JPH044268A - Anti-harmful organism coating composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition exhibiting anti-harmful organism activity against bacteria, fungi and algae with high safety by mixing titanium oxide with a specific amount of a metallic salt of an organic acid. CONSTITUTION:Titanium oxide is mixed with a metallic salt of an organic acid (e.g. salt of metal such as zinc, copper cobalt or tin of organic acid such as stearic acid, oleic acid or acetic acid) in an amount of 0.5-20mol% calculated as a metal to the titanium oxide to afford the aimed composition.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a coating composition having anti-pest properties.

[Technical background of the invention]

In general, mold and algae are likely to grow on the exterior walls of buildings and other structures, as well as on the ceilings and walls of bathrooms and kitchens, which can impair their beauty, reduce durability, and deteriorate the sanitary environment. or

In addition, products that use many materials such as metals and plastics, such as various industrial equipment, aircraft, automobiles, home appliances, and packaging materials, are susceptible to deterioration due to so-called microbial corrosion caused by mold and bacteria. . Damage caused by these types of pests is rapidly increasing over a wide range of areas due to the urbanization of social life and global warming, and there is an urgent need to solve the problem.

On the other hand, various methods have been proposed to prevent damage caused by the pests. For example, algal blooms,
To prevent the growth of algae, add benzothiazole-based or phenylurea-based algae-preventing agents to exterior and interior wall paints,
It is also known to use agents such as metal compounds such as organic mercury compounds and organic tin compounds, and organic chlorine or organic sulfur compounds as antibacterial and antifungal agents. However, the method using the above-mentioned algaecides does not have sufficient sustainability of the algae-preventing effect, and the anti-bacterial and anti-mold method using the above-mentioned metal compounds is highly toxic and poses a problem of environmental pollution. Regulations are being put in place for the use of organic chlorine and organic sulfur compounds.
There are many problems that require improvement, such as the tendency to discolor and stain objects to be treated.

By the way, the present inventors have been conducting various studies for some time on increasing the added value of titanium oxide powder as a functional material or making it into a composite material, and in the process, titanium oxide powder and the titanium oxide powder When blending a specific amount of an organic acid metal salt compound with respect to powder into a coating composition,
More effective against algae than when only organic acid metal salt compounds are combined.
Anti-pest effects such as anti-fungal and anti-bacterial properties are enhanced;
In addition, this effect is excellent in sustainability, and titanium oxide can be added to high value as a functional material without impairing its coloring properties or chemical stability. It breeds in clusters on the exterior walls of buildings in hot and humid areas such as subtropical regions.
An extremely effective anti-algae agent against contamination caused by Trentepohlia and A-nacystis, which seriously contaminate painted exterior walls or corrode them, impairing their durability. In addition, compared to the case where zinc or copper metals are supported on titanium oxide, color staining can be virtually avoided, and dispersibility in various media systems is better. The present invention was completed based on the knowledge that the material can be further expanded in applicability as a functional material.

[Disclosure of the invention]

That is, the present invention is an anti-pest coating composition characterized by containing titanium oxide and an organic acid metal salt compound in an amount of 0.5 to 20 mol % based on the metal based on the titanium oxide.

In the titanium oxide used in the present invention, Ti:0 is approximately 1
: Ordinary titanium dioxide (Tilt ・n
Hg01n = 6 or less), Ti: So-called low-order titanium oxide in which O is present in various proportions, titanium m whose main component is titanium dioxide; These include titanium oxide composite pigments and synthetic rutile pigments. These have an average particle size of usually 0.01 to 3 μm, preferably 0.02 to 1 μm.
, more preferably 0.03 to 0.4 μm. The above-mentioned titanium oxide can be produced by various methods, such as (1) titanium dioxide powder obtained by vapor phase oxidative decomposition of titanium tetrachloride, (2) titanium sulfate solution, titanium tetrachloride solution. Alternatively, one obtained by hydrolyzing an organic titanium compound solution in the presence of seeds for nucleation if necessary, (3) a titanium dioxide powder obtained by firing the above (2), (4 ) Various low-order titanium oxide powders obtained by heat reduction treatment of those obtained in (1), (2), and (3) above, and (5) those obtained in (2) above. Examples include titanium oxide composite pigments in which a color-forming metal component is added to and reacted with heat.

The anti-pest organic acid metal salt compounds used in the present invention include various metal salts of aliphatic, alicyclic, and aromatic organic acids, such as zinc, copper, cobalt, nickel, tin, and zirconium salts. , titanium, chromium, manganese,
Salts of iron, cadmium, lead, etc. can be mentioned, and specific compounds include, for example, stearic acid, oleic acid, acetic acid, naphthenic acid, rosin acid, benzoic acid, salicylic acid, etc., and zinc, copper, cobalt, nickel, zirconium ,
Examples include metal salts such as tin, which may be used alone or in combination of two or more types.The amount of the anti-pest organometallic compound is usually 0.000000000000000000000000000000000000000000000000000000000000000000,000. It is 5 to 20 mol%, preferably 1 to 10 mol%. If the blending amount is too low than the above range, the desired anti-pest effect will not be achieved, and if the blending amount is too high, it will not only be cost-effective but also have poor dispersibility in various resin media as described below. or the color toning properties of titanium oxide may be easily damaged.

The anti-pest coating composition of the present invention is useful as a surface finishing coating for textiles, paper, leather, etc., in addition to various paints, and can be prepared by various methods known per se. can.

For example, predetermined amounts of titanium oxide and organic acid metal salts are blended into aqueous or non-aqueous resin solutions or emulsion resins, and if necessary, commonly used coloring pigments, extender pigments, plasticizers, solvents, etc. are added. It can be prepared using various kneading and dispersing machines, such as ball mills, pebble mills, roll mills, speed run mills, etc. The amount of titanium oxide blended is 30 to 90% based on the weight of the pesticidal coating composition. Various resin solutions and emulsion resins can be used in the coating composition, including oil-based resins such as alkyd-based, acrylic-based, vinyl-based, epoxy-based, urethane-based, and polyester-based; Examples include emulsion resins such as acrylic emulsions and vinyl acetate emulsions, water-soluble alkyd resins, and water-soluble acrylic resins.

The anti-pest coating composition of the present invention is useful against various algae, bacteria, molds, etc., and the algae include terrestrial algae, aquatic algae, etc.
For example, Trendporia lagenifera (Tren
tepohlia lagenifera), Trentepohliaod
ora ta), Anarchistis montana (Anac
ystismontana), Anacystis thermal (^nacystisthersale), Chloro-coccum sp.
p, ), Scytonema hoffmannii
hoLwannii), Calotrix pariechina (
Calo-thrix parietina), Schizothrix calsicola (Schizothrix
calcicola), Chlorella vulgaris (Chl
orella vulgaris), Chlorella homosphaera (Chlorella homosphae)
ra), Scenedesmus quadricauda (Scened
es+wus quadricauda), Navicula viridis,
Anabaena flos-aquae (^nabaena fl
osaquae), Microcystis inserta (M
icroc-ystis 1ncerta), Oscillatoria tenuis (Oscillatoria tenis)
uis). Examples of the bacteria include various Durum-positive bacteria (eg, Bacillus subtilis HBacillus 5ubtilis).

Staphylococcus aureus; 5taphylo
coccusauretls% Streptococcus biogenes; 5t-reptococcus pyog
enes, etc.), Durham-negative bacteria (e.g. Nisierisia coli; Escherichia coli.

Salmonella Typhimurium; Sal+nonel
la typ-himurium, Talebsiella pneumonia;
ae, Serratia marcescens; 5erratia
+1larcescens, Proteus morganii; Proteus morganii, Proteus vulgaris; Pr-oteus vulgaris, Pseudomonas aeruginosa; Pseudomon
as aeruginosa, Vibrio parahaemolyt
icus), and fungi such as Trichophyton mentagrophytes
mentagraphites.

Trichophyton rubrumHTrichophyton
rubrua+.

Penicillium chrysogenum i Pen1cilliu
+m chry-sogenum, Penicillium citrinum; Pen1cil-iu+++ citr
inum, Talatosporium fulvum Hci-ado
sporius fulvum, Aspergillustus;
Aspergillus fus+igatus, Aspergillus niger; Aspergillus ni
ger, Talatosporium herbalum; Clados
Examples include porium herbarum.

The anti-pest coating composition formulated as described above can be applied as various anti-pest materials known per se. For example, it is extremely suitable for imparting anti-pest effects such as anti-algae, anti-mold and anti-bacterial properties to various industrial and household structures, facilities and equipment over a long period of time. The present invention will be further explained below by giving Examples and Comparative Examples.

[Example of the present invention]

Examples include 10 g of titanium oxide (CR-90, manufactured by Ishihara Sangyo), 3.75 g of zinc naphthenate (3.75 g of Znn content double weight%), and acrylic resin (8-180, manufactured by Dainippon Ink Chemical Co., Ltd.) 5.
6 g of toluene and 4 d of toluene were mixed and dispersed for 1 hour in a paint shaker using glass beads as a dispersion medium to obtain the desired paint composition (Sample A).

Example 2 Titanium dioxide (manufactured by Ishihara Sangyo, CR-90) 10 g, zinc acetate [Zn(CH3COO)z.2H20] 0.
4 g in 10 d of pure water along with a dispersant, antifoaming agent, and wetting agent.
and dispersed in a paint shaker for 1 hour. 5.6 g of emulsion resin (Boncoat 6290, manufactured by Dainippon Ink Chemical) was added thereto, and the mixture was further dispersed in a paint shaker for 1 hour to obtain the desired paint composition (Sample B).

Example 3 In Example 1, except that 3.75 g of cobalt naphthenate (co content 28% by weight) was used in place of zinc naphthenate, the same treatment as in Example 1 was performed to obtain the desired paint. A composition was obtained (Sample C).

Example 4 In Example 1, except that 7.5 g of nickel naphthenate (Ni content: 4% by weight) was used instead of zinc naphthenate, the same process as in Example 1 was performed to obtain the desired paint. A composition was obtained (Sample D).

Example 5 In Example 1, except that 7.5 g of zirconium naphthenate (Zr content: 4% by weight) was used instead of zinc naphthenate, the same treatment as in Example 1 was performed to obtain the desired paint. A composition was obtained (Sample E).

Example 6 A target coating composition was obtained in the same manner as in Example 1, except that 1 g of tin octylate was used in place of zinc naphthenate (Sample F).

Example 7 In Example 2, copper acetate (Cu(C
The desired coating composition was obtained by processing in the same manner as in the same example except that 0.4 g of HsCOO)z·HzO) was used (Sample G).

Comparative Example 1 A coating composition was obtained in the same manner as in Example 1 except that zinc naphthenate was not added (Sample H).

Comparative Example 2 In Example 1, the amount of zinc naphthenate added was 0.2 g.
A coating composition was obtained by processing in the same manner as in the same example (Sample ■), except that .

Test Example The coating compositions of Samples A to ① obtained in the above-mentioned Examples and Comparative Examples were applied onto a polyethylene terephthalate film using a doctor blade (100 μm thick) and dried to prepare coating film samples.

Ethanol (70% by weight) on agar gel (1.5% by weight)
) was placed on the paint film sample (3cm x 3cm), each of the test algae described below was transplanted onto the paint film, and cultured under fluorescent light irradiation in a constant temperature bath at 23°C. After 10 days, the transplanted algae were The degree of growth was determined by inoculating the test molds listed below on the paint film at 28°C.
The growth of the inoculated molds was determined after 1 month (+: growth inhibition, ++: withering, -: no growth inhibition effect). The results are shown in the table.

1. Test pest ■), Algae A: Trentepohlia lagenifera
B: Trentepohlia odorata C: Chlorella vulgaris 2), Mold D: Cladosporium herbarum [
[Effects of the Invention] The anti-pest coating composition obtained by the present invention is highly safe and effective against bacteria, mold, algae, etc. without impairing the original characteristics of titanium oxide particles and avoiding environmental pollution. It can exhibit anti-pest activity and has great industrial value as a treatment material to impart anti-pest properties in a wide range of fields of use and as a coloring material.

Claims (1)

[Claims] An anti-pest coating composition comprising titanium oxide and an organic acid metal salt compound in an amount of 0.5 to 20 mol % as metal based on the titanium oxide.