JP2709589B2 - Resin products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to synthetic and natural resin products.

[0002]

2. Description of the Related Art Resin products are manufactured in complicated shapes such as films, wools, sheets, plates, tubes, containers, and the like, because of the advantage that resins can be easily molded. It's being used. Because of its water resistance, it is widely used in building materials, bath products, toilet articles, kitchen items, gardening items, etc. When molds grow on these resin products, deterioration occurs. That is, since mold is a heterotrophic type, it is necessary to obtain nutrients from other sources, and when molds inhabit on the resin, they take nutrients from the resin and cause deterioration of the resin. Originally, resins are those that do not generate microorganisms such as molds and bacteria except for some resins such as melamine, polyvinyl acetate, viscose rayon, etc.In fact, in order to adapt each resin product to its use, Since additives such as coloring agents, stabilizers, plasticizers, and lubricants are blended, these blends become nutrients for harmful microorganisms, and discolor or become brittle, resulting in microbial degradation.
For this reason, many kinds of antibacterial and antifungal agents for kneading resin are actually sold.

[0003] However, among the antibacterial and antifungal agents kneaded into conventional resin products, there are those that have pollution problems and those that increase the cost. In particular, the resin products have iron parts, When coexisting with an iron product that is bonded to a product, it has been difficult to obtain a preferable resin product because the bonding with the iron part may be weakened by iron rust.

[0004]

The problems of the conventional resin products to be solved by the present invention are that microbial degradation is apt to occur, discoloration due to iron rust when coexisting with iron products, bonding with iron products. Is vulnerable. SUMMARY OF THE INVENTION An object of the present invention is to provide a resin product which solves such conventional problems at low cost without causing environmental pollution such as no pollution.

[0005]

In order to solve the above-mentioned problems, the present invention provides an antibacterial property (the function of inhibiting or suppressing the growth of microorganisms such as bacteria, fungi, and algae is referred to as an antibacterial property, hereinafter referred to as an antibacterial property). One or more metal ions selected from the group consisting of silver, copper, and zinc as ions having an antibacterial agent) and a group consisting of calcium carbonate, calcium phosphate, and ceramic materials that adsorb and carry the ions. a carrier composed mainly of one or more of the supported material selected from among, in the three-dimensional structure of a single crystal 4
An object of the present invention is to provide a resin product containing an antibacterial / rust preventive agent mixed with a zinc oxide whisker having a projecting portion in the direction by mixing or coating.

[0006]

According to the present invention, there is provided a substance which uses silver ions, copper ions or zinc ions, which are generally pollution-free and are also used in drinking water purifiers, as antibacterial ions having antibacterial performance, and adsorbs and carries the same. Calcium carbonate and calcium phosphate (naturally, hydroxyapatite is also referred to as apatite represented by the chemical formula of Ca ₁₀ (PO ₄ ) ₆ (OH) _2, a phosphate mineral group that is commonly produced a lot),
Ceramic material (the naturally acid clay, ceramic material, such as child Sensoba) using factors such materials become multi surface area at and inexpensive non-polluting substances, in the ion carrier in monocrystalline
Since it is a resin product containing an antibacterial and rust preventive agent mixed with zinc oxide whiskers having protrusions in four directions in a three-dimensional structure, even if it is a resin alone product, it coexists with iron parts or iron products However, microorganisms such as bacteria, molds, and algae, black agar-like substances called slime, and iron rust are not attached, and the microorganisms are less deteriorated than conventional products, and are hygienic, clean, and beautiful.

The remarkable effect of the present invention is that, in addition to the above, (1) the zinc oxide whisker to be blended is a single-crystal three-dimensional structure.
Since the crystal has a protruding portion in four directions and has a unique shape that is not found in other crystals, it grows in four directions. (A) It has strong activity and stability, and has silver ion, copper ion, and zinc. It significantly increases the antibacterial performance of ions and the like. Therefore, not only is the antibacterial and rust-preventive agent of the antibacterial and rust-preventive agent high, but also the resin with excellent antibacterial and rust-preventive performance even when the cost is reduced by making the content of expensive silver or copper extremely small. A product is realized.

(B) In order to enhance the antibacterial performance of silver ions, copper ions, zinc ions and the like by using zinc oxide whiskers, silver, copper, zinc, etc. are reduced to 1/10 to 1/1000 of conventional zinc oxide whiskers. Since the amount of antibacterial ions can be reduced as compared with non-containing antibacterial ions, the amount of metal ions eluted in water can naturally be made much smaller than the emission standard.
Therefore, antibacterial and safe for environmental preservation and impact on human body
This is to realize a resin product with rust prevention function.

(C) The zinc oxide whisker has a fiber length of 2 to 2.
It is in the range of 3 μm to several 100 μm, and has a specific gravity of 5.7.
(Air permeation method), sublimation temperature 1720 ° C, tensile strength 270
~280kgf / cm ^2, bending strength 440kgf / c
m ² , flexural modulus 20,000 to 21,000 kgf /
It has properties such as cm ² and can realize a resin product with enhanced mechanical strength.

(2) The adsorption carrier is an inexpensive and non-polluting substance generally used, such as calcium carbonate, calcium phosphate, and ceramics. A water-soluble metal salt solution such as silver nitrate, copper sulfate, or zinc sulfate is used. In such a case, the carrier can be adsorbed and supported simply by immersing the carrier in these solutions. In each case, a sufficiently large specific surface area can be obtained.

[0011]

EXAMPLES (Example 1) Resin tiles usually referred to as P-tiles and plastic styles are arranged on a washroom, a kitchen floor, or a wall surface and adhered with an adhesive. Example 1 shows an example in which the present invention is applied to this resin tile.

First, copper 5 was added to 120 grams of a 5% sulfuric acid solution.
The gram is dissolved to form a copper sulfate solution, water is added to make 1 liter of a water-soluble metal salt solution, and an 8.5% aqueous ammonia solution is added thereto to form a complex ionized copper sulfate complex ion solution. 0.5 μm particle size, 40 m ² /
g calcium carbonate powder 10kg and 110
C. and sufficiently adsorbed and supported while stirring well. At this time, the water and ammonia in the solution completely vaporize,
Copper is uniformly supported on the particle surface of the calcium carbonate powder. The above calcium carbonate powder shows PH7 when suspended in water. The above-mentioned calcium carbonate powder carrying copper has a particle size of 150 mesh and a specific surface area of 60 m ² /
g and suspended in water, the aqueous solution is PH7
10 kg of hydroxyapatite powder and a small amount of a binder were mixed, and the mixture was heated to 110 ° C. with the above-mentioned copper calcium carbonate powder and 2 kg of zinc oxide whiskers using a mortar until the respective raw materials were sufficiently dispersed. After stirring, the mixture was extruded into a white sphere of about 2.5φ by an extruder and dried at 80 to 100 ° C. for about 4 hours to obtain a white sphere. Then, the white sphere particles are mixed with the ABS resin fluid as the base material of the resin tile, and at the same time, the AB material of the base material is mixed.
The S resin and the mixed ABS resin having different flow characteristics and hues were mixed and molded into a plate to obtain a marble-patterned resin tile. The zinc oxide whiskers used for the white spheres manufactured in Example 1 had a single crystal , three-dimensional structure, and projecting portions in four directions as shown in the electron micrograph in FIG.
It is obtained in the form shape with.

[0013] When the resin tile constructed in Example 1 was stuck on the floor of the washroom, no mold was generated, and no iron rust was generated on the iron ring around the drain pipe of the washroom set. Was something. This iron ring is a first embodiment of the present invention.
No iron rust is generated due to contact with the resin tile. Further, since zinc oxide whiskers are mixed in the resin tile of the first embodiment, the resin tile has a higher mechanical strength than the resin tile not mixed.

The effect is the same when hydroxyapatite or acidic clay is used as a carrier in place of the calcium carbonate of Example 1, and silver or zinc may be used instead of copper.

In order to determine the relationship with the antibacterial and other effects of the zinc oxide whiskers in Example 1, the amount of the zinc oxide whiskers was changed so that the weight ratio was 0% to 30%.

[0016]

[Table 1]

The antibacterial performance of the materials A, B, C and D according to Table 1 was tested as follows. That is, the molds used in the test are Group 1 Asbergillus niger, Group 2 Penicillium citrinum, Group 4 Cladosporium Cladosporioides, Group 5 Ketomium globosum, and fungi according to JIS 2911 "Mold resistance test method". Five species of Candida albicans were used. In the test method, the subrow-agar medium is poured into a petri dish, and materials A, B, C, and D are uniformly and thinly arranged on the surface. After applying the test bacteria uniformly on the whole surface, placing them in a weather meter, setting the conditions at a temperature of 28 ° C. and a humidity of 70 to 75%,
After standing for 0 hour, the state of propagation of the test bacteria was examined, and the results are shown in Table 2.

[0018]

[Table 2]

As shown in Tables 1 and 2, Material A without zinc oxide whisker had no antibacterial effect of inhibiting mold and fungi, and Material B with zinc oxide whisker containing 10%, 20% and 30%, respectively. , C, and D have an antibacterial effect, and it was found that the addition of zinc oxide whiskers improved the antibacterial effect without increasing the amount of copper ions.

While the conventional disinfectant containing copper ions as an antibacterial agent contains about 10% by weight of copper, the white sphere of Example 1 contains 0.02% of copper by weight. And the amount is very small.

Next, three beakers containing 500 ml of tap water were prepared, and the materials A, B, C, and D were separately charged so that the weight ratio was 0.4%.
A 0.5φ steel wire was immersed sufficiently in water in the same manner as in 20 cm. With the passage of days, the steel wire rusted and brown iron rust floated in the water. The steel wire left at room temperature for 50 days was taken out of the water, the weight before and after the test was measured, and the results were obtained by comparing the percentage of rusting with the percentage of the decrease in the weight of the steel wire. In the same manner as in the test of the rust prevention effect, green algae (Sayamidori) were put into a beaker filled with 500 ml of water, and the materials A, B, C, and D were tested for the anti-algal effect. The results are shown in Table 3 in the same table as the results of the rust prevention.

[0022]

[Table 3]

According to the results shown in Table 3, the data A containing no zinc oxide whisker had little effect on rust prevention and algae prevention, whereas the data B, C and D showed a remarkable effect. Was.

According to the results shown in Tables 1, 2 and 3, when the resin tile of the first embodiment is used, the growth of microorganisms such as bacteria, fungi and algae is suppressed, and at the same time, iron rust is reduced. This also suppresses the occurrence, and indicates that the resin tile in Example 1 is excellent in hygiene and aesthetic appearance.

In the first embodiment, the antibacterial and rust preventive agent is formed into a white sphere, mixed with a base resin of a resin tile together with a mixed resin that forms a marble pattern, and then molded into a tile shape. After the tile is formed, an antibacterial / rust preventive agent may be applied to the surface of the tile.

Example 2 A polyethylene film serving as a substrate was heat-sealed on the back surface of a raised portion of polypropylene raised by a needle punch to obtain a floor carpet. An iron wire is sewn on the floor carpet, an electric current is applied to generate heat as a resistance wire, and the floor carpet is used as a heating carpet on a kitchen floor.

In the second embodiment, the antibacterial and rust preventive agent of the first embodiment is converted into resin pellets and mixed into a polyethylene film as a base of the floor carpet at the time of molding to form a carpet. The means for pelletizing the antibacterial and rust preventive agent obtained in Example 1 into resin will be described below.

In Example 1, a mixed powder 1 of calcium carbonate and hydroxyapatite uniformly supporting copper, a zinc oxide whisker 1 and a polyethylene 8 were mixed in a weight ratio and extruded as a pellet by a resin extruder to be molded. . This polyethylene is combined with an antibacterial and antirust agent to form a film from polyethylene pellets, which is formed into a film.

Since the floor carpet of the second embodiment is made of polyethylene pellets mixed with the antibacterial and rust preventive agent of the first embodiment, microorganisms such as mold are generated even when used in a kitchen. In addition, the heater wire of the iron wire is sewn in, but no iron rust is generated on the iron portion. The floor carpet can also be used for a vehicle carpet such as a car carpet.

[0030]

As is clear from the above description of the examples, the resin product of the present invention is free from microbial deterioration such as bacteria, fungi and algae, and inhibits or suppresses the generation and growth of agar-like substances and iron rust. Very small amount of ions such as silver, copper, and zinc, which play a central role in antibacterial performance, have strong antibacterial and anticorrosive properties, are environmentally safe and pollution-free, as are carriers and zinc oxide whiskers. It has no pollution and low cost, and has many effects such as being strengthened by zinc oxide whiskers.

[Brief description of the drawings]

FIG. 1 shows a single crystal contained in an antibacterial and rust preventive agent used in an embodiment of the present invention in four directions in a three-dimensional structure.
Electron micrograph of zinc oxide whiskers with protrusions

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08K 9/02 KCN C08K 9/02 KCN C08L 101/00 C08L 101/00 // C08L 101: 00

Claims (5)

(57) [Claims] 1. An antibacterial ion comprising one or more metal ions selected from the group consisting of silver, copper, and zinc, and calcium carbonate, calcium phosphate, and a ceramic material adsorbing and supporting said metal ions. A carrier mainly composed of one or a plurality of carriers selected from a group, and a protrusion in four directions in a single crystal three-dimensional structure
A resin product containing an antibacterial and rust preventive combined with zinc oxide whiskers having 2. An antibacterial ion comprising one or more metal ions selected from the group consisting of silver, copper, and zinc, and calcium carbonate, calcium phosphate, and a ceramic material adsorbing and supporting said metal ions. A mixed powder consisting of a carrier mainly composed of one or more carriers selected from the group; and a single crystal having a three-dimensional structure.
A resin product formed from a large number of resin pellets mainly composed of a mixture of a zinc oxide whisker having protrusions in four directions and an unmolded resin material. 3. The resin product according to claim 1, which is combined with an iron product. 4. The method according to claim 1, wherein the metal that elutes the metal ion is contained in an amount of up to 1% of the total weight of the carrier that adsorbs and supports the metal ion and the zinc oxide whisker.
The resin product as described. 5. The resin product according to claim 1, wherein the zinc oxide whisker has a lower limit of 1/9 in weight ratio with respect to the carrier that adsorbs and supports metal ions.