JPH01268764A - Antimicrobial pigment powder - Google Patents

Abstract

PURPOSE:To obtain the subject powder, capable of improving persistence of antimicrobial effects and having coloring material characteristics, such as high hiding power, essential to an inorganic pigment and useful as a treating material for imparting antimicrobial activity, by supporting an antimicrobial metal on particle surfaces of a specific inorganic pigment. CONSTITUTION:The objective powder obtained by supporting an antimicrobial metal (e.g., metallic copper) on particle surfaces of an inorganic or extender pigment (e.g., zinc oxide or magnetite) consisting essentially of at least one element of Al, Ba, Ca, Cd, Co, Cr, Fe, Mg, Pb, Si, Sb or Zn.

Description

[Detailed description of the invention] [Technical field of invention] The present invention relates to a pigment powder having antibacterial properties.

[Technical background of the invention]

Pigments and extender pigments are used in large quantities in a wide variety of fields, including for various coloring and protective coloring in paints and printing inks, and for filling and coloring plastics, rubber, fibers, etc. In particular, inorganic pigments generally have greater negative repellency and greater durability against sunlight and heat than organic pigments, and their demand is increasing as the field of use for coloring materials expands. In addition, extender pigments are
Along with the expansion of the fields of application of the above-mentioned inorganic pigments, such as adjustment of the properties of paints and inks, improvement of coating film characteristics and printing characteristics, reinforcement of filled moldings, etc., the fields of application are also expanding year after year.

Incidentally, in recent years, in the field of use of various products to which coloring materials using the above-mentioned headless pigments and extender pigments are applied, various types of damage caused by microorganisms such as mold and bacteria, and other harmful organisms to industrial products, structures, etc. has increased. Many proposals have been made to prevent this.

One of them is what is called copper or silver? Antibacterial agents have been attempted in which, for example, various soluble copper salts, copper complex compounds, etc. are adsorbed onto solid particles such as resin particles or zeolite, making use of the antibacterial properties of a metal.

However, the above-mentioned antibacterial agents do not have sufficient long-lasting antibacterial performance, and it is difficult to obtain fine particles. , the dispersibility in various media such as coating agents for paper processing is not sufficient, and furthermore, in order to obtain sufficient antibacterial effects, it is necessary to increase the amount added, and as a result, coated products and molded products using them There is a desire to improve the color tone of products, etc., and it is difficult to obtain the desired color tone. In recent years, the above-mentioned improvements have been particularly strongly desired in cases where particularly beautiful coloring is required, such as home appliances and high-end furniture that have been subjected to antibacterial treatment.

[Purpose of the invention]

The present invention solves the above-mentioned problems and provides an antibacterial-imparted product that can impart excellent antibacterial properties and further improve the color toning properties of antibacterial-treated products. There is a particular thing.

[Summary of the invention]

The present invention is based on the process in which the present inventors have been conducting various studies on inorganic pigments and extender pigments for some time to make them more functional as coloring materials and give them high added value. We focused on material composites and expansion of application fields through application to antibacterial-supported powders, and as a result of further investigation, we found that particle powders of specific inorganic pigments and extender pigments have a high adhesion of antibacterial metal components on the particle surface. is extremely excellent, and therefore the sustainability of the antibacterial metal effect can be increased, and the color toning properties of application products using antibacterial metal-supported products can be further improved. Based on this knowledge, the present invention was completed. That is, the present invention
+ B a + Ca + Cd + Co, Cr
, F e +Mg, Pb, Si, Sb, or Zn. It is.

In the present invention, the inorganic pigment or extender pigment (hereinafter referred to as substrate constituent particles) supporting an antibacterial metal component is A
l, Ba+ Ca, Cd, Co, Cr, Fe
, Mg, Pb, Si, Sb, or Zn. For example, (1) white pigments such as zinc oxide, antimony white, and lithopone; (2) Magnetite (
iron black), black pigments such as chrome black, yellow lead, cadmium yellow,
Yellow pigments such as yellow iron oxide, (3) red pigments such as iron oxide (pengara lead red), (4) blue pigments such as swarm, navy blue, and cobalt blue, chromium oxide, chromium green, etc. (5) Extender pigments such as charcoal, talc, alumina white, silica white, barium sulfate, and barium carbonate.

Various metals can be used as the antibacterial metal supported on the base particles, and preferred examples include various copper metals such as copper metal, Cu-Zn, Cu-5n, and Cu-Zn-P. Examples include alloys, metallic silver, and metallic zinc, and these may be supported alone or in combination of two or more. The amount of the metal component supported is usually 0.00 as the supported metal based on the weight of the base material particles.
It is 1 to 35%, preferably 0.01 to 30%. If the supported amount is too low than the above range, the desired antibacterial effect will not be achieved, and if it is too large, it will not only be cost-effective, but also have poor dispersibility in the antibacterial property imparting treatment medium, color tone, etc. It may be easily damaged. In the present invention, in order to support the antibacterial metal on the base particles,
This can be done by various methods, for example (1
1. A reducing agent and, if necessary, various auxiliary agents such as a buffer, a complexing agent, and a PL+ regulator are added to the metal ion aqueous solution containing the metal component to form a plating bath, and the substrate constituent particles are added to the plating bath. A method in which the metal ions are deposited as a metal film on the surface of the particles by immersing the powder and stirring for a predetermined period of time to deposit the metal ions on the surface of the particles is a so-called electroless plating method. If the component particles are immersed in an aqueous solution of palladium, tin, etc. in advance to adhere them to the surface of the base component particles, the antibacterial metal component can be more efficiently deposited into a film, and furthermore, the adhesion can be improved. (2) The base component particle powder and the antibacterial metal powder are loaded into a dry or wet compaction mill, such as a ball mill or an edge runner mill, and mixed under compaction. , a method for supporting antibacterial substrate constituent particles on the surface of the substrate constituent particles, (3) various metal compounds containing antibacterial metal components, such as alkyl metal compounds,
A method in which an antibacterial metal is supported on the surface of particles by thermally decomposing an organometallic complex compound or the like on the particles constituting the base. Note that when carrying out the above-mentioned supporting treatment, it is desirable to carry out the process in an atmosphere of an inert gas such as nitrogen gas to prevent oxidation as much as possible.

The antibacterial pigment powder supported in the above manner can be used in a wide range of applications, such as paints, plastic moldings, paper, fibers, etc., by applying various methods known per se. industrial and household electrical equipment,
It has excellent performance in antibacterial treatment of furniture, interior decoration materials, packaging materials for tableware, medical hygiene materials and equipment, environmental hygiene equipment and facilities, etc., and also has features as a conductive material. It is possible to obtain it, and it is industrially useful.

The present invention will be further explained by giving examples and comparative examples below.

[Example of the present invention]

Example 1 Ferrous sulfate solution (mother liquor Fe concentration 100 g/j!) 3
1 was heated to 79 to 80°C, and while stirring, an aqueous solution of caustic soda was added dropwise to bring the pH of the mother liquor to 5.2. Air was then blown in, and at the same time, an aqueous solution of caustic soda was further added dropwise to maintain the pH. The reaction was allowed to proceed for 90 minutes to form a precipitate. The resulting slurry was filtered, washed with water, and dried.
Black granular magnetite was obtained (substrate constituent particles, average particle size 0.05 μm). 250 g of the magnetite was suspended in water to prepare an aqueous slurry (244 g/1). Take 250 ml of the slurry and add 1 ml of brass powder (Metal Foil Powder Industries BI?A-AT-200) to it.

After thoroughly mixing with a Henschel mixer, the mixture was placed in a brass ball mill (mill internal volume: 47!, filled with 500ml of 61IIlφ brass balls, slurry volume: 250ml).
! , rotation speed 15 rpm) for 240 minutes. After ball milling, the slurry was taken out, diluted, and sedimented and separated repeatedly to separate brass powder particles and magnetite particles.The slurry after 0 fractionation was filtered, washed with water, and dried to support a brass alloy on the surface of the base particles. An antibacterial pigment powder was obtained.

Example 2 In Example 1, the aqueous slurry of substrate constituent particles 25O
n+7! Inside, silver powder particles (width metal foil powder industry Agc
-AO) A total of 10 g of the target antibacterial pigment with metallic silver supported on the surface of the base particles was processed in the same manner as in the same example except that a porcelain ball mill and balls were used. A powder was obtained.

Example 3 In Example 1, the aqueous slurry of substrate constituent particles 250
mj! Inside, copper powder (width metal foil powder industry CU-ΔT-
200) was added and processed in the same manner as in the same example except that a copper ball mill and balls were used.
A target antibacterial pigment powder having metallic copper supported on the surface of the base particles was obtained.

Example 4 350g of magnetite powder used in Example 1 was
It was fired in an electric furnace at 800° C. for 60 minutes to obtain reddish brown granular hematite (α-Fez03) (substrate constituent particles, average particle size 0.17 μm). Aqueous slurry (251 g/i!) was prepared by suspending 250 g of the above-mentioned hematite in water.

Take 250ml of the slurry and add brass powder (
Width metal foil powder industry BI? 10 g of A-AT-200) was added, thoroughly mixed using a Henschel mixer, and then subjected to a compaction treatment for 240 minutes in a brass ball mill (same as in Example 1). Thereafter, the slurry was taken out and dilution and sedimentation separation was repeated to separate brass powder particles and hematite particles. The slurry after fractionation was filtered, washed with water, and dried to obtain the desired antibacterial pigment powder having a brass alloy supported on the surface of the particles constituting the substrate.

Example 5 In Example 4, 10 g of silver powder particles (Fukuda Metal Foil & Powder Industries Agc-AO) were added to 250 ml of the aqueous slurry, and a porcelain ball mill and balls were used. A desired antibacterial pigment powder having metallic silver supported on the surface of the particles constituting the substrate was obtained by processing in the same manner as in the above case.

Example 6 In Example 4, 1 copper powder particle (metal foil powder industry CU-AT-200 for width) was added to 250 ml of aqueous slurry.
The desired antibacterial pigment powder having metallic copper supported on the surface of the base particles was obtained by processing in the same manner as in the same example except that a copper ball mill and balls were used.

Example 7 Alumina powder (KP-20, A1□o, to Order Kagaku Co., Ltd.)
99.99%, average particle size 0.4μ, specific surface area 7m/gs
10 g of the base constituent particles) were put into palladium sol t (1 (p d-c t t aqueous solution to which sodium dodecylbenzenesulfonate was added and reduced with NaBII4) 5001117i, which had been heated to 65°C in advance. After stirring for a minute, the alumina particles were tilted and washed with water to adhere palladium to the surface of the alumina particles.
l/R, formaldehyde 2.2 mol/j! , lofsil salt 0.5 mol/R1Na0111. Omol/
l, NazCOz 0.25mol/l,
Add EDTA O, 06 mol/l) at 40°C.
), stirring was continued for 40 minutes at the same liquid temperature to deposit a metallic copper film on the surface of the particles constituting the substrate. Thereafter, the alumina particles were separated by filtration, washed with water, and dried to obtain the desired antibacterial pigment powder.

Example 8 In Example 7, silica powder (
The quartz powder manufactured by Hideko Omu is ground in a ball mill to obtain an average particle size of 0.8.
The desired antibacterial pigment powder was obtained by processing in the same manner as in the same example, except that 10 g of the antibacterial pigment was used.

Example 9 In Example 7, kaolin powder (
The desired antibacterial pigment powder was obtained by processing in the same manner as in the same example, except that 10 g of Joshia Kaolin 1lydrite R1 (average particle size 0.8 μm), manufactured by Sanyo Boeki, was used.

Example 10 The same procedure as in Example 7 was used except that 10 g of barium sulfate (Hirai Chemical, -grade reagent, average particle size 0.7 μm) was used instead of alumina powder. An antibacterial pigment powder was obtained.

Example 11 Zinc oxide powder (Hakusui Chemical @ No. 1 Zinc White Zn099.5%
After suspending 20 g of the above (average particle size 0.3 to 0.5 μ) in 400 ml of ethylene gelcol, this suspension was put into a four-bottle flask equipped with a stirrer, and while nitrogen gas was introduced, Stirred for 30 minutes under non-oxidizing atmosphere. Then C
6.7 g of u (Csl (+0z)
I(C5ll?O□)2 was thermally decomposed. The suspension was then filtered and washed (washed with toluene) to obtain a cake.

This cake was gently dried at a low temperature to obtain the desired antibacterial pigment powder with metallic copper supported on the particle surface.

Example 12 In Example 11, calcium carbonate powder (Nippon Lime Industry @ C3-A type CaC0°9) was used instead of zinc oxide powder.
9.9%, average particle size of 0.5 μm or less) except that 20 g of the intended antibacterial pigment powder with metallic copper supported on the particle surface was prepared in the same manner as in the same example. Obtained.

Example 13 In Example 11, talc powder (Hirai Chemical, reagent SiO□52.2%, MgO31.5%) was used instead of zinc oxide powder.
%, AlzOff 1.9%) was used in the same manner as in the same example, to obtain the intended antibacterial pigment powder having metallic copper supported on the particle surface.

Example 14 The same case as in Example 11 except that 20 g of iron oxide (Hirai Chemical, reagent CR-Fe001199.5%, average particle size 0.1 μm, yellow) was used instead of zinc oxide powder. The desired antibacterial pigment powder with metallic copper supported on the particle surface was obtained by processing in the same manner as above.

Example 15 In Example 11, barium carbonate powder (Hirai Chemical, reagent BaC0+ 99.5% or more) was used instead of zinc oxide powder.
The desired antibacterial pigment powder having metallic copper supported on the particle surface was obtained by processing in the same manner as in the same example except that 20 g was used.

Reference Example To the antibacterial pigment powder pot Log obtained in Examples 1 to 15, acrylic resin (Dainippon Ink Acrydic) was added at a volume ratio of 1:1ffi, and 20 ml of 1-luene was added.
Left Devil paint shaker (inner volume 200
ml, glass peas 1. A coating liquid was prepared by mixing and dispersing the mixture in a 0mmφ filling). This coating liquid was applied onto a PET film using a doctor blade. After drying to the touch, the coated products (S+, S
Z+ "'S11+ Coating film thickness 11-14μm, total thickness 1
10 to 115 μm, diameter 23 mmφ) was obtained.

S, created as above, 53, S4, S6
, Sl, Sl, S11. SI2 coating sample, So:
Untreated PET film, C: Use a copper plate as a sample piece, and add this sample piece to 100% sterile physiological saline added with 0.10% peptone.
Pour two of each sample (side-by-side) into a petri dish holding ml of each sample, inoculate a predetermined amount of bacteria, and check the number of bacteria at the culture temperature (35°C) relative to the number of bacteria immediately after. The antibacterial properties of The results are shown in the table below. The following three types of bacteria were used in the test.

B + ; E, Col+ (E. coli) B xi
s, tap, aureus (staphylococcus)
B3; T, 5choenleini
(Number of pieces added: 2) [Effects of the invention] The antibacterial pigment powder obtained by the present invention has an antibacterial metal component firmly supported on the surface of the base particles, and has a long-lasting antibacterial effect. It can be expected to increase the coloring properties of inorganic pigments, and has the coloring properties such as high coloring power, coloring power, and dispersibility that are inherent to inorganic pigments, as well as the reinforcing performance of the coloring properties that are inherent to extender pigments, making it suitable for a wide range of applications. It has great industrial utility value as an antibacterial treatment material and as a lumbering material.

Claims (1)

[Claims] Al, Ba, Ca, Cd, Co, Cr, Fe, Mg, P
1. An antibacterial pigment powder, characterized in that an antibacterial metal is supported on the particle surface of an inorganic pigment or extender pigment whose main component is at least one of the following elements: b, Si, Sb, or Zn.