JP2003226846A - Antibacterial, antifungal and antialgal coating compositions for aboveground structures - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an antibacterial, antifungal and algae-proofing coating material composition having antibacterial, antifungal and algae-proofing activities with excellent long-term preservability, and having excellent stability and safety by making a guanidine-based organic compound (guanidine polyhexamethylene phosphate) contained in a coating material. <P>SOLUTION: A urethane resin, a vinyl acetate resin, a vinyl chloride resin, a phthalic acid resin, an alkyd resin, an epoxy resin, a phenol resin, a melanin resin, an acryl resin, a fluororesin, and a resin mixed with these resins are used as the resin for the coating material composition. Preferably, the content of the guanidine-based organic compound is 0.1-20.0 wt.% based on the coating material composition, and the amount of a formulated plasticizer usable in combination therewith is ≤10.0 wt.% based on the resin weight. If necessary, a coloring raw material (e.g. a carbon-based coloring dye and a cyanine-based coloring dye) or an extender (e.g. talc, baryta and zinc white) can be formulated therewith. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

The present invention prevents the generation of bacteria, fungi, algae, etc. in the interior and exterior walls of buildings, above-ground structures such as buildings, and in kitchen facilities and kitchen equipment, refrigerators, kitchen appliances, and water-surrounding facilities such as bathrooms and bathtubs. The present invention relates to an antibacterial / antifungal / algae coating composition for preventing.

[0002]

2. Description of the Related Art Many kinds of bacteria, fungi and algae exist in the natural world. For example, molds such as Aspergillus, Penicillium, Ketomium, and Cladosporium, and algae such as Chlorococcum, Trentporia, and Nostock are observed on the outer wall of a building. The erosion of these microorganisms damages the landscape, deteriorates and deteriorates buildings, and lowers the functions of equipment. Therefore, preventive measures have been taken and early removal measures have been taken.

Bacteria, fungi, and algae that have conventionally been generated on the inner and outer walls of buildings, kitchen equipment, etc. are treated with cleaning agents such as acids and surfactants.
Alternatively, it has been removed by washing with a chlorine-based germicide such as sodium hypochlorite. In addition, by applying organic or inorganic antibacterial and antifungal agents to the material, or by using products and equipment mixed with antibacterial and antifungal agents during manufacturing,
It suppressed the development of fungi and algae.

[0004]

However, in the case of cleaning with a cleaning agent or a sterilizing agent, the duration of effectiveness is short, and it is necessary to perform cleaning again in the short term. In addition, antibacterial and antifungal algae mixed products and conventional antifungal agents supported on water-absorbent materials have limitations in place and range of use due to problems such as toxicity and stability. There were cases where it could not be used for non-water-absorbing materials such as cooking utensils, refrigerators, bathtubs, drains, etc.

For example, organotin compounds (eg tributyltin, triphenyltin), which are considered to be useful from the viewpoint of effectiveness.
Alternatively, other metal compounds (zinc pyrithione) and the like are highly toxic and are restricted in use. In recent years, the use and production of organotin compounds have been drastically reduced due to reports of environmental hormone problems (imposex phenomenon of snails). Further, the photocatalytic antibacterial agent (for example, titanium oxide) has a drawback that it cannot exhibit its performance in a situation where a sufficient amount of light cannot be obtained.

Furthermore, most of these inorganic and organic antifungal and antialgal paints are insoluble compounds, and therefore, in most cases, organic solvents must be used as media for their formulation. Organic solvents have recently been shunned because of their odor, flammability, and carcinogenicity.

Therefore, the present invention has a high degree of safety in place of the conventional antibacterial and antifungal / algae coating composition, prevents the generation of bacteria, molds and algae for a long period of time, and can be easily used for various purposes. It is an object of the present invention to provide a possible antibacterial, antifungal and antialgal coating composition.

[0008]

[Constitution of the invention]

According to the present invention, guanidine polyhexamethylene phosphate represented by the following chemical structural formula is used as an active ingredient in an antibacterial / antifungal / antialgae coating to obtain immediate effect on various microorganisms. , Has been shown to be persistent and meet the above objectives.

Structural formula: Guanidine polyhexamethylene phosphate

It has been found that, by changing the degree of polymerization of the above compounds, the compounds with m and n of 3 or more, that is, the compounds having a molecular weight of 1,000 or more, exhibit remarkable effects.

The antibacterial, antifungal and antialgal paint composition of the present invention can be mixed with the paint according to a known method. The content in the paint expected to be effective is 0.1 to 0.1 in terms of component ratio.
It is 20.0% by weight, preferably 1.0 to 15.0% by weight.

The paint resin used in the antibacterial and antifungal algae paint composition of the present invention is one of the substrates for forming a coating film, and the same ones used in conventional paints are also used. It is possible. For example, one or more kinds of synthetic resins such as urethane resin, vinyl acetate resin, vinyl chloride resin, phthalic acid resin, alkyd resin, epoxy resin, phenol resin, melanin resin, acrylic resin, and fluororesin, and natural resin can be used together. Any resin may be used. The compounding ratio of the resin and the antibacterial / antifungal / algae coating composition is not particularly limited.

Here, the plasticizer is based on the amount of resin for paint,
It is preferable to mix it at a ratio of 1/10 or less.

The antibacterial / antifungal / algae coating composition of the present invention may optionally contain a coloring material (eg, carbon dye, cyanine dye, etc.) or an extender pigment (eg, talc, barita, zinc flower, etc.). In addition, water or various solvents can be added to adjust the physical properties (viscosity, etc.) of the paint.

The type of solvent used is, for example,
Water, alcohols (methanol, ethanol, n-propyl alcohol, ethylene glycol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane) , Trichlorofluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone methylbutyl ketone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, etc.), nitriles (Acetonitrile, acrylonitrile, etc.), amines (ethylamine, dimethylamine, triethylamine, isobutylamine, etc.), aliphatic or aromatic hydrocarbons (n-
Hexane, cyclohexane, etc.) and the like. However, it is not particularly limited as long as it can dissolve or disperse the above coating resin or each component.

In formulating the antibacterial and antifungal and antialgal coating composition of the present invention, a surfactant is used for the purpose of emulsification, dispersion and the like. As such a surfactant, typical ones described below such as nonionic type, cationic type, anionic type and zwitterionic type (amino acid type, betaine type) can be used. However, the present invention is not limited to the example. The examples are listed below. As the nonionic type, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc., as the cation type, alkylamines, etc., as the anionic type, higher alcohol sulfate ester salt, Alkylbenzene sulfonate, higher alcohol phosphoric acid ester salt and the like, and zwitterionic type such as methyl laurylaminopropionate and stearyl dimethyl betaine can be used.

In addition to these, polyvinyl alcohol, carboxymethyl cellulose, gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate,
Various auxiliary agents such as titanium oxide can be used in combination.

The antibacterial and antifungal and antialgal coating composition of the present invention alone has a sufficient antibacterial and antifungal and antialgal spectrum, but if necessary, a general antibacterial and antifungal and antialgal agent, for example,
N '-(3,4dichlorophenyl) -N, N-dimethylurea, 3-iodo-2-propynylbutylcarbamate, diiodomethyl-p-tolylsulfone, 1,2-benzisothiazolin-3-one, 2-methylthio-4 −
Tert-Butylamino-6-cyclopropylamino-S-thiazine, 2- (4-thiocyanomethylthio) benzothiazole, 2,3,5,6-tetrachloro-4-
(Methylsulfonyl) pyridine, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4 -Isothiazolin-3-one, tetrachloroisophthalonitrile, N- (fluorodichloromethylthio) -phthalimide, N-dichlorofluoromethylthio-N ', N'-dimethyl-Np-tolylsulfamide, α [2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,
2,4-triazole-1-ethanol, N, N-dimethyl-N′-phenyl- (fluorodichloromethylthio) -sulfamide, or zinc (2-pyridylthio-1-oxide), kappa (2-pyridylthio-)
1-oxide), titanium oxide, zinc oxide, silver compounds and the like, and it is possible to use in combination with at least one compound. However, any compound that does not react with the components in the above paint and has high stability may be used, and the compound that can be compounded only in these exemplified antibacterial and antifungal and antialgal paint compositions is not limited.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the antibacterial / antifungal / algae coating composition of the present invention will be described below.

In this Example, guanidine polyhexamethylene phosphate (hereinafter referred to as PHMG) was treated as the main agent of the antibacterial / antifungal / algae preventive agent of the present invention, and in Comparative Examples, 2-Methylthio-4-tertiarybutylamino-, which has a proven record as an algae fungicide
6-cyclopropylamino-S-thiazine (hereinafter referred to as AT
), 4,5-dichloro-2-n-octyl-4-
Isothiazolin-3-one (hereinafter referred to as WT), 3-
Iodo-2-propynyl butylcarbamate (hereinafter referred to as I
B), diiodomethyl-p-tolyl sulfone (D
I) and kappa-2-pyridylthio-1-oxide (hereinafter referred to as CP) were used alone or in combination to prepare a coating material. In this test, an acrylic emulsion resin was used for all samples, and in the comparative examples, insoluble components were all dissolved with butyl acetate.

Regarding the blending ratio of the coating composition, Table 1 below shows a total of 4 kinds of Examples of the present invention, and Table 2 shows a total of 12 kinds of Comparative Comparative Examples. The unit in the table represents% by weight.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Test: Confirmation of Adhesion] As an overcoat for a building coating surface, an antibacterial / antifungal / algae coating composition having the composition shown in Tables 1 and 2 was applied and the adhesion was confirmed. First, 1m ×
A 1 m × 5 mm cedar timber test piece and a slate plate were coated with a colored paint and sufficiently dried, and then the antibacterial and antifungal algae paints of Examples and Comparative Examples were respectively applied at a thickness of 100 g / m ² , It was dried. A fragment of this test sample was measured with a Ducycle weather meter (Suga Test Instruments Co., Ltd.)
An accelerated weathering test was performed. As the test conditions, a step of repeating light irradiation at 60 ° C. (2.8 mW / m ² ) and a wet atmosphere at 40 ° C. (relative humidity 100%) every 6 hours was performed for a total of 500 hours. The adhesion of the sample after the test is shown in Table 3.

[0025]

[Table 3]

As shown in Table 3, the antibacterial / antifungal / algae coatings of Examples 01 to 04 do not affect the adhesion to the coated surface and maintain good adhesion in both the cedar and slate plate samples. We were able to. In addition, discoloration, fading,
No changes such as deterioration were observed. On the other hand, in the comparative example, deterioration of the coated surface was observed in the sample containing copperpyridione. From this, in the antibacterial and antifungal algae coating composition of the present invention used in Examples, in adhesion and weather resistance,
It was proved that it had no adverse effect.

[0027]

[Execution test: Outdoor fungicidal and algae proof performance confirmation] Field test A cedar board and a slate board (2m x 2m) coated with a thin finish coating on the outer wall face north to avoid direct sunlight. It was created at an angle of 80 degrees. On the surface thereof, 50% by weight of sand as an aggregate was mixed with 50% by weight of the antibacterial / antifungal / algae coating composition shown in Tables 1 and 2 above. The paints of Examples and Comparative Examples containing these aggregates were applied to an installed reinforced concrete plate at a thickness of 150 g / m ² . At the start of the test, diatoms, filamentous algae, green algae, whiskers,
A mixed spore suspension of algae such as spotted algae and cyanobacteria and molds such as Aspergillus, Penicillium, Cladosporium, Rhizopus, and Mucor is sprayed, and the fungi and algae on the painted surface are sprayed. The presence or absence of breeding was observed for half a year. The results are shown in Table 4-1 and Table 4-2. As for the symbols in the table, a minus sign is shown for a sample whose algae reproduction has not been confirmed, and a plus sign is shown for a confirmed sample. The number of plus signs was increased according to the degree of breeding.

[0028]

[Table 4-1]

[0029]

[Table 4-2]

From the results shown in Table 4 above, the algae and molds did not grow even after 6 months on the surfaces of the cedar and slate boards coated with the antibacterial / antifungal / algae coating according to the example, It was demonstrated that the antibacterial and antifungal and antialgal paints according to the examples have an excellent antialgal and antifungal effect. On the other hand, in some of the comparative examples, algae or mold growth was observed immediately after the initiation, and in most of the comparative examples, algae or fungi were observed to proliferate.

[0031]

[Test: Confirmation of antibacterial and antifungal performance] A 5 mm thick gypsum mortar was coated with the antibacterial and antifungal algae coating composition used in Tables 1 and 2 at a thickness of 50 g / m ² . After being sufficiently dried, a sample plate of 40 mm × 20 mm × 5 mm was prepared, and the sample plate was vertically pierced on a normal agar medium containing a single bacterium. After culturing in a 37 ° C. constant temperature bath for 3 days, the presence or absence of an inhibition zone was examined. The antibacterial performance of the antibacterial / antifungal / algae coating composition is shown in Table 5 by a minus sign for those in which the inhibition zone was formed and a plus sign in the case where it was not formed. On the other hand, in order to evaluate the antifungal performance against a single fungus, Waxman agar medium was covered with a sample plate, and 2 ml of a single fungal suspension containing an organic nutrient was sprayed on the sample plate. 27
After culturing for 2 weeks in a constant temperature bath at 90 ° C. and a relative humidity of 90%, the area of fungal generation on the surface of the sample plate was examined. In Table 6, when the mold generation area of the sample plate of each antibacterial and antifungal algae coating composition is 0%,
If the sign is −1% to less than 33%, the sign + is 33.
% To less than 66% are indicated by a ++ sign, and 66% or more are indicated by a ++ sign.

[0032]

[Table 5]

[0033]

[Table 6-1]

[0034]

[Table 6-2]

From Table 5, Table 6-1 and Table 6-2, the antibacterial and antifungal antialgae coating composition of the present invention shows that a small amount of various bacteria,
It has been demonstrated that it is possible to inhibit the growth of fungi and is more effective than existing antibacterial and antifungal and antialgal coating compositions.

[0036]

As can be seen from the above results, the antibacterial / antifungal / algae coating composition of the present invention can be used as an outer wall of a building without impairing the scenery, and has antibacterial / algal / antifungal properties. Have
It also proves that the paint has excellent adhesion and weather resistance.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Norio Someya             3-11, Kamishinjo, Higashiyodogawa-ku, Osaka-shi, Osaka             Daiwa Chemical Industry Co., Ltd. (72) Inventor Takayuki Tsurudome             3-11, Kamishinjo, Higashiyodogawa-ku, Osaka-shi, Osaka             Daiwa Chemical Industry Co., Ltd. (72) Inventor Kim Jin Man             Kanaya, Suizen-ku, Water Source City, Gyeonggi-do, Republic of Korea             Dong LG Village APT 306-             1303 (72) Inventor Cheki Sung             South Korea, Yeongdeungpo-gu, Seoul               710-7 F-term (reference) 4J038 BA221 CD031 CD091 CF021                       CF101 CG141 DA041 DA161                       DB001 DD121 DG001 HA216                       JB20 JB23 JB24 JB29 JC12                       JC14 JC16 JC18 JC38 KA02                       NA05 PB05

Claims (5)

[Claims] 1. An antibacterial / antifungal / algae coating composition for a ground structure, which comprises a guanidine compound (guanidine polyhexamethylenephosphate) as an active ingredient in the coating composition. 2. The base of claim 1 is not limited to a phosphate, but a guanidine whose base moiety is an inorganic salt such as hydrochloride, sulfate or nitrate, or an organic acid salt such as carboxylic acid. An antibacterial and antifungal antialgae coating composition for a ground structure containing a base compound as an active ingredient. 3. An antibacterial / antifungal / algae coating composition containing 0.1 to 20.0% by weight as an active ingredient of the antibacterial / antifungal / antialgae paint. 4. A urethane resin as a resin for the coating composition,
Antibacterial and anti-bacterial properties including synthetic resins such as vinyl acetate resin, vinyl chloride resin, phthalic acid resin, alkyd resin, epoxy resin, phenol resin, melanin resin, acrylic resin, fluororesin and natural resin Mold algae coating composition. 5. N '-(3,4) as an antibacterial and antifungal agent.
Dichlorophenyl) -N, N-dimethylurea, 3-iodo-2-propynylbutylcarbamate, diiodomethyl-p-tolylsulfone, 1,2-benzisothiazolin-3-one, 2-methylthio-4-tert-butylamino-6 -Cyclopropylamino-S-thiazine, 2- (4-thiocyanomethylthio) benzothiazole, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3- (3,4-dichlorophenyl)- 1,1-dimethylurea, 2-n-octyl-4
-Isothiazolin-3-one, 4,5-dichloro-2-
n-octyl-4-isothiazolin-3-one, tetrachloroisophthalonitrile, N- (fluorodichloromethylthio) -phthalimide, N-dichlorofluoromethylthio-N ', N'-dimethyl-Np-tolylsulfamide , Α [2- (4-chlorophenyl) ethyl] -α
-(1,1-Dimethylethyl) -1H-1,2,4-triazole-1-ethanol, N, N-dimethyl-N '
-Phenyl- (fluorodichloromethylthio) -sulfamide, or zinc-2-pyridylthio-1-oxide, kappa-2-pyridylthio-1-oxide,
The antibacterial, fungicidal and algae composition according to any one of claims 1 to 3, containing at least one or more organic compounds, inorganic compounds and organic-inorganic composites selected from metal compounds such as titanium oxide, zinc oxide and silver compounds. Coating composition.