JPH11293153A - Paint composition and coating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating composition that makes good use of the color intrinsic to an aggregate not coloring with pigment and causes no discoloration in the transparent resin part in the coating films, and shows excellent seaweedproofness, mildewproofness and durability. SOLUTION: In a clear coating that becomes clear, when its coating film is formed and dried, (A) 100 pts.wt. of a synthetic resin (for example, a poly-urethane resin or the like) are mixed with 0.3-5 pts.wt. of (B) a triazine, for example, 2-methylthio-4,6-bis (ethylamino)-s-triazine or the like) and (C) an imidazole, for example, thiabendazole or the like. The formulation ratio of the component A to the component B is, for example, in the range of 10/1-1/10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint having excellent anti-algal and antifungal properties, excellent durability and durability, and a coating method using this paint for buildings and structures.

[0002]

2. Description of the Related Art Conventionally, when a paint is applied to a surface of a building such as a building, a condominium, a detached house, a bridge, a retaining wall, or the like, with a color of aggregate, the resin portion in the paint is yellowed. No paint having excellent antialgal and antifungal properties was found.

A coating material for forming a transparent coating film having anti-algal and fungicidal properties is disclosed in JP-A-6-264008, which is used for glass, metal, plastic, and the like. It was not possible to form a certain film thickness.

[0004]

Among the architectural finishing coating materials, the color unique to the aggregate is utilized, and a paint that is not pigmented has excellent anti-algal and anti-mold properties and does not discolor the transparent resin portion in the coating film. To provide a durable paint.

[0005]

According to the present invention, by employing the following composition, it is possible to obtain a finished surface which is excellent in anti-algal and anti-algal properties or excellent in durability and durability. Claim 1
In the invention of the present invention, the clear coating composition that becomes transparent when dried and formed into a film contains 0.3 to 5 parts by weight of an anti-algal and fungicide containing a triazine compound and an imidazole compound with respect to 100 parts by weight of the synthetic resin component. The main point is.

According to the second aspect of the present invention, the base material is made of a skin-based coating composed of a synthetic resin and an aggregate arbitrarily selected from ceramic granules, pre-colored fine aggregate or natural fine aggregate. The gist of the invention is to overcoat a surface coated with a material with a clear paint containing a triazine compound and an imidazole compound as anti-algal and anti-fungal components.

Hereinafter, matters constituting the present invention will be described in detail. The paint of the present invention contains a synthetic resin component and an anti-algal and anti-fungal agent as main components. Further, the skin-based coating material according to claim 2 contains a synthetic resin component and a fine aggregate as main components.

The form of the synthetic resin component is not limited as long as it becomes transparent when dried and formed into a film. That is, a synthetic resin solution, a synthetic resin aqueous solution, and a synthetic resin emulsion can be used as long as they become transparent after film formation and do not cause problems in water resistance, weather resistance, durability, and the like.

As a kind of the synthetic resin, for example, there is a resin mainly composed of a vinyl resin, an acrylic resin, a polyurethane resin, an acryl-silicone resin, a fluororesin or the like. Resins are preferred.

It is most preferable to use a triazine-based compound and an imidazole-based compound in combination as an anti-algal and fungicide. Examples of the triazine-based compound include 2-methylthio-4,6-bis (ethylamino) -s -Triazine, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 2-methylthio-4-tetrabutyl-6-cyclopropylamino-s-
Triazine, hexahydro-1,3,5-triethyl-
There is s-triazine, and examples of imidazole-based compounds (including benzimidazole-based compounds) include thiabendazole (TBZ), 2- (carbomethoxyamino)-
There are benzimidazole, 2-methoxycarbonylaminobenzimidazole, 6-dichloro-1-phenoxycarbonyl-2-trifluoromethylbenzimidazole, and 4,5,6,7-tetrachloro-2-trifluoromethylbenzimidazole.

In the combined use of the triazine compound and the imidazole compound, the mixing ratio is
It is selected from the range of 10: 1 to 1:10, but the preferred range is 3: 1 to 1: 3. For example, if only a triazine compound is used, the durability of the fungicidal effect may be inconvenient. If only the imidazole compound is used, the durability of the alga protection effect may be inconvenient.

Preferred examples of the alga- and fungicide include organic urea compounds such as manganese ethylenebisdithiocarbamate, zinc dimethyldithiocarbamate, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, and 2-benzimidazolylcarbamic acid. There are methyl and 3-iodo-2-propargylbutylcarbamic acids, and thiazoline-based compounds include 1,2-benzisothiazoline (BIT), 2-methyl-4-isothiazolin-3-one, and 2-n-octyl-4. -Isothiazolin-3-one, 2- (4-thiocyanomethylthio) benzothiazole (TCMTB), sodium 2-mercaptobenzothiazole, 2-thiocyanomethylthiobenzothiazole, 2-mercaptobenzothiazole, 2- (thiocyano Chirusuruhoniru) is benzothiazole.

Other anti-algal and fungicide agents include benzyl bromoacetate, α-bromocinnamaldehyde (BCA), 2,4,5,6-tetrachloroisophthalonitrile and 4-chlorophenyl which are halogen compounds. −
3′-iodopropargyl formal, 2,3,3-triiodoallyl alcohol (TIAA), 1 [(diiodomethyl) sulfonyl] -4-methylbenzene,
Pentachlorophenol (P
CP), pentachlorophenyl laurate, o-phenylphenol (OPP), parachlorometaxylenol (PCMX), parachlorometacresol, and guanidine-based compounds dodecylguanidine hydrochloride, polyhexamethylene biguanidine hydrochloride, glucone Acid chlorhexidine, and pyridines such as sodium-2-pyridinethiol-1-oxide, bis (2-pyridylthio-1-oxide) zinc, and 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine There is an amide compound, dithio-2,2'-bis (benzylmethylamide), and inorganic salts such as silver nitrate and silver perchlorate;
There are silver acetate, copper nitrate, copper sulfate, copper chloride, copper perchlorate, copper acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc perchlorate, and zinc acetate.

Among these anti-algal and fungicide groups, when the organic urea-based compound or the thiazoline-based compound alone is used, the durability of the alga- and fungicide is not good, and a halogen-based compound or an inorganic salt is used. In this case, discoloration during the weather resistance test is apt to occur, which is not good. When the above triazine-based compound or imidazole-based compound also contains a halogen element, there is a possibility of discoloration in a weather resistance test.
According to the results obtained from the experiment, in addition to the combination of the triazine-based compound and the imidazole-based compound, it is possible to use a combination of an organic urea-based compound and a thiazoline-based compound. May be effective against fungi or spores. The amount of the anti-algae / anti-fungal agent may be selected from the range of 0.3 to 5 parts by weight based on 100 parts by weight of the solid content of the synthetic resin component after testing.

Fine aggregates, which are aggregates of skin-based coating materials, include crushed granules of white or chromatic ceramics, cold water sand or silica sand, aggregates colored with paint for glass beads, plastic beads or Its granules, granite,
Crushed natural stones such as serpentine, obsidian, and fluorite, canary,
Hakuo, cold water, cherry blossoms, light snow, Mino haze, serpentine and other marble granules, silica sand, natural fine gravel (kinka, oiso, cherry sand)
And arbitrarily selected from these fine aggregates for use.

The grain size of the fine aggregate is 0.05 to 5.0.
It is selected with an appropriate width from the range of mm. However, in the case of using fine aggregate having a particle size of only 0.05 mm or less, the painting workability or the finished pattern becomes monotonous, and fine aggregate having a particle size of 0.5 to 2.0 mm is used. It is better to include it. The amount of the fine aggregate is 400 to 200 parts by weight per 100 parts by weight of the solid content of the synthetic resin component.
It is better to select from a range of 0 parts by weight. When the amount is less than 400 parts by weight, the concealing power is insufficient, the design is poorly changed, and cracks are likely to occur. Sufficient performance cannot be obtained in terms of weather resistance.

In the coating composition of the present invention, in addition to the above-mentioned main components, the following components to be added to a conventional finish material for construction are added within a range not to impair the purpose of the present invention. Its components include surfactants such as antifoaming agents, dispersants and wetting agents, solvents such as film-forming aids and antifreezing agents, dyes for coloring, pigments for obtaining metallic luster or pearl luster, and viscosity. There are components used in ordinary paints, such as thickeners for viscosity adjustment.

In the application of the coating composition, a primer is used as an undercoat on an undercoat such as concrete, mortar, ceramic siding, metal siding, or the like. There is an example of applying the paint of the present invention. The coating amount of the paint of the present invention is selected from 10 to 300 g / m ^{2 in} terms of dry weight.

In order to impart anti-algal and anti-fungal properties to the skin-based coating material, which is the original object of the present invention, a skin-based coating material having no anti-algal and anti-fungal properties is coated in advance, It can be used as a top coat of a coating material, or can be used as a top coat of another multilayer finish coating material or a thick finish coating material.

The coating composition of the present invention can be used even in the case of retrofitting, and is also used for a base having an old coating film. The old paint film refers to a building or a structure in which the surface of a building is coated with a finishing coating material for building, a wood coating, a metal coating, or the like.

[0021]

EXAMPLES In Examples and Comparative Examples, paints were prepared according to the formulations shown in Table 1 below. One of them was subjected to a storage stability test, and the prepared paint was applied to a flexible board or a filter paper was prepared. It was painted on and subjected to various tests.

[0022]

[Table 1]

The numerical values in Table 1 indicate parts by weight. The compounding amount of the synthetic resin emulsion represents the weight in terms of solid content, and the description of the compounding water is omitted. The viscosity when mixed as a paint is 40-300 dP using a simple viscometer.
It was adjusted to fall within a · s (decipascal seconds). An acrylic ester-based synthetic resin is used for the synthetic resin emulsion a, and vinyl acetate is used for the synthetic resin emulsion b.
A synthetic resin of veova resin was used, a synthetic resin a was a vinyl acetate-acrylic synthetic resin, and a synthetic resin b was an acrylic-silicon synthetic resin. Algae prevention
A fungicide a is a triazine compound, and b is a benzimidazole compound. For c, a halogen compound was used, and for d, a phenol compound was used. A mixture of a polyhydric alcohol solvent and an ester solvent was used as a film-forming aid. Methylcellulose was used as the thickener.

In the storage stability test of the paint, JIS A6
909, and the viscosity and properties of the paint before and after the test when the paint in the same container was placed in a thermostat at 50 ° C. for 4 weeks. In the low-temperature stability test according to JIS A6909, a cycle of placing the paint in a container in a thermostat at -5 ° C for 18 hours and in a curing room at 20 ° C for 6 hours is repeated three times.

Hereinafter, various tests performed using a plate coated with the coating material having the above composition will be described. In the discoloration test, a discoloration test specified in JIS A6909 was performed. In the discoloration and discoloration test, exposure was performed for 48 hours using a UV carbon fade meter and a test method without using blue scale, and the sample was allowed to stand in a dark room for 24 hours. Then, comparison using a gray scale, and the presence or absence of cracks and peeling were confirmed.

In the algal control test, evaluation was performed by a test method based on a mold resistance test according to JIS A6909.
As a procedure, prepare a medium solution consisting of the following composition,
Heat and boil for 1 hour. Next, the mixture was poured into a sterilized petri dish and solidified. At the center of the medium, a 30 × 30 mm coated piece is placed so as to be cultured. 1 ml of the algae spore suspension is evenly spread on the coated piece and the medium. The dish is covered with a lid, and is placed under the conditions of 28 ° C., 100% RH, and illuminance of 1500 lux for one month. 0, 1, depending on algae development
The evaluation is performed based on the evaluation criteria of 6 levels of 2, 3, 4, and 5.

The evaluation standards are set by the Japan Paint Manufacturers Association in order to know the antifungal and antialgal effects of the sample coating film, and the degree of occurrence is indicated by a number as follows. 0. Not at all. 1. Very few occurrences are observed. 2. Occurrence is observed on 1 to 10% of the sample surface. 3. Occurrence is observed on 10 to 30% of the sample surface. 4. Occurrence is observed on 30 to 70% of the sample surface. 5. Occurrence is observed on 70% or more of the sample surface.

Medium Composition 1 Composition 1 Pure water 1000 ml Agar 10 g Potassium nitrate 1.21 g Magnesium sulfate 2.46 g Potassium diphosphate 1.23 g Ferric sulfate 0.05 g Sodium citrate 0.19 g

The algae spore suspension is obtained by dispersing algae for an algal test used in the paint industry in sterile distilled water, and is classified into Pleurococcus sp.
p. : Green single cell) and the genus Oscilato
ria sp. : Blue-green thread).

In the antifungal test, evaluation was performed according to the method described in the mold resistance test method specified in JIS Z2911.
The procedure was almost the same as when the algae control test was carried out, except that the composition of the medium was as shown in Composition 2 below, and the test suspension shown below was used as a mixed suspension of mold spores. The culture conditions were 28 ° C., 100% RH and dark room conditions, and the culture period was one week.

The test result is indicated by a mold resistance of 5
In place of the three-stage display, which is a method of displaying test results in JIS Z2911, the anti-mold,
Following the indication of the anti-algal effect, it was as follows. Note that the results of the Japan Paint Manufacturers Association are displayed in six stages, with smaller values indicating better results, but in this evaluation, larger values indicate better results. 5 No growth of hypha was observed on the medium or the surface of the test piece. 4 Very few hypha growth was observed on the medium surface. 3 Except for around the test piece on the surface of the culture medium, the growth of hypha was observed. No hyphal growth was observed on the surface of the test piece. 2 Growth of hypha is observed on the entire surface of the medium and a part of the periphery of the test piece. 1 Growth of hypha is observed over the surface of the medium and the entire surface of the test piece.

Composition 2 Pure water 1000 ml Glucose 40 g Peptone 10 g Cold water 25 g

The spore suspension of the mold is the first of the test molds.
Group, group 2 or group 4, aspergillus niger FERM S-2, penicillium
Funiculosum FERM S-6, Cladosporium
It is a mixture of five mold spores of Cladosporioides FERM S-8, Aureobasidium pullulans FERM S-9, and Gliocladium virens FERM S-10.

In the combined test of the alkali resistance test and the discoloration test, the alkali resistance test A specified in JIS A6909 was performed, and then the discoloration test specified in JIS A6909 was performed. The discoloration and fading test is the test described above. In the alkali resistance test, the side and the back of the coated plate were sealed with an epoxy resin, and the coated plate was immersed in a saturated aqueous solution of calcium hydroxide at 20 ° C. to 1/3 to 1/2 the coated surface. It was immersed for 24 hours. After immersion in alkaline water, the plate was washed with water, dried for one day, and then subjected to a discoloration test.

In the discoloration / discoloration test and the combined test of anti-algal and antifungal properties, the above-described discoloration and discoloration test was performed, and then the anti-algal test and the anti-mold test were performed. After the discoloration test, the test plate
For use in the following algal protection test and the like, the test pieces were cut into appropriate sizes and used.

The resistance to repeated action of warming and cooling
In the compound test of the antifungal property, a repetition test of a warm age specified in JIS A6909 was conducted, and then an algal test and an antifungal test were performed. In the repetition test, the test plate was kept at 20 ° C ±
After immersing in water at 2 ° C for 18 hours, cool in a thermostat at -20 ° C ± 3 ° C for 3 hours, and in a thermostat at 50 ° C ± 3 ° C for 3 hours.
A 24-hour cycle of heating for 10 hours is repeated 10 times.

Table 2 below shows the results of the various tests described above. In Table 2, in the storage stability of the paint, a circle indicates that there was no abnormality, and a cross indicates that gelation of the paint occurred. Further, in the discoloration / fading test, a mark “○” indicates that there was no occurrence of discoloration, cracking and peeling, and a mark “X” indicates that yellowing of the coating film occurred. In the combined test of the alkali resistance and the discoloration test, the mark ○ indicates that no abnormalities such as discoloration, cracking and peeling occurred, and ×
The mark indicates that yellowing of the coating film occurred. In the warm-age repeated test, the mark ○ indicates that no abnormalities such as blisters, cracks and peeling occurred, and the mark × indicates that blisters of the coating film occurred.

[0038]

[Table 2]

Next, the clear paints of Examples 1, 6 and Comparative Examples 1 and 3 of the present invention were applied to a plate undercoated with the following paint at a required amount of 300 g / m ^2. However, the coated plate overcoated with the clear paint is also included in the above-mentioned tests.
A combined test of alkali resistance and discoloration, a combined test of repetition of heating and cooling and anti-algae / anti-mold properties were performed.

The paint 1 used for the undercoating is a skin-based coating material for coloring the aggregate, and the fine aggregate a is added to the acrylic resin emulsion 100 parts by weight (in terms of solid content).
0 parts by weight, 340 parts by weight of fine aggregate b, 15 parts by weight of a film-forming aid, and 2.5 parts by weight of a thickener.
50 dPa · s (decipascal second). It should be noted that the fine aggregate a has no. 7 silica sand (0.39 mm from 0.09 mm is 95%).
% Or more), and fine aggregate b is made of colored aggregate No. 8 silica sand (0.1 mm from 0.04 mm is 95% or more), and fine aggregate c is used as fine aggregate b. No.5 silica sand (0.2
Aggregate colored 0.85 mm to 95% or more was used. The color tone was set to white in order to facilitate confirmation of yellowing of the resin component.

The paint 2 used for the undercoating is a lysine or lysine paint which forms a sand-wall-like finished surface. 230 parts by weight of titanium oxide is added to 100 parts by weight (in terms of solid content) of an acrylic synthetic resin emulsion. 310 parts by weight of calcium carbonate, 15 parts by weight of additives such as wetting or dispersing agent, defoamer, thickener, 275 parts by weight of water containing water in synthetic resin emulsion, and 930 parts by weight of cold water sand as aggregate Is blended.

The paint 3 used for the undercoat is a so-called metallic paint, which is an acrylic resin varnish 42.3.
Parts by weight, 6.2 parts by weight of aluminum paste, 0.6 parts by weight of additives such as viscosity modifier and anti-settling agent, ultraviolet absorber, aromatic hydrocarbon or alcohol, ester,
It contains 50.9 parts by weight of a solvent containing a ketone.

Table 3 below shows the test results of the coated plate having the clear coating. The composite test 1 in Table 3 is a composite test of alkali resistance and discoloration resistance, the composite test 4 is a test of hot and cold repetition and algae resistance test, and the composite test 5 is a test of hot and cold repetition. This indicates the test for antifungal properties. In the table, the results are indicated by the symbols ○ or numerical values in the same manner as in Table 2.

In the exposure test a, a board coated with the undercoat paint and the clear paint was placed on an exposure table on a building roof in Kakamigahara City, Gifu Prefecture, and the influence under the natural environment was examined. The exposure table was facing south at an exposure angle of 30 degrees, and the test specimen was placed at a position of 50 cm to 1 m from the rooftop floor. The exposure period was 2 years. Evaluation of the exposure test confirmed the presence or absence of cracks, peeling, blistering, whitening and yellowing.

In the exposure test b, using the same test specimen as the test a, a test specimen was set up in Takebuya in Kakamigahara city, Gifu prefecture. The test specimen was exposed vertically to the north so that the lower end of the test specimen was 10 cm above the ground. The exposure period was set to 2 years, and the evaluation was performed by confirming the same items as those in the test a and the occurrence and degree of occurrence of mold and algae.

[0046]

[Table 3]

In the results of the exposure test in Table 3,
In the evaluation 0, no abnormality was observed at all. In the evaluation a in the test a, the discoloration was observed although the fading was hardly conspicuous. In the evaluation 3, the yellowing of the test body was observed and conspicuous. . In the evaluation 1 in the test b, the yellowing of the test specimen was hardly noticeable but it was recognized. In the evaluation 3, the occurrence of mold or algae was observed and was noticeable. In the evaluation 4, the evaluation 4 was the occurrence of mold and algae. Is quite noticeable, indicating that it was quite noticeable. This criterion is
"Durability improvement technology of exterior finish" Supervised by Minister of Construction Technical Research Office, published March 25, 1987, based on the secondary diagnosis method on page 26 in Gihodo Shuppan Co., Ltd. is there.

[0048]

The coating composition of the present invention is excellent in stability, and can maintain the anti-algal and antifungal properties in the performance of the coated film even after the durability test.
Further, since yellowing does not occur in the coating film of the clear paint, an excellent appearance can be maintained for a long time.

Furthermore, even when the clear paint of the present invention is applied after coating with paint by coloring aggregates, paint for forming a pattern, or paint for imparting coloring or metallic or pearly luster, the anti-algal and anti-fungal properties are maintained. be able to. Thus, an effective coating film can be provided even for a newly constructed building or a renovated property where algae and fungi are likely to occur.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 7/12 C09D 7/12 Z // A01N 43/50 A01N 43/50 43/64 43/64

Claims (2)

[Claims] 1. A clear coating composition which becomes transparent when dried and formed into a film, containing a triazine compound and an imidazole compound per 100 parts by weight of a synthetic resin component.
A coating composition comprising 0.3 to 5 parts by weight of an antifungal agent. 2. The underground is coated with a skin-based coating material whose main component is an aggregate selected arbitrarily from synthetic resin and ceramic granules, pre-colored fine aggregate or natural fine aggregate. A coating method, characterized by overcoating a surface with a clear paint containing a triazine-based compound and an imidazole-based compound as anti-algal and fungicidal components.