 mm. An exposure test was performed on the concrete piece having the obtained coating film in the same manner as in Example 1. Table 1 shows the results
Shown in

Comparative Example 5 Instead of nickel phthalocyanine powder, the average particle size was 20
A coating material was prepared in the same manner as in Example 5 except that a μm nickel powder was used and a tungsten oxide powder having an average particle size of 10 μm was used instead of calcium tungstate. In addition,
The average particle size of the dispersed particles at the time of dispersion kneading was limited to 15 μm. The obtained paint was applied to concrete pieces in the same manner as in Example 1 to form a coating film, and an exposure test was performed. Table 1 shows the results.

Example 6 Dispersant (Naphthalenesulfonic acid condensate sodium salt) 1
0.0 parts by weight, 20.0 parts by weight of nickel phthalocyanine powder having an average particle size of 2 μm, 10.0 parts by weight of water-soluble sodium tungstate, and 60 parts by weight of water were mixed. The mixture was sufficiently dispersed and kneaded using a sand mill filled with glass beads having a diameter of 1 mm until the particle diameter of the dispersed particles became 1 μm or less. The obtained kneaded material was mixed with a water-based acrylic resin Emas John (trade name “Dianal LX-434”, manufactured by Mitsubishi Rayon Co., Ltd., resin content 60% by weight) 1
000 parts by weight and a water-based acrylic resin Emas John (manufactured by Mitsubishi Rayon Co., Ltd., trade name "Dianal LX-10
0 ", resin amount 47% by weight) and mixed with 500 parts by weight to prepare a coating material. The obtained paint was applied to a 5 × 5 cm piece of concrete to form a coating film having a thickness of 0.04 mm. An exposure test was performed on the concrete piece having the obtained coating film in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 6 An average particle size of 20 instead of nickel phthalocyanine powder was used.
A coating material was prepared in the same manner as in Example 6, except that a μm nickel powder was used and a tungsten oxide powder having an average particle size of 10 μm was used instead of calcium tungstate. In addition,
The average particle size of the dispersed particles at the time of dispersion kneading was limited to 15 μm. The obtained paint was applied to concrete pieces in the same manner as in Example 1 to form a coating film, and an exposure test was performed. Table 1 shows the results.

Example 7 Dispersant (Naphthalenesulfonic acid condensate sodium salt) 1
0.0 parts by weight, 20.0 parts by weight of nickel phthalocyanine powder having an average particle diameter of 2 μm, 10.0 parts by weight of calcium tungstate having an average particle diameter of 3 μm, and 60 parts by weight of water were mixed. The mixture was sufficiently dispersed and kneaded using a sand mill filled with glass beads having a diameter of 1 mm until the average particle size of the dispersed particles became 1 μm or less. The obtained kneaded material is converted to an aqueous polyester resin emulsion (Toyobo Co., Ltd.)
Product name "Pyronal MD1980", resin amount 30
(Weight%) of 6000 parts by weight to prepare a paint. The obtained paint was applied to a 5 × 5 cm piece of concrete to form a coating film having a thickness of 0.02 mm. An exposure test was performed on the concrete piece having the obtained coating film in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 7 Instead of nickel phthalocyanine powder, the average particle size was 20
A coating material was prepared in the same manner as in Example 7 except that a μm nickel powder was used and a tungsten oxide powder having an average particle size of 10 μm was used instead of calcium tungstate. In addition,
The average particle size of the dispersed particles at the time of dispersion kneading was limited to 15 μm. The obtained paint was applied to concrete pieces in the same manner as in Example 1 to form a coating film, and an exposure test was performed. Table 1 shows the results.

[0030]

[Table 1]

From the results shown in Table 1, it is known that the coating film formed by the coating material of the embodiment in which nickel phthalocyanine powder and calcium tungstate are blended has nickel powder and nickel powder, which are known to have growth inhibitory activity against sulfur-oxidizing bacteria. It can be seen that the decrease in pH is significantly suppressed as compared with the coating film formed by the coating material of the comparative example containing the tungsten oxide powder. Therefore, it can be seen that, in the paint, the paint containing the nickel phthalocyanine powder and the tungstate of the present invention can effectively inhibit the growth of sulfur-oxidizing bacteria and prevent deterioration of the object to be coated.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasunori Kimura 2-3-13 Kyobashi, Chuo-ku, Tokyo Inside Toyo Ink Manufacturing Co., Ltd. (72) Inventor Yukiko Higo 2-3-1 Kyobashi, Chuo-ku, Tokyo No. Toyo Ink Manufacturing Co., Ltd. F-term (reference) 4J038 EA011 HA246 JC38 PC02 PC04 PC08

Claims (2)

[Claims] 1. A paint containing a sulfur-oxidizing bacterial growth inhibitor, comprising nickel phthalocyanine powder and / or nickel phthalocyanine derivative powder, a tungstate, and a paint component containing a resin. 2. The mixing ratio of the nickel phthalocyanine powder and / or the nickel phthalocyanine derivative powder is 0.001 to 5 parts by weight with respect to 100 parts by weight of the resin in the coating composition, and the mixing ratio of the tungstate is The sulfur-oxidizing bacterial growth inhibitor-containing paint according to claim 1, wherein the amount is 0.001 to 5 parts by weight based on 100 parts by weight of the resin in the paint component.