JP2002114947A - Coating composition and method for preparing coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition from which a constant amount of a proliferation inhibitor against microbes is always eluted notwithstanding the constitution of the coating composition to exhibit excellence in persistency and sustained-release property even when it is applied on a part where adhesion of water and dew condensation are liable to occur, and to provide a method for preparing the coating composition. SOLUTION: The coating composition is prescribed so that it has a constitution permitting leaching by water of a proliferation inhibitor against microbes when a coating film is formed therefrom, and the proliferation inhibitor against microbes is microcapsulated. This permits to maintain the amount of the proliferation inhibitor against microbes eluted by water from the coating film substantially always constant notwithstanding the constitution of the coating composition, so that persistency of the effects and sustained-release property of the proliferation inhibitor against microbes in the coating composition can be stabilized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition containing a microbial growth inhibitor and a method for preparing the coating composition.

[0002]

2. Description of the Related Art Conventionally, in order to suppress the growth of harmful microorganisms, various coating compositions have been compounded with a microbial growth inhibitor exhibiting antibacterial, antifungal and antialgal properties. Widely used. If a coating film is formed with such a coating composition, the growth of harmful microorganisms can be suppressed, so that such microorganisms easily grow,
For example, it is widely used for painting outer walls of architectural buildings and the like, and inner walls and ceilings of bathrooms.

[0003]

However, moisture such as rainwater or water vapor adheres to the outer wall of an architectural building, the inner wall and ceiling of a bathroom, etc., and is easily condensed at all times. In many cases, the microbial growth inhibitor leaches out due to excessive moisture and the efficacy is not maintained.

[0004] Further, the degree of leaching of the microorganism growth inhibitor varies depending on the composition of the coating composition to be blended.
Irrespective of the composition of such a coating composition, it is strongly desired to always elute a certain amount of the microorganism growth inhibitor to develop a coating composition having good sustainability and sustained release.

[0005] The present invention has been made in view of such circumstances, and its object is to always apply to a portion where moisture tends to adhere and dew, regardless of the composition of the coating composition. It is an object of the present invention to provide a coating composition in which a certain amount of a microbial growth inhibitor is eluted and which has good sustainability and sustained release, and a method for preparing the coating composition.

[0006]

In order to achieve the above object, the present invention provides (1) a coating composition containing a microbial growth inhibitor, wherein the coating composition comprises A coating composition having a composition for leaching a microbial growth inhibitor with water, wherein the microbial growth inhibitor is microencapsulated; (2) a coating composition formed from the coating composition for water. (1) wherein the amount of the microbial growth inhibitor eluted from the coating film is prescribed so as to be substantially constant regardless of the composition of the coating composition. Paint composition,
(3) The amount of the microbial growth inhibitor eluted from the microcapsules in water is substantially equal to the amount of the microbial growth inhibitor eluted from the coating film formed by the coating composition in water. The coating composition according to the above (1) or (2), which is characterized in that it is applied to a site to which moisture easily adheres. (5) The coating composition according to any one of (1) to (4), wherein the coating composition is applied to a land-based building; A coating composition for eluting a substantially constant amount of the microbial growth inhibitor in water at all times from water, regardless of the composition of the coating composition, from a coating film formed by the coating composition containing a growth inhibitor. A method for preparing a product, comprising: It is intended to provide a method for preparing a coating composition, which comprises microencapsulating a growth inhibitor.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The coating composition of the present invention contains a microbial growth inhibitor as an active ingredient. Microbial growth inhibitors are compounds that exhibit antibacterial, antifungal and antialgal properties, and various industrial germicides such as bactericides, antibacterial agents, antifungal agents, preservatives, and antialgal agents. included.

As such a microorganism growth inhibitor, for example, thiophene compounds such as 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide, for example, 2-n-octyl-4-isothiazoline −
3-one, 2-ethyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-
Chloro-2-t-octyl-4-isothiazoline-3-
On, 5-chloro-2-ethyl-4-isothiazoline-
3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-
4-isothiazolin-3-one, 4,5-dichloro-2
-Cyclohexyl-4-isothiazolin-3-one, 2
Isothiazoline-based compounds such as -methyl-4,5-trimethylene-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, n-butyl-benzoisothiazolin-3-one, for example, 3-iodo- 2-
Propynyl-butyl-carbamate, diiodomethyl-
Organic iodine compounds such as p-toluylsulfone and p-chlorophenyl-3-iodopropargyl formal, for example, 4,5-dichloro-1,2-dithiol-
Dithiol compounds such as 3-one, for example, thiocarbamate compounds such as tetramethylthiuram disulfide, for example, nitrile compounds such as 2,4,5,6-tetrachloroisophthalonitrile, for example, N- (fluorodichloro Methylthio) -phthalimide, N- (fluorodichloromethylthio) -N, N'-dimethyl-N
Haloalkylthio compounds such as -phenyl-sulfamide, for example, 2,3,5,6-tetrachloro-4-
Pidyline-based compounds such as (methylsulfonyl) pyridine, for example, pyrithione-based compounds such as zinc pyrithione and sodium pyrithione, for example, benzothiazole-based compounds such as 2- (4-thiocyanomethylthio) benzothiazole, for example, 2-methylthio-4 Triazine compounds such as -t-butylamino-6-cyclopropylamino-s-triazine, for example, methyl-2-benzimidazole carbamate, 2- (4-thiazolyl)
-Imidazole compounds such as benzimidazole, for example, 1-[[2- (2,4-dichlorophenyl)-
1,3-dioxan-2-yl] methyl] -1H-1,
2,4-triazole, (±) -α [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl)
-1H-1,2,4-triazole- (1) -ethanol (tepconazole), (±) -1- [2- (2,4-
Triazole-based compounds such as dichlorophenyl) -4-propyl-1,3-dioxan-2-ylmethyl] -1H-1,2,4-triazole, for example, 3-benzo [b] thien-2-yl-5,6- Dihydro-1,4
Oxathiazine-based compounds such as 2-oxathiazine-4-oxide, for example, 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitropropane 1,3-
Alcohol compounds such as diols, for example, 3-
Urea compounds such as (3,4-dichlorophenyl) -1,1-dimethylurea, and amide compounds such as 2,2-dibromo-3-nitrilopropanamide.

These microbial growth inhibitors may be used alone or in combination of two or more. Preferably,
Thiophene-based compounds, isothiazoline-based compounds, and organic iodine-based compounds are exemplified.

[0010] In the coating composition of the present invention, such a microbial growth inhibitor is microencapsulated. Microencapsulation of microbial growth inhibitors can be achieved by chemical, physicochemical, physical and mechanical methods, etc.
A known method can be used.

In the chemical method, for example, an interfacial polymerization method, i
An n situ polymerization method, a cured film in liquid method, or the like is used. In the interfacial polymerization method, for example, a polybasic acid halide and a polyol are interfacially polymerized to form a polyester film, a polybasic acid halide and a polyamine are interfacially polymerized to form a polyamide film, and a polyisocyanate. A method of interfacially polymerizing a polyol to form a film made of polyurethane, and a method of interfacially polymerizing a polyisocyanate and a polyamine to form a film made of polyurea are used. In the in situ polymerization method, for example, a film made of polystyrene copolymer is formed by copolymerizing styrene and divinylbenzene, and a film made of polymethacrylate copolymer is formed by copolymerizing methyl methacrylate and n-butyl methacrylate. Is used. In the liquid curing method, for example, gelatin, polyvinyl alcohol, epoxy resin,
A method of curing sodium alginate or the like in a liquid is used.

Examples of the physicochemical method include a phase separation method from an aqueous solution such as a simple coacervation method, a complex coacervation method, a pH control method, and a non-solvent addition method, and a phase separation method from an organic solvent. The coacervation method is used. As the film-forming component, for example, gelatin, cellulose, gelatin-gum arabic and the like are used. Further, an interfacial sedimentation method using polystyrene or the like may be used.

The physical and mechanical methods include, for example, a spray drying method, an air suspension coating method, a vacuum evaporation coating method, an electrostatic coalescence method, a melting dispersion cooling method, and an inorganic wall encapsulation method. As the film-forming component, for example, gelatin, gum arabic, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, sodium alginate and the like are used.

In the present invention, of these methods,
Which method is to be used may be appropriately determined depending on the type, purpose and use of the microorganism growth inhibitor, and for example, an interfacial polymerization method is often used.

[0015] The coating composition of the present invention contains the microbial growth inhibitor thus microencapsulated. The compounding ratio of the microencapsulated microorganism growth inhibitor in the coating composition is 0.005 to 10% by weight, preferably 0.01%, as the microorganism growth inhibitor.
~ 5% by weight.

The coating composition of the present invention is not particularly limited as long as it has a composition capable of leaching the microbial growth inhibitor with water when a coating film is formed. , A resin, and if necessary, an extender pigment, a coloring pigment, and other additives. In the coating composition of the present invention, although not particularly limited, preferably, the elution rate of the microencapsulated microbial growth inhibitor immediately after preparation (cumulative elution amount after 1 day / total amount of microbial growth inhibitor × 100) Is preferably adjusted to 1 to 80%, more preferably 5 to 60%.

The resin is not limited at all. For example, acrylic resin, acrylic-styrene resin, styrene resin, vinyl chloride resin, vinyl acetate resin, vinyl acetate-acryl resin, vinyl acetal resin,
Fluorine resin, polyester resin, amino resin, epoxy resin, polyurethane resin, silicone resin, and the like are used. Among these, acrylic resins and vinyl acetate-acrylic resins are preferably used. These resins are preferably emulsion resins as described later, and as the emulsion resin, an acrylic emulsion resin is preferably used.

As the extender, for example, calcium carbonate, talc, clay, barium sulfate, silica, calcium carbonate and the like are used.

As the coloring pigment, for example, inorganic pigments such as titanium white, red iron oxide, chromium oxide, graphite and zinc oxide, and organic pigments such as Hansa Yellow, Lake Red, Phthalocyanine Blue and Shinkasha Red are used.

In the coating composition of the present invention,
As a ratio of the resin and the pigment (including the extender pigment and the color pigment), PVC (pigment volume concentration), that is, (pigment (volume) / (pigment (volume) + resin solid content (volume))) × 100, 20-80, furthermore 30-7
It is preferably 0. When the PVC is in the above range, the dissolution rate of the coating composition can be easily adjusted to the above-described preferable range.

As other additives, for example, various additives such as antioxidants, ultraviolet absorbers, preservatives, fungicides, algicides, antibacterials, and microbial growth inhibitors are used.
It is appropriately blended according to the purpose and use of the coating composition.

The coating composition of the present invention can be used as an aqueous coating composition. For use as an aqueous coating composition, it may be prepared by suspending or emulsifying each component including the microencapsulated microbial growth inhibitor in water at an appropriate ratio.

Of these, the coating composition of the present invention is preferably prepared as an aqueous coating composition, more specifically, an emulsion coating. Above all, if it is blended into a zero VOC paint, it is environmentally friendly and maintains the stability of the microbial growth inhibitor-containing microcapsules in good condition.
Sustained efficacy and sustained release can be further improved.

In order to prepare the coating composition of the present invention as a water-based coating composition, more specifically, as an emulsion coating, for example, after preparing a mill base containing an extender pigment and a coloring pigment, Each component as letdown is blended sequentially. For the preparation of the mill base, for example, water is added to the extender or the color pigment, and if necessary,
After adding known additives such as an antifreezing agent (such as ethylene glycol), a dispersant, a wetting agent, and an antifoaming agent, the mixture is mixed and stirred. And, in the mill base thus prepared, as a letdown, an emulsion resin and a microbial growth inhibitor-containing microcapsule, and if necessary,
Surfactant, film forming aid (high boiling point solvent, etc.), defoamer, p
After adding known additives such as an H adjuster and a thickener, stirring and mixing may be performed.

In particular, in the preparation of such an emulsion paint, as a composition for leaching the microbial growth inhibitor with water when a coating film is formed, PVC is preferably 20 to 8%.
0, preferably 30 to 70, and when the antifreezing agent is not blended, or when blended, is 20% by weight or less, preferably 0.001 to 15% by weight,
The film-forming aid is not blended, or when blended, is formulated so as to be 100 parts by weight or less, preferably 0.001 to 90 parts by weight, based on 100 parts by weight of the resin solids. Is preferred. With such a preparation, the microencapsulated microbial growth inhibitor can be easily eluted from the formed coating film in a substantially constant elution amount regardless of the composition.

In the coating composition of the present invention, the microbial growth inhibitor, which is an active ingredient, is microencapsulated. Irrespective of this, it can be substantially always constant. That is, if the composition of the coating composition in which the microorganism growth inhibitor is blended is different, the dissolution rate of the microorganism growth inhibitor is usually different due to the difference in the composition of the coating composition. By microencapsulating the growth inhibitor, not due to the composition of the coating composition, but only to the composition of the macrocapsules,
The elution amount of the microorganism growth inhibitor can be controlled, that is, the amount of the microorganism growth inhibitor eluted from the microcapsules with respect to water and the amount of the microorganism growth inhibitor eluted from the coating film with respect to water are substantially reduced. Since they can be matched, it is possible to stabilize the sustainability and sustained release of the efficacy of the microbial growth inhibitor in the coating composition without considering the composition of the coating composition. The range allowed as substantially constant is, for example, the elution rate of a specific sample (cumulative elution amount mg / total microorganism growth inhibitor m
g × 100 (%)), the elution rate of the reference sample ± 15 to 20 (%), and further ± 10 to 15%
Is preferably within the range.

[0027] Therefore, the coating composition of the present invention can be widely applied to industrial products having such a portion to which water easily adheres.
A certain amount of microbial growth inhibitor is always eluted even when applied to areas where moisture such as rainwater or water vapor tends to adhere to the surface, such as the outer walls of building buildings, floors of living rooms and bathrooms, inner walls, and ceilings, and where moisture is constantly condensed. As a result, good sustainability and sustained release can be exhibited.

The coating composition of the present invention is prepared, for example, as a clear coating without adding a coloring pigment or extender, and is used for paper and synthetic resin such as wallpaper, wood such as decorative board and synthetic board, and cement. It may be used as a coating composition for inorganic substrates such as concrete and concrete, and boards such as ceiling materials and wall materials.

[0029]

The present invention will be described more specifically with reference to the following examples and comparative examples.

Production Example 1 (Production of Microcapsule Water Dispersant (1)) 6 g of 2-n-octyl-4-isothiazolin-3-one (hereinafter referred to as OIT) and 3-iodo-2-propynyl-butyl- After dissolving 6 g of carbamate (hereinafter referred to as IPBC) in 8 g of Allosizer 202 (ethyl biphenyl, boiling point: 286 ° C., manufactured by Nippon Steel Chemical Co., Ltd.), the solution was heated to 60 ° C. 80
Takenate L-5060 (diphenylmethane-4,4'-diisocyanate (hereinafter MD)
Called I. ))-Caprolactone-modified polyisocyanate: amine equivalent 670, manufactured by Takeda Pharmaceutical Co., Ltd.)
0.72 g and millionate MR200S (polymethylene polyphenyl polyisocyanate: amine equivalent 132
An oil phase was prepared by mixing and dissolving 1.68 g of a trinuclear or higher polynuclear compound (50% by weight or more) and Nippon Polyurethane Industry Co., Ltd. In addition, this oil phase was Takenate L-5060: Millionate MR200S = 30: 7.
0 (weight ratio) and an amine equivalent of 175 were prepared.

On the other hand, in 70 g of water, 9 g of a 5 wt% aqueous solution of polyvinyl alcohol, 9 g of a 2 wt% aqueous solution of sodium carboxymethylcellulose, and 20 wt% of an aqueous solution of Demol NL (anionic surfactant, manufactured by Kao Corporation) 3
The aqueous phase was prepared by mixing g at room temperature.

Next, the oil phase was added to the aqueous phase. K. The mixture was dispersed by stirring with an auto homomixer for several minutes. The rotation speed of the mixer at this time was 5000 min.
^-1 . During the stirring, 10 g of an aqueous solution containing 0.60 g of ethylenediamine was dropped. Then
The obtained aqueous dispersion was reacted in a constant temperature bath at 75 ° C. for 3 hours with gentle stirring to obtain an aqueous dispersion containing microcapsules enclosing OIT and IPBC. To this is added a 0.1N aqueous hydrochloric acid solution to adjust the pH to 7.
Then, pure water was added to obtain a microcapsule aqueous dispersant (1) having an OIT-IPBC content of 5% by weight.

Production Example 2 (Production of Microcapsule Aqueous Dispersant (2)) Except that the amounts of the components shown below were changed, the same operation as in Production Example 1 was carried out to obtain an OIT-IPBC content of 5% by weight. A microcapsule aqueous dispersant (2) was obtained. In addition,
The oily phase was Takenate L-5060: Millionate M
R200S = 50: 50 (weight ratio), amine equivalent 222
Was prepared.

Takenate L-5060 1.25 g Millionate MR200S 1.25 g Ethylenediamine 0.50 g Production Example 3 (Production of Microcapsule Aqueous Dispersant (3)) In place of 0.72 g of Takenate L-5060 and 1.68 g of Millionate MR200S, Millionate M
OIT-R was prepared in the same manner as in Production Example 1, except that 5.10 g of R200S was used, and 0.90 g of ethylenediamine was used instead of 0.60 g of ethylenediamine.
A microcapsule aqueous dispersant (3) having an IPBC content of 5% by weight was obtained. In addition, this oil phase is Takenate L-50.
60: Millionate MR200S = 0: 100 (weight ratio), prepared as a composition with an amine equivalent of 132.

Production Example 4 (Production of Microcapsule Water Dispersant (4)) 3 g of OIT and 3 g of IPBC were added to Allosizer 202
After dissolving in 14 g, the solution was heated to 60 ° C.
To this, millionate M previously dissolved at 80 ° C.
An oil phase was prepared by mixing and dissolving 5.10 g of R200S. In addition, this oil phase is Takenate L
-5060: Millionate MR200S = 0: 100
(Weight ratio), and a composition having an amine equivalent of 132 was prepared.

On the other hand, 4.5 g of a 5 wt% aqueous solution of polyvinyl alcohol, 4.5 g of a 2 wt% aqueous solution of sodium carboxymethyl cellulose, and 2 g of a 20 wt% aqueous solution of Demol NL were mixed at room temperature with 30 g of water.
An aqueous phase was prepared.

Next, the oil phase was added to the aqueous phase. K. The mixture was dispersed by stirring with an auto homomixer for several minutes. The rotation speed of the mixer at this time was 5000 min.
^-1 . During the stirring, 10 g of an aqueous solution containing 0.90 g of ethylenediamine was dropped. Then
The obtained aqueous dispersion was reacted in a constant temperature bath at 75 ° C. for 3 hours with gentle stirring to obtain an aqueous dispersion containing microcapsules enclosing OIT and IPBC. To this is added a 0.1N aqueous hydrochloric acid solution to adjust the pH to 7.
Then, pure water was added to obtain a microcapsule aqueous dispersant (4) having an OIT-IPBC content of 5% by weight.

Production Example 5 (Production of Microcapsule Aqueous Dispersant (5)) Except that the amounts of the components shown below were changed, the same operation as in Production Example 1 was carried out to obtain an OIT-IPBC content of 5% by weight. A microcapsule aqueous dispersant (5) was obtained. In addition,
The oily phase was Takenate L-5060: Millionate M
R200S = 15: 85 (weight ratio), amine equivalent 151
Was prepared.

Takenate L-5060 0.35 g Millionate MR200S 1.98 g Ethylenediamine 0.67 g Production Example 6 (Production of microcapsule aqueous dispersant (6)) Except that the amount of each component shown below was changed, Production Example By the same operation as in 1, microcapsule aqueous dispersant (6) having an OIT-IPBC content of 5% by weight was obtained. In addition,
The oily phase was Takenate L-5060: Millionate M
R200S = 15: 85 (weight ratio), amine equivalent 151
Was prepared.

Takenate L-5060 0.70 g Millionate MR200S 3.96 g Ethylenediamine 1.34 g Production Example 7 (Production of microcapsule aqueous dispersant (7)) E-16C (solid hollow porous silica, manufactured by Suzuki Yushi Co., Ltd.)
200 g was impregnated with a solution of 20 g of OIT dissolved in a solvent of methyl ethyl ketone, and dried at 50 ° C. for 2 hours. The obtained powder was dispersed in 4000 g of a 2% by weight aqueous solution of gelatin 21 (gelatin, manufactured by Nitta Gelatin Co., Ltd.), and the dispersion was dried at 150 ° C. and 3000 using a spray drying apparatus.
Under the conditions of rotation / minute, gelatin coated microcapsules were obtained. It was further dispersed in water to obtain a microcapsule aqueous dispersant (7) having an OIT content of 5% by weight.

Comparative Production Example 1 (Production of Liquid Formulation (8)) 5 g of OIT and 5 g of IPBC were mixed with methyl carbitol 9
The solution (8) was obtained by dissolving in 0 g.

Preparation of Coating Compositions 1-4 In the ratio (% by weight) shown in Table 1, first, titanium white and extender were added to water, and further, ethylene glycol, a dispersant, a wetting agent, and an antifoaming agent were added. After that, a mill base was prepared by stirring and mixing. Next, the emulsion resin (A)-
(C), a film forming aid, an antifoaming agent, a preservative, a thickener (A) and (B), and water were sequentially added, followed by stirring and mixing to prepare coating compositions 1 to 4. In Table 1, together with the PVC of each of the coating compositions 1 to 4,
As for the film-forming auxiliary, the number of parts by weight based on 100 parts by weight of the resin solid content is added in parentheses. Details of each component are shown below.

[0043]

[Table 1] (Mill base) Titanium white: rutile type titanium oxide (trade name: TITANI
X JR-900, manufactured by Teica Co.) extender pigment: calcium carbonate (trade name: Whiten SB,
Dispersant: sodium polycarboxylate (trade name: Orotan 850, manufactured by Rohm and Haas) Wetting agent: alkyl ether sulfate (trade name: Triton CF-10, Union Carbide) Defoaming agent: Mixture of mineral oil and polyethylene glycol type nonionic surfactant (trade name: Nopco 8043-L, manufactured by San Nopco Co., Ltd.) (Letdown) Emulsion resin (A): Acrylic-styrene emulsion Resin (trade name: Ultrasol C-62, manufactured by Ganz Kasei Co., Ltd., solid content 55% by weight) Emulsion resin (B): vinyl acetate-acrylic emulsion resin (trade name: Boncoat 9124, Dainippon Ink Co., Ltd.) Emulsion resin (C): acrylic emulsion resin (solid content 55% by weight) Trade name: AE-318, manufactured by Nippon Synthetic Rubber Co., Ltd., solid content: 55% by weight) Film-forming auxiliary: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (trade name: CS -12, manufactured by Chisso Corporation) Antifoaming agent: mixture of mineral oil and polyethylene glycol type nonionic surfactant (product side: NOPCO 8034-L, manufactured by San Nopco) Preservative: nitrogen halide sulfur compound (product) Thick-off agent (A): 2% by weight aqueous solution of urethane-modified polyether-based thickener (trade name: RM-8W, manufactured by Rohm and Haas Co.) Agent (B): hydroxyethyl cellulose (trade name:
SP-600, manufactured by Daicel Corporation) 2% by weight aqueous solution Test Example 1 (Leachability of active ingredient from microcapsule aqueous dispersant and liquid) Microcapsule aqueous dispersants (1) to (7), liquid (8)
In 400 mL of ion exchange water
Added and shaken at 25 ° C. After the lapse of the number of days shown in Table 2, the elution amount of each active ingredient eluted in water was measured by liquid chromatography, and the elution rate (cumulative elution amount m
g / total amount of active ingredient mg × 100). Table 2 shows the results.

[0044]

[Table 2] Test Example 2 (Leachability of active ingredient from coating composition) As shown in Table 3, microcapsule aqueous dispersants (1) to (5), (7), and liquid agent (8) were added to coating composition 4. Each of Examples 1 to 6 was added so as to be 2.5% by weight.
And the coating composition of Comparative Example 1 was prepared. Thereafter, a coating film was prepared from these coating compositions. Each coating film was added to 100 mL of ion-exchanged water and stored at 25 ° C.
After the lapse of the number of days shown in (1), the elution amount of each active ingredient eluted in water was measured by liquid chromatography, and the elution rate (cumulative elution amount mg / total active ingredient amount mg × 100) was determined. Table 3 shows the results.

[0045]

[Table 3] From Table 3, the elution amount of the active ingredient eluted from the coating compositions of Examples 1 to 6 is based on the amount of the active ingredient from the microcapsule aqueous dispersants (1) to (5) and (7) shown in Test Example 1. It can be seen that the amount substantially coincides with the elution amount.

Test Example 3 (Leachability of Active Ingredient from Different Kinds of Coating Compositions) As shown in Table 4, each of the coating compositions 1 to 3 was provided with a microcapsule aqueous dispersant (6) or a liquid (8). To
The coating compositions of Examples 7 to 9 and Comparative Examples 2 to 4 were prepared by adding 2.5% by weight. Thereafter, a coating film was prepared from these coating compositions. Each coating film was added to 100 mL of ion-exchanged water, stored at 25 ° C. and stored.
After the lapse of the number of days shown in (1), the elution amount of each active ingredient eluted in water was measured by liquid chromatography, and the elution rate (cumulative elution amount mg / total active ingredient amount mg × 100) was determined. Table 4 shows the results.

[0047]

[Table 4] Table 4 shows that the coating compositions of Comparative Examples 2 to 4 differ in the amount of the active ingredient eluted depending on the composition of each coating composition. On the other hand, in the coating compositions of Examples 7 to 9, it can be seen that the elution amount of the active ingredient is substantially constant regardless of the composition of each coating composition. Further, it can be seen that the elution amounts of these active ingredients substantially correspond to the elution amounts of the active ingredients from the microcapsule aqueous dispersant (6) shown in Test Example 1.

Test Example 4 (Mold resistance) As shown in Table 5, each of the coating compositions 1 to 3 was coated with the aqueous dispersion (6) or the liquid (8) of the microcapsules.
Examples 10 to 1 were added so as to be 0.25% by weight.
2 and Comparative Examples 5 to 7 were prepared, and a fungicide test was carried out using each of them. The mold prevention test was performed according to the following procedure. The fungicide test was conducted by using the microcapsule aqueous dispersant (6) or liquid (8)
In addition to those containing 0.25% by weight, those not containing them were also tested as controls. The results are also shown in Table 5.

As the test mold liquid, Aspergillus niger, Penicillium citrinum (Pe
nicillium citrinum) and a mixture of Cladosporium cladosporioides.

No. (5) A coating composition having the same weight as that of the filter paper was uniformly applied on the filter paper and dried to prepare a coating sample. Using the obtained coating sample, the antifungal effect was evaluated by the following test method.

1) Test Method (1) A coated sample was cut into a size of 30 × 30 mm, and the test piece was air-dried for 24 hours.

(2) The test piece was immersed in 200 mL of water at 40 ° C. for 4 days or 6 days and air-dried for 24 hours.

(3) A glucose agar medium sterilized by an autoclave was poured into a petri dish having a diameter of 9 cm, and a test piece was stuck on the center of the solidified agar plate.

(4) The test fungus solution was sprayed on the test piece, cultured at 28 ° C., and the growth of the mold on the test piece was determined on the fourth week.

(5) Further, (3) and (4) were repeated.

(6) Four weeks after the cultivation (eight weeks in total), the degree of mold growth on the test piece was determined. The criteria are as follows. Table 5 shows the results.

2) Judgment criteria-: No mold growth was observed on the test piece.

±: Very little mold growth was observed on the test piece.

+: Mold growth was observed on 1/3 or less of the test piece.

++: Mold growth was observed on 2/3 or less of the test piece.

+++: More than 2/3 mold growth on the test piece was observed.

[0062]

[Table 5] From Table 5, in Comparative Examples 5 to 7, even if the immersion conditions are the same, if the composition of the coating composition is different, a variation occurs in the fungicidal effect. It can be seen that such variations are very small.

In Tables 1 to 5, "-" in the columns other than the fungicide resistance indicates the case where no compounding was performed or the case where no measurement was performed.

[0064]

As described above, according to the coating composition of the present invention, the microbial growth inhibitor, which is an active ingredient, is macro-encapsulated. The amount can be substantially always constant, regardless of the composition of the coating composition. That is,
If the composition of the coating composition is mixed with a microorganism growth inhibitor, usually due to the difference in the composition of the coating composition,
Although the dissolution rate of the microbial growth inhibitor is different, in the present invention, the microbial growth inhibitor is microencapsulated, not the composition of the coating composition, but only the macrocapsule composition. The elution amount can be controlled, that is, the elution amount of the microorganism growth inhibitor from the microcapsules with respect to water and the elution amount of the microorganism growth inhibitor from the coating film with respect to water can be substantially matched. Therefore, even if the composition of the coating composition is not taken into account, it is possible to stabilize the sustainability and sustained release of the efficacy of the microorganism growth inhibitor in the coating composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C09D 7/12 C09D 7/12 F term (Reference) 4H011 AA02 AA03 BA01 BA06 BB10 BB13 BC18 BC19 DA06 DA17 DH02 DH05 DH10 DH25 4J038 CC021 CD021 CD091 CE061 CF021 CG001 DA111 DB001 DD001 DG001 DL031 JA31 JB10 JB18 JB21 JB24 JB27 JB29 JB32 JB35 JB36 JC01 JC06 JC12 JC18 KA02 KA21 LA03 MA08 MA10 PC05 PC04 PC04 PC10

Claims (6)

[Claims] 1. A coating composition containing a microbial growth inhibitor, wherein the coating composition has a composition for leaching the microbial growth inhibitor with water when a coating film is formed; The coating composition, wherein the agent is microencapsulated. 2. The composition is formulated such that the amount of the microbial growth inhibitor eluted from a coating film formed by the coating composition with respect to water is substantially constant regardless of the composition of the coating composition. The coating composition according to claim 1, wherein 3. The elution amount of the microbial growth inhibitor from the microcapsules in water substantially coincides with the elution amount of the microbial growth inhibitor from a coating film formed by the coating composition on water. The coating composition according to claim 1, wherein the coating composition is formulated to perform coating. 4. The coating composition according to claim 1, wherein the coating composition is applied to a site to which moisture easily adheres. 5. The coating composition according to claim 1, wherein the coating composition is applied to a land structure. 6. A coating film formed from a coating composition containing a microbial growth inhibitor, wherein a substantially constant amount of the microbial growth inhibitor is always added to water regardless of the composition of the coating composition. A method for preparing a coating composition for elution, wherein the microbial growth inhibitor is microencapsulated.