JPS63251483A - Alga-preventive and mildewproofing paint composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having resistances to algae and mildew with excellent persistence, and excellent stability and safety, by incorporating an alga-preventive and mildewproofing agent comprising a core substance comprising organic polymer beads and encapsulated with a specified metallic shell substance into a paint. CONSTITUTION:A core substance comprising the beads of an organic polymer such as PS, having an average particle diameter of 0.1-500mum and static build-up characteristics in terms of a volume resistivity of 10<9>OMEGA.cm or higher is encapsulated in a capsule, formed from a metallic shell substance having an average particle diameter of 0.01-50mum and comprising a transition metal element selected from Cu, Zn, Ag, Co, Ni, Mn, Fe, and Pt, or at least one compound selected from the oxides, complexes or salts thereof, by the heat impact method to give an alga-preventive and mildewproofing agent. This agent is then incorporated into a paint.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an anti-algae and anti-mold paint that is low in toxicity and has excellent long-term sustainability, and is mainly used in the construction field. [Prior Art] In general, anti-fungal paints, whether water-based or solvent-based, are prepared by mixing an anti-mold agent into a liquid paint, stirring it, applying it onto the object to be coated, forming a cured film, and then applying the cured coating. It prevents and suppresses the growth of mold on the membrane. Moreover, as for the above-mentioned antifungal agent, agrochemical-based organic synthetic chemicals are often used. On the other hand, it has been known for a long time that certain metals, such as Cu, Zn, Ag, and Fe, have antibacterial properties and have been used as bactericidal agents. Therefore, as a method for efficiently maintaining and using such metals, methods such as use by physicochemical adsorption on silica gel, zeolite, etc. are known. [Problem to be solved by the invention] In antifungal paints that use synthetic organic chemicals such as pesticides, these chemicals exhibit their antifungal effects by being eluted by water (or other media). Although it can be seen to be fast-acting against mold, it requires the addition of a large amount to obtain a long-term, sustained effect, which increases costs and also causes problems such as discoloration of the paint film and decreased water resistance. There are many things happening. Next, in methods in which specific metals are used by physicochemical adsorption onto silica gel, zeolite, etc., the carrier itself has high activity, and when applied to paints, the use is limited due to aggregation of paint binders, etc. It happens. In addition, elution due to metal falling off is observed, which poses a safety problem. Furthermore, there are problems such as discoloration of the coating film and a decrease in weather resistance. Furthermore, as a result of investigating microbial contamination in buildings, the present inventors found that in addition to the generally well-known contamination by mold (fungi), contamination by algae (green algae, etc.) is significant, especially on exterior walls. We found that this was a contributing factor. Most of the agricultural chemicals and organic synthetic drugs currently on the market are ineffective against these algae. [Means for Solving] Therefore, in order to provide an anti-algae and anti-mildew paint composition that is stable, safe and long-lasting and used in the present invention, the present inventors have overcome the above-mentioned conventional techniques. As a result of extensive research, it was discovered through various experiments that metal shell materials exhibit a wide range of resistance not only to mold but also to algae, leading to the completion of the present invention. That is, as an anti-algae and anti-mold agent in the paint, the metal elements are Cu,
,Zn, ,Ag, ,C01Ni, ,Mn, ,Fe. Compounds consisting of metals with antibacterial properties selected from transition metal elements such as PT, metal oxides, metal complex compounds, or metal salts (average particle size 0.01 to 50μ
m) using organic polymer beads (average particle size 0.1 to 500 μm) such as polystyrene or polymethyl methacrylate as a core material, by a heating shock method (for example, Nara Kikai Seisakusho: Hybridization System). An object of the present invention is to provide an anti-algae and anti-mold paint composition which is stable and safe and has long-term sustainability, which is characterized by using an encapsulated product. [Structure of the Invention] The encapsulation technology using the heating shock method utilized in the present invention is a technology that has recently attracted attention as a mechanochemical microencapsulation method, and is a technology that has attracted attention in recent years as a mechanochemical microencapsulation method. As a result, a very stable bond is formed, and since this bond is not based on a chemical reaction, the characteristics of the core material and coating material of the encapsulated material are not lost. In the present invention, the organic polymer beads used as the core substance of the encapsulated algae and fungicidal agent are beads having a spherical or nearly spherical continuous surface, and have an average particle diameter of 0.
Must be between 1 and 500 μrn. 500IIm
If the particle size is larger than 0.1 μm, the particle size cannot be maintained due to the grinding effect during the encapsulation process using the heating impact method.
In the following, sufficient encapsulation as a nuclear material is not achieved in the encapsulation process using the heating shock method. Further, the composition of the organic polymer beads is an organic polymer having a volume resistivity of 10 ohm-cm. This means that the present encapsulation method is mechanochemical encapsulation, and the frictional electrification between the core material and the shell material causes 1
It takes advantage of the fact that secondary electrostatic bonding occurs. For that reason,
The organic polymer heather serving as the core material must have a volume resistivity value of 10 ohm-cm or more or more. Further, unless the chargeability of the core material and the shell material have different signs, strong bonding cannot be obtained and sufficient encapsulation cannot be achieved. The organic polymer heat used in the present invention can be one having a resin composition that does not meet the above conditions, such as polyurethane resin,
Examples include polystyrene resin, polyvinyl acetate resin, polybutadiene resin, polyvinyl alcohol + A4 resin, polyethylene) L4 resin, polypropylene resin, polymethacrylate resin, polyamide resin, polyacrylate resin, cellulose plasti-7 resin, and the like. Next, the metal shell material is selected from metals or metal compounds having antibacterial properties, but transition metals Cu, Zn, Ag, C
It consists of one or more metals selected from 01N iXMn, Fe, Pt, metal oxides, metal complex compounds, or metal salts. In order to effectively act on the organic polymer heath, which is the core material, the average particle diameter of these metallic shell materials is set to 0.00000000000000000000000000000000000000000000000000000000000000000000,000,0000000000000000000,000,
It is defined in the range of 01 to 50 μm. Average particle size is 50
If the average particle size is 0.01 μm or more, the difference in average particle size with the nuclear material will be too small, making it unsuitable.If the average particle size is 0.01 μm or less, the particles will become extremely small, resulting in practical problems such as particle re-agglomeration. There is a point. The encapsulated algae-proofing and anti-caking agent used in the present invention efficiently and stably coats the organic polymer bead core with the metal shell material having antibacterial properties, so the amount of metal shell material having antibacterial properties used is The amount used is much smaller than in the past, and it is extremely safe as it does not fall off. Furthermore, since organic polymer beads are used as the core, the specific gravity of the encapsulated algae and fungicidal agent of the present invention is much smaller than the specific gravity of the metal shell material itself having antibacterial properties. As a result, the encapsulated algae and fungicide has excellent dispersibility and dispersion stability in the algae and fungicide paint composition, and is also effective when the paint is applied to the object to be coated to form a coating film. It is thought that it works. The coating composition of the present invention can be applied to various objects by the same coating method as general coating compositions, and the coating film formed has extremely excellent anti-algae and anti-mildew properties, and is more effective than conventional ones. It is a highly safe coating composition that has excellent durability, weather resistance and discoloration resistance of the coating film. Hereinafter, the present invention will be explained in detail according to Examples. [Example] (Example 1)

[Creation of encapsulated algae and fungicide]

Prepare 40 parts by weight of zinc oxide (ZnO) (average particle size 0.5 μm) as an antibacterial metal shell material and 100 parts by weight of polystyrene beads (average particle size 200 μm) as a core material, and mix these. Thereafter, encapsulation was performed by a heating shock method (for example, Nara Kikai Seisakusho: Hybridization System).

[Creation of anti-algae and anti-mold paint composition]

Next, a water-based paint was prepared using the encapsulated algae and fungicidal agent according to the formulation shown below. Acrylic emulsion (solid content 50% by weight) 32.0 parts by weight Titanium oxide (
rutile) 28.0 parts by weight calcium carbonate
15.0 parts by weight Thickener 5.0 parts by weight Additives 4.0 parts by weight Water
15.0 parts by weight Encapsulated algae and fungicide 1.0 parts by weight (total 100.
．． (0 parts by weight) The obtained paint was stable over a long period of time without separation or new buildup.

[Confirmation of mold resistance]

The above paint was subjected to a mold resistance test according to rJIs Z 2911 7, "Testing of Paints", and the growth of mold was observed. In order to promote the growth of mold, a spore suspension was sprayed every week. As shown in Table 1, it has excellent anti-fungal properties and durability.

[Confirmation of algae resistance]

Next rJls Z 2911 7. An anti-algae test was conducted using a suspension of chlorella (D algae) in place of the spore suspension in accordance with the "Paint Test", and the status of algae growth was observed. Regarding the anti-algae test, 1. A suspended solution of chlorella (green algae) was sprayed onto a coating film test piece attached to an agar medium for green algae shown below, and cultured under irradiation with a fluorescent lamp. In addition, for accelerated culture, a chlorella suspension was sprayed every week. As shown in Table 2, it has excellent anti-algae properties and long-lasting effects. Encapsulation was performed using Hybridization System (Manufacturer: Hybridization System).

[Creation of anti-algae and anti-mold paint composition]

Next, a water-based paint was prepared using the encapsulated algae and fungicidal agent according to the formulation shown below. Acrylic resin (solid content 50% market weight) 55.0 parts by weight Titanium oxide (
Rutile) 30.0 parts by weight additive
5.0 parts by weight Solvent (toluene) 9.0 parts by weight Encapsulated algae and fungicide 1.0 parts by weight (total
(100.0 parts by weight) The resulting coating material was stable over a long period of time without separation or aggregation.

[Confirmation of mold resistance]

The above paint was subjected to a mildew resistance test in the same manner as in Example 1. As shown in Table 1, it has excellent anti-fungal properties and durability. Agar medium for green algae KNO30, 25g Kl-h Po, 0. 175
gKzHPO+ 01075gMg
SO+ ・7 H□0 0.075gNaC10,
025g CaC1z ・2H200,01g FeSO+ ・7H200,02g Agar 15.0g Distilled water 1000ml (100O,0
) (Example 2)

[Creation of encapsulated algae and fungicide]

As an antibacterial metal shell material, copper (Cu) (average particle size 0.
Prepare 5 parts by weight of zinc oxide (ZnO) (average particle size 0.5 μm), 35 parts by weight of zinc oxide (ZnO) (average particle size 0.5 μm), and 100 parts by weight of polyurethane beads (average particle size 100 μm) as a core material, mix these, and carry out. Same as Example 1, heating 1h bombardment method (
For example, Nara Kikai [Confirmation of algae-proofing property] The above paint was subjected to an algae-proofing test in the same manner as in Example 1. As shown in Table 2, it has excellent anti-algae properties and long-lasting effects. (Comparative Example 1) In the water-based paint formulation shown in Example 1, 1.0 part by weight of the encapsulated algae and fungicide was added to a commercially available pesticide-based fungicide (isophthalo-based).
A substituted product was prepared and evaluated in the same manner as in Example 1. The results are shown in Table-1 and Table-2. (Comparative Example 2) The solvent-based paint formulation shown in Example 2 was prepared by replacing 1.0 part by weight of the encapsulated algae and mold prevention with 0.05 part by weight of copper powder and 0.30 part by weight of zinc oxide. Example 2
The evaluation was carried out in the same way. The results are shown in Table-1 and Table-2. (Comparative Example 3) A water-based paint formulation shown in Example 1 was prepared in which 1.0 part of the encapsulated algae- and anti-mold was replaced with water, and evaluated in the same manner as in Example 1. The results are shown in Table-1 and Table-2. (Comparative Example 4) A water-based paint formulation shown in Example 1 was prepared in which 1.0 part by weight of the encapsulated anti-algae and anti-mold was replaced with copper sulfate, but the paint was new and could not be made into a paint. Therefore, it was not possible to evaluate the anti-algae and anti-mold properties. Test result evaluation 3: No growth of mold or algae observed. 2: Growth of mold or algae is observed. l: Significant growth of mold or algae. Furthermore, regarding each paint of Examples 1 to 2 and Comparative Examples 1 to 3, "
A weather resistance test was conducted for 250 hours using a Sunshine Carbon Arc Weather Meter (Suga Test Instruments) in accordance with JTS K 5400 6.17 Accelerated Weather Resistance Test, and changes in the coating film were observed. The results are shown in Table-3. Here, ΔYI: Yellowing degree after 250 hours of irradiation with Sunshine Carbon Arc Weather Meter ΔY I = Y + −Y IYI: Yellowness in standard state Y■: Yellowing degree after 250 hours of irradiation with Sunshine Carbon Arc Weather Meter, that is, The larger ΔYl is, the more yellowing occurs, and the smaller the value, the better the yellowing resistance. From the results in Table 3, Example 1, Example 2 and Comparative Example 3
It can be seen that the yellowing of Comparative Example 1 and Comparative Example 2 is greater than that of Comparative Example 1 and Comparative Example 2. In addition, no abnormality of the coating film other than yellowing was observed in any of the test specimens. Table 3 Yellowing degree determined by accelerated weathering test [Effect of the invention] As is clear from the above examples, the algae- and anti-mold paint composition of the present invention is stable, safe and effective against both algae and algae. It is an extremely useful invention that has excellent resistance to all types of cancer and has excellent long-lasting effects. -And more-

Claims (4)

[Claims] (1) A paint composition characterized in that an algae-proofing and mold-proofing agent is used in the paint, in which organic polymer beads are used as a core material and are encapsulated with a metal shell material. is a metal selected from transition metal elements, a metal oxide, a metal complex compound, or one or more compounds consisting of a metal salt, and is stable, safe, and long-lasting. An anti-algae and anti-mold paint composition. (2) Volume resistivity value is 10^9 ohm-cm (5
0% RH (23°C) or higher, and the average particle size is 0.1
~500μm organic polymer beads as core material,
The anti-algal and anti-fungal paint composition according to claim 1, which uses an anti-algal and anti-fungal agent encapsulated with a metal shell material having an average particle size of 0.01 to 50 μm. (3) The metal shell substance is a transition metal element such as Cu or Zn.
, Ag, Co, Ni, Mn, Fe, and Pt, metal oxides, metal complex compounds, or metal salts. The anti-algae and anti-mold paint composition according to claim 1, characterized in that an anti-algae and anti-mold agent is used. (4) The first claim is characterized in that the organic polymer beads and the metal shell material are substances with different chargeability, and an algae and fungicide encapsulated using these is used.
The anti-algae and anti-mold paint composition described in .