JPH03264501A - Antinoxious organic powder and antinoxious organic composition containing the same - Google Patents

Abstract

PURPOSE:To obtain antinoxious organic powder having excellent antinoxious organic activities such as algicidal, antifungal, antimicrobial activities, etc., imparted thereto with good persistence without impairing essential features of basic particles by supporting an organic acid metal salt compound on the particle surfaces of hydrous titanium oxide or titanium oxide. CONSTITUTION:An organic acid metal salt compound, preferably a metal salt such as zinc, copper, cobalt, nickel, tin or zirconium salt of an organic acid, preferably an alicyclic, aliphatic or aromatic organic acid such as naphthenic acid, acetic acid or benzoic acid, especially zinc naphthenate in an amount of normally 0.01-10%, preferably 0.1-5% expressed in terms of metal based on the weight of the basic particles is supported on the particle surfaces of hydrous titanium oxide or titanium oxide to afford antinoxious organic powder utilizable within a wide range of fields as a treating material for imparting antinoxious organic properties or coloring material, since the aforementioned excellent antinoxious organic activity can be exhibited without impairing features of basic particles such as coloring characteristics, chemical stability, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hydrated titanium oxide or titanium oxide powder having anti-pest properties and an anti-pest composition containing the same.

[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. There may be none.

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

On the other hand, various methods have been proposed to prevent damage caused by harmful organisms, such as algae growth,
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 organic mercury compounds, metal compounds such as organic tin compounds, and organic chlorine or organic sulfur compounds as antibacterial agents. However, the method using the above-mentioned algae-proofing agent does not have sufficient sustainability of the algae-preventing effect, and the method of preventing fatty bacteria and mold using the above-mentioned metal compound is highly toxic and pollutes the environment. This has become a problem and regulations are being put in place for its use.Furthermore, methods that use organic chlorine and organic sulfur compounds have many problems that require improvement, such as discoloration and staining of the object to be treated. .

By the way, the present inventors have been researching the use of hydrous titanium oxide or titanium oxide powder as a functional clay material for some time.
We have been proceeding with various horizontal divisions, such as single-value addition or composite materialization, and in the process, we focused on the application of the anti-pest powder as base particles, and we have further advanced the horizontal division. As a result, these titanium oxide-based or hydrous titanium oxide-based powders maintain excellent anti-pest effects such as algae-proofing, mold-proofing, and bactericidal-proofing by supporting organic acid metal compounds on their particle surfaces. In addition, it is possible to add high value as a functional composite material without impairing the coloring properties or chemical stability of the base particles. , Tren tepob, which grows in large numbers on the exterior walls of buildings in humid areas, conspicuously contaminates painted exterior walls, or even corrodes them, making their durability questionable.There is an urgent need to solve this problem. It has extremely excellent anti-algae properties against contamination by I ia ) and Anacystis , and substantially avoids coloring and contamination compared to cases where metals such as zinc and copper are supported as anti-algae ingredients. The present invention has been completed based on the findings that it can be used as an amulet and has better dispersibility in various media systems, and that its applicability as an a-functional amulet can be further expanded. .

=4= [Disclosure of the Invention] That is, the present invention provides: (1) An anti-pest powder characterized in that an organic acid metal salt compound is supported on the surface of hydrous titanium oxide or titanium oxide particles.

(2) The anti-pest powder according to claim (1), wherein the metal component of the organic acid metal salt compound is zinc, copper, cobalt, nickel, tin, or zirconium.

(3) The anti-pest powder according to claim (1), wherein the organic acid metal salt compound is a metal salt compound of an alicyclic organic acid.

(4) The anti-pest powder according to claim (1), wherein the organic acid metal salt compound is an aliphatic organic acid metal salt compound.

(5) The anti-pest powder according to claim (1), wherein the organic acid metal salt compound is an aromatic organic acid metal salt compound.

(6) The anti-pest powder according to claim (3), wherein the alicyclic organic acid component is naphthenic acid.

(7) The anti-pest powder according to claim (4), wherein the aliphatic organic acid component is acetic acid.

(8) The anti-pest powder according to claim (5), wherein the aromatic organic acid component is benzoic acid.

(9) The anti-pest effect according to claim (3), wherein the organic acid metal salt compound is zinc naphthenate.

(10) An anti-pest paint composition comprising the anti-pest powder according to claim (1).

(11) Thermosetting resin or thermoplastic resin in Claim No. (
An anti-pest resin composition comprising the anti-pest powder according to claim 1), and (12) an anti-pest resin composition comprising the anti-pest powder according to claim 1 in rubber. Anti-pest rubber M characterized by compounding and preventing
Regarding the i precepts.

In the present invention, the hydrated titanium oxide or titanium oxide (hereinafter referred to as base particles) supporting the anti-pest organic acid metal salt compound includes hydrated titanium oxide expressed as so-called TiO□・n1120, as well as various hydrated dioxides. What is called titanium, ordinary titanium dioxide with a Ti:O ratio of about 1:2, so-called lower titanium oxides with various Ti:O ratios, and titanium whose main component is titanium dioxide. In addition to nickel-antimony pigments and titanium-chromium-antimony pigments, they include various titanium oxide composite pigments and base rutile pigments. These have an average particle size of usually 0.01 to 3 μm, preferably 0.01 to 3 μm. (12~1
μm1 More preferably, it is 0.03 to 0.4 μm.

The base particles 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, or Hydrous titanium dioxide obtained by hydrolyzing an organic titanium compound solution in the presence of seeds for nucleation if necessary, (3) titanium dioxide powder obtained by subjecting hydrous titanium dioxide to the bottom of a mine, (4) (1), (2) above
, various lower titanium oxide powders obtained by heating and reducing the hydrous titanium dioxide precipitate and titanium dioxide powder obtained in (3), and (5) hydrous titanium oxide obtained in (2) above. Examples include titanium oxide composite pigments obtained by adding a color-forming metal acid to a precipitate and causing a heating reaction.

In the present invention, the anti-pest organic acid metal salt compound supported on the base particles includes various metal salts of aliphatic, alicyclic and aromatic organic acids, such as zinc, copper,
Examples include salts of cobalt, nickel, tin, zirconium, titanium, chromium, manganese, iron, cadmium, lead, etc. Specific compounds include stearic acid, oleic acid, acetic acid, naphthenic acid, rosin acid, benzoic acid, etc. Examples include metal salts of zinc, copper, cobalt, nickel, zirconium, tin, etc., such as acid, salicylic acid, etc.
It may be carried alone or in combination. The amount of the anti-pest organometallic compound supported is:
Usually 0.01 as a metal based on the weight of the base particle.
-10%, preferably 0.1-5%. If the supported amount is too small than the above range, the desired anti-pest effect will not be achieved, and if the supported amount is too large than the above range, it will not only be cost-effective but also have poor dispersibility in the anti-pest imparting treatment medium. and color toning properties are likely to be impaired.

In the present invention, the supporting treatment of the anti-pest organic acid metal salt compound on the base particles can be carried out by various methods, such as (1) carrying the organic acid metal salt compound in a solvent or an aqueous medium; (2) A method in which the hydrous titanium oxide or titanium oxide of the base particles is made cloudy with stirring in a solution dissolved in M, and then evaporated to dryness or filtered and then dried. (3) A method in which an organic acid metal salt compound solution in an organic solvent is added to the suspension under stirring, followed by evaporation to dryness or filtering and then drying. This can be carried out by adsorbing and adhering to the substrate particles by a method such as spraying onto the substrate particles and then drying.

The anti-pest powder of the present invention is useful against various algae, bacteria, molds, etc. Examples of the algae include terrestrial algae and aquatic algae. Lagenifera (TrenLep)
ohlia Iagenifera), Trentepohlia odoreta (Trentepohlia odo)
(rata) Abcystis monkna
tis montana), Anacystis tl+ermale, Chlorococcum sp.
, ), Scytonema hoffmannii
ofmannii), Kawa1-rhythx varietina (
Calothrix parietina), Schizothrix ca
lcicola), Chlorella vulgaris (Chlo
Rella vulgaris), Chlorella bomosphaera
), Scenedesmus quadricauda
smus quadricauda), Navicula viridis, Anabaena flo
s-aquae), Microcystis inserta (formerly crocystisjncerLa), OscillaLoria tenuis (OscillaLoria tenuis)
). In addition, examples of the bacteria include various Durum-positive bacteria (such as Bacillus subtilis;
118th c 1us 5ubtilis.

Staphylococcus aureus; 5tapbylo
coccusaureus, Suj leptococcus biogenes.

5treptococcus pyogenes, etc.)
, Durham-negative bacteria (e.g. N. coli; 1E
scl+erichia coli.

Salmonella typhimurium; Salmonell
atyphimurium, Klebsiella pneumoniae
, Serratia marsetuscens i 5erratia m
arcescens, Proteus morgani; Pr
oteus morganii, Proteus vulgaris; Proteus vulgaris, Pseudomonas aeruginosa;
Vibrio parahaemolyticus; Vibrio parahaemolyticus
), and fungi such as Trichophyton mentagrophytes i, Tricbophyton me
ntagraphytes, l-lycophyton
Rubrum; Trichopyhton rubrum
, Penicillium chrysogenum: Penicill
Chrysogenum, Penicillium citrinu
m, Talatosborium fulvum; C1adospor
ium fulvum, AsperHillus 11
fumigatus.

Aspergillus cladosborius L herbarum; Cladospo
Candida albicans, Candida albicans, and the like.

The anti-pest powder loaded as described above is
It can be applied as various anti-pest materials known per se. For example, it can be added to various aqueous or non-aqueous paint compositions, as well as resin and rubber moldings, and the resulting algae-proofing material can be used in various industrial applications. It is extremely suitable for providing long-term anti-pest effects such as anti-algae, anti-mold and anti-bacterial properties to commercial and household structures, facilities and equipment. The present invention will be further explained below by giving Examples and Comparative Examples.

[Example of the present invention]

Example 1 Zinc naphthenate (zinc content = 8% by weight) 12.5
g was dissolved in toluene 2 (10 mn), and 50 g of diacid = titanium 12 oxide (manufactured by Ishiwa Sangyo: CR-90) was added to this solution to disperse and suspend it, and the mixture was stirred at room temperature for 1 hour to carry out the support treatment. did.

Thereafter, it was filtered, dried and ground to obtain the desired anti-pest powder (Sample A).

Example 2 In Example 1, zinc acetate (Zn(CIzCOO)z·211zo) 3.4 was used instead of the zinc naphthenate solution.
The desired anti-pest powder was obtained by treating in the same manner as in the same example, except that 10 g was dissolved in water 2 (10 ml) and this solution was used for supporting treatment (sample B).

Example 3 In Example 2, zinc salicylate (
Zn(C6114(Oll)Coo)z・311zO
) 6 g was dissolved in water 2 (10 ml) and treated in the same manner as in the same example, except that this solution was used to support the target anti-pest powder (Sample C). .

Example 4 In Example 2, copper acetate (Cu(
CllffCOO)2 ・1120) 3.2g of water 2
(Sample D) was treated in the same manner as in the same example except that it was dissolved at 10 mN and used for supporting treatment (Sample D).

Example 5 In Example 1, titanium dioxide was dispersed and suspended in water 2 (10 components), and then 4 g of cobalt naphthenate (cobalt content: 8% by weight) was gradually added dropwise to carry out the supporting treatment. The desired anti-pest powder was obtained by processing in the same manner as in the same example (Sample E).

Example 6 In Example 5, the desired antiresistance was obtained by treating in the same manner as in Example 5, except that 6 g of nickel naphthenate (nickel content: 5% by weight) was used instead of cobalt naphthenate. A pestic powder was obtained (sample F).

Example 7 In Example 5, zirconium naphthenate (zirconium content = 4% by weight) was used instead of cobalt naphthenate.
The desired anti-pest powder was obtained by processing in the same manner as in the same example except that 6 g was used (Sample G).

Example 8 The desired anti-pest powder was obtained in the same manner as in Example 5, except that 2 g of tin octylate was used instead of cobalt naphthenate (sample H).

Test Example I For each sample obtained in the example (A to old and control sample (I: not treated with an organic acid metal salt compound),
Anti-pest properties were tested using the following method.

1. Test Pest 1〉, Algae A: Trentepohlia odorata B: Chlorella homosphaera C:
Chlorella vulgaris 5 2), Bacteria D: Bacillus subtilis E: Staphylococcus aureus F:
Escherichia coli 3), mold G: Cladosporium herbarum 2,
Medium (1), algal nibroti-ose agar medium (Proteo
se-agar medium) (2), bacteria:
Bouillon-agar medium
(3), Mold: Sabouraud-agar medium 3,
Method: Add 2 g of sample powder to 10 mR of each agar medium, stir thoroughly with a test tube ξ shaker to suspend, then pour into a = 16 petri dish with a diameter of 9 cm, and apply each separately cultured pest on the surface. , cultivated for a certain period of time (algae @: 14 at 23°C)
Bacteria: 2 days at 37°C, Mold = 28”C
The effect was determined by the degree of growth on agar (for 7 days).
+: growth inhibition, ++: withering, -: no growth inhibition effect).

The results are shown in Table 1.

Table 1 In Table 1, the metal content is the luminescence method analysis value (wt%) for the supported sample. Test Example 2 Sample A obtained in Example 1 and control sample ■ were mixed with emulsion resin (Dainippon Ink Chemical Industrial made: Boncourt 62
90) to produce a white paint (PVC 50%). This paint was applied onto a polyethylene terephthalate film using a doctor plate (1 (10 μm thick)) and dried to prepare a paint film sample.

Agar 10d (1.5% by weight) was poured into a 9crn shear, a paint film sample (3cm x 3cm) sterilized with ethanol (70% by weight) was placed on top of it, and the algae of Trend Boria lagenifera were transplanted onto the paint film. The cells were cultured in a constant temperature bath at 23°C under fluorescent light and irradiation. After 10 days, the growth level of the transplanted algal bodies was determined.

In the case of Control Sample I, the algae spread and proliferated on the paint film, whereas in the case of Sample A of Example 1, the algae died.

〔Effect of the invention〕

The anti-pest powder obtained by the present invention can exhibit anti-pest activity against bacteria, mold, algae, etc. without impairing the original characteristics of the base particles, and can be used in a wide range of fields. It has great industrial value as a treated material to impart anti-pest properties and as a lumbering material.

Claims (12)

[Claims] (1) An anti-pest powder characterized by having an organic acid metal salt compound supported on the surface of hydrous titanium oxide or titanium oxide particles. (2) The anti-pest powder according to claim (1), wherein the metal component of the organic acid metal salt compound is zinc, copper, cobalt, nickel, tin, or zirconium. (3) The anti-pest powder according to claim (1), wherein the organic acid metal salt compound is a metal salt compound of an alicyclic organic acid. (4) The anti-pest powder according to claim (1), wherein the organic acid metal salt compound is an aliphatic organic acid metal salt compound. (5) The anti-pest powder according to claim (1), wherein the organic acid metal salt compound is an aromatic organic acid metal salt compound. (6) The anti-pest powder according to claim (3), wherein the alicyclic organic acid component is naphthenic acid. (7) The anti-pest powder according to claim (4), wherein the aliphatic organic acid component is acetic acid. (8) The anti-pest powder according to claim (5), wherein the aromatic organic acid component is benzoic acid. (9) The anti-pest powder according to claim (3), wherein the organic acid metal salt compound is zinc naphthenate. (10) An anti-pest paint composition comprising the anti-pest powder according to claim (1). (11) Thermosetting resin or thermoplastic resin in Claim No. (
An anti-pest resin composition comprising the anti-pest powder described in item 1). (12) An anti-pest rubber composition comprising rubber and the anti-pest powder according to claim (1).