JPH01115958A - Macromolecular body - Google Patents

Abstract

PURPOSE:To obtain a macromolecular body which reduces changes in properties, and has long-durative bactericidal action, by using a clay mineral which can exchange cations between layers bearing bactericidal metal ions. CONSTITUTION:The subject macromolecular body is produced by adding a clay mineral including (B) bactericidal metal ions such as gold, silver or copper ions in (A) a clay mineral which is composed of a laminar silicate mineral belonging to the smectite group, cation-exchangeable between layers, to (C) a macromolecular body in an amount 0.01-50wt.%, preferably 0.05-40wt.%. For example, (A) is allowed to hold (B) and the product is admixed to (C) immediately before molding or at its monomer state, or A is added to C, molded, then the formed macromolecular body is ion-exchanged so that B is held with A in C to give the subject macromolecular body.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polymer characterized by containing a clay mineral having a bactericidal effect. More specifically, we are developing a clay mineral-containing polymer that contains exchangeable clay minerals with cations that retain metal ions that have a bactericidal effect. This is what we provide.

[Prior Art] Organic polymers have a number of different chemical structures ranging from solids to highly viscous liquids, and are currently widely used in products. However, these polymers are susceptible to attack by microorganisms because they allow moisture, nutrients, etc. to accumulate in their network structures and foams. Under these circumstances, efforts are being made to impart various antibacterial properties to these polymers, but the mechanism can be roughly divided into eluted type, which acts by eluting from the polymer into water, such as diphenyl ether. There are two types, such as organic silicon ammonium salts, which do not elute from polymers.

In the eluting type, the antibacterial debris itself is eluted, so there are concerns about safety for the human body and the effects on the surrounding area. In addition, the antibacterial activity was short-lived because the antiseptics were eluted and the content of the polymer was reduced.

On the other hand, the non-eluting type does not have these drawbacks and is considered preferable as an antibacterial agent. Metal ions such as silver ions, copper ions, and zinc ions have long been known to have antibacterial properties, and if these metal ions are retained in polymers and imparted with antibacterial properties, non-eluting antibacterial agents can be created. It can be expected to be widely used as Examples of methods for retaining metal ions in a polymer include a method in which the metal itself is retained, a method in which the metal powder itself is added to the polymer, and a method in which organic functional groups having ion exchange ability or complex forming ability are added to the polymer. There are methods such as containing a metal ion in a molecule and holding a metal ion in the organic functional group.

However, the method of using metal itself instead of polymer has the disadvantage that it is not compatible with the polymer.
Furthermore, since a relatively large amount is required, the number of MM increases and the cost increases. Furthermore, in a method in which a polymer contains an organic functional group having an ion-exchanging ability or a complex-forming ability and a metal ion is retained in the organic functional group, the interaction between the organic functional group and the polymer cannot be ignored. In order to avoid significant changes in the physical properties of polymers, the types and amounts of polymers and organic functional groups have to be within extremely narrow ranges.

[Problems to be Solved by the Invention] In view of the above-mentioned circumstances, the present inventors have conducted intensive research and found that a polymer containing clay minerals that retain metal ions having a bactericidal effect has been found to solve the above-mentioned drawbacks. The present invention has been completed based on this knowledge.

[Means for Solving the Problems] That is, the present invention is a polymer body characterized by containing a clay mineral that retains one or more metal ions having a bactericidal effect.

The configuration of the present invention will be described below.

The clay mineral used in the present invention is a layered silicate mineral belonging to the genus smectite in which interlayer cations can be exchanged,
Common examples include montmorillonite, beidellite, nontronite, zabonite, and hectorite, which may be natural or synthetic.

Commercially available products include Knivia, Smectone (all manufactured by Kunimine Industries), Peagum (Vanderbilt), and Laponite (
Laborte), fluorine tetrasilicon mica (Tobi Industries), etc. can be used.

In carrying out the present invention, one or more types of clay minerals may be arbitrarily selected and used from among these clay minerals.

Cations such as sodium ions and lithium ions usually exist between the layers of these clay minerals, electrically neutralizing the entire clay mineral, but these cations are exchangeable and easily exchange with other cations. You can change the position. This cation exchange capacity is Oshima 6 per 100g of clay mineral.
0 to 150 milliequivalents.

The metal ion having a bactericidal effect used in the present invention is silver, copper or zinc. 1 from these metal ions
One species or two or more species are arbitrarily selected and used.

The polymer used in the present invention is a synthetic or semi-synthetic organic polymer and is not particularly limited. Examples of these include thermoplastic synthetic polymers such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polynisdel, polyvinyl alcohol, polycarbonate, polyacetal, ABS resin, acrylic resin, fluororesin, polyurethane elastomer, and polyester elastomer. Molecules, thermosetting synthetic polymers such as phenolic resin, urea resin, melamine resin Hn, unsaturated polyester 4M resin, epoxy resin, urethane resin, regenerative or semi-synthetic polymers such as rayon, cupro, acetate, triacetate-1, etc. Examples include.

The clay mineral-containing polymer of the present invention is composed of a clay mineral that retains metal ions having a bactericidal effect and an organic polymer.

The proportion of the clay mineral retaining metal ions having a bactericidal action according to the present invention is preferably 0.01 to 50%, more preferably 0.05 to 40%, based on the polymer.

The method for producing the polymer of the present invention is not particularly limited, but it can be obtained, for example, by the following method. In other words, metal ions that have a bactericidal effect are retained in clay minerals, and this is added to and mixed with organic polymers, or clay minerals are added to organic polymers, molded, and then the molded polymer is ion-exchanged. Examples include a method in which clay minerals within the polymer body retain metal ions having bactericidal properties through treatment.

To explain these in detail, the former method involves adding water-soluble metal salts such as chlorides, nitrates, sulfates, and acetates of silver, zinc, copper, etc. to water and/or an organic solvent.
Then, a water-swellable clay mineral is dispersed therein, the precipitated clay mineral is dispersed, and if necessary, the clay mineral is washed and dried to obtain a clay mineral retaining metal ions having a bactericidal action. As the organic solvent, common solvents such as ethanol, methanol, and acetone are used. The concentration of the water-swellable clay mineral during production is not particularly limited, but if it exceeds 20% by weight, stirring becomes difficult and ion exchange becomes difficult.

It is desirable that the amount of metal ions exchanged is the same as the cation exchange capacity, but antibacterial activity can be exhibited even at about 10% by weight. When ion exchange is performed with such metal cations, clay minerals lose their gelling ability even when dispersed in water.

Further, even if metal ions other than silver, copper, and zinc, such as sodium, potassium, calcium, or other metal ions, coexist, the bactericidal effect is not hindered, so the residual or coexistence of these ions is not a problem.

Next, a clay mineral holding metal ions is added to and mixed with the organic polymer to obtain the polymer of the present invention. The mixing ratio is approximately 0.0, although it is desirable to contain more if the exchange ratio is small due to the amount of metal ion exchange.
5 to 10% is sufficient.

The timing and method of addition and mixing are not particularly limited. In short, the most suitable method may be adopted depending on the properties of the complete molecule used, the characteristics of the process, etc.

Usually, a method of adding and mixing just before molding is suitable. However, in some cases it may be preferable to add it to the monomer for better particle dispersion.

Next, as a manufacturing method for the latter, clay minerals are added to the polymer and mixed without ion exchange treatment. The timing and method of addition and mixing are not particularly limited. The obtained clay mineral-containing molecular body is made into a molded body and then subjected to ion exchange treatment. The type and shape of the molded body are not particularly limited, and may be an intermediate molded body such as a pellet, or may be in the form of a final product. The treatment method is basically similar to the method of ion exchange treatment of clay minerals described above, in which the clay mineral-containing polymer molded body is treated with a solution of water-soluble metal salts having a bactericidal effect.

In addition to the above-mentioned essential components, the polymer of the present invention contains an organic solvent, a polymerization catalyst, a stabilizer, a matting agent, a brightener, an organic or inorganic pigment, an inorganic filler, and various plasticizers. It may be blended within a range that does not impair the effect.

The polymer of the present invention can be molded into various shapes and sizes. For example, granules, films, glue fibers, ′?
! It can be made into a type F container, a vibrator, or any other molded object, and can be used in an extremely wide range of applications that require sterilizing power.

Furthermore, since the polymer of the present invention also has the functions inherent in clay minerals, it is possible to utilize both antibacterial properties and the functions inherent in clay minerals.

For example, it is possible to utilize the combined effect of clay mineral's original function of moisture absorption and adsorption and antibacterial effect.

It is also possible to incorporate other functional substances into the resin to exhibit a combined function of the above effects and other functions. Other functional substances include activated carbon and silica gel. In the case of activated carbon, the deodorizing and adsorption effect is enhanced, and in the case of silica gel, the moisture absorption effect is enhanced.

[Effects of the Invention] In the present invention, metal ions having bactericidal activity can be dispersed and retained within the polymer body using clay minerals as a carrier, so the metal ions are widely distributed compared to methods that use the metal itself, resulting in a greater bactericidal effect. is characterized by being large. Moreover, since the metal ions are stably retained in the clay mineral for a long period of time, it has excellent long-term bactericidal effect and can be applied to various polymers and has high industrial applicability.

[Example] Next, the present invention will be roughly explained in detail with reference to Examples.

Note that the present invention is not limited to these. Prior to the examples, the test method will be described below.

(1) Test method for evaluating antibacterial activity The shake flask method was used to evaluate antibacterial activity. That is, a molded body of a clay mineral-containing polymer serving as a sample is shredded,
Tested rri @ 1~2 x 10' (:2/l1ll
) Phosphate buffer (PH7,2) 7
Add 1.5g±0.1g to 0ml. The mixture was shaken at 25±2°C, and the number of viable bacteria was measured after 6 hours to determine the rate of decrease in the number of viable bacteria.

-A decrease y! E (%) = -X 100 Δ; Number of viable bacteria per 1 mt after shaking B; Number of viable bacteria per 1 tmL before shaking The medium used for both viable cell count measurement and preculture was Nutrient Ag.
ar (Dirco) was used.

The sample country is 5 taphylococcus aur.
Klebsiella pneumoni
ae, Pseudomonus aeruginos
a. Eseherichia coli was used.

(2) Mildew resistance test is based on Jis-Z-2911-1976
The mold resistance testing method specified in the wet method was used. That is, a mold spore dispersion liquid was sprayed onto a clay mineral-containing polymer molded sample, and the temperature was 28±2°C and the humidity (R11) was 95±5.
% for 28 days, the samples were observed and the results are shown in Table 1.

(Left below) Table 1 The test bacteria include Aspergillus niger.
, Penicillium funiculosum
was used. Potato dextrose agar medium (Eikensha) was used for preculture.

Table 2 lists the prepared clay minerals containing metal ions with bactericidal activity.

The preparation method is silver nitrate 51.0 to retain silver ions.
g, copper sulfate (pentahydrate) to retain copper ions
37.5g, nitric acid to retain zinc ions! II
44.6 g of lead (hexahydrate) is dissolved in 3 L of ion-exchanged water, 100 g of clay mineral is dispersed therein, and the mixture is stirred for 5 hours. Thereafter, the precipitate was filtered, washed with water, dried at 100° C., and pulverized to obtain the above metal ion-supported clay mineral.

Table 2 List of Antibacterial Clay Minerals Example 1 Antibacterial Polyurethane Foam A standard polyether paste polyurethane foam for the present invention is manufactured as follows.

First, component "A" and component "B" are prepared.

Component A'' is toluene diisocyanate with an isocyanate index of 105, and component B is the following mixture.

Boranol CP3810 (Dow Chemical Company) 100 parts by weight deionized water 4.5 Niax@A-1 (Union Carbide Company) 0.09 Silicone surfactant (Shinshu Silicone Company F-258) 0.8 Methylene chloride 3. 25 Generally, the conventional method is to combine the rB'' components in a suitable container and homogenize using a stirrer such as a disper. Then add component "A" and homogenize "A" and "B" again. Allow the foam to expand within the container.

The amount of antibacterial clay mineral blended in the present invention is polyol 100
Expressed as a percentage of parts. During the manufacturing process, the site where the fungal clay mineral is added is rB even in component "A".

However, it is important to mix it homogeneously.

Samples containing the antibacterial clay minerals shown in Table 2 were prepared using the above polyurethane foam manufacturing method, and the antibacterial properties were evaluated. The results are shown in Table 3.

In the shake flask method, ■5 taphylococcu
s aureus＊■Pseudomonus aer
Asper uginosa was used in the mold resistance test.
gillus niger was used.

Roughly test the above sample according to JIS L-0217 (1,05 method)
The antibacterial properties were evaluated after washing according to the same procedure and repeated 50 times, and the results are shown in Table 4.

Table 4 As is clear from Tables 3 and 4, it can be confirmed that the clay mineral-containing polymer of the present invention has strong antibacterial activity and is durable.

Example 2 Antibacterial polyurethane film A polyurethane film was prepared by the following method.

Polyisocyanate solution *100 parts by weight Dimethylformamide (DMF) 10 methyl ethyl ketone (
MEK) 20 *Takenate 300 (Takeda Pharmaceutical Company) When uniformly mixing the above, add 0 of the antibacterial clay mineral of the present invention.
．． 1 or 0.5 part was added. Approximately 70 μm of the mixture was applied onto a release paper, and a film was formed using a dry 17+ machine (80° C.).

Table 5 shows the results of antibacterial activity evaluation of each prepared sample.

(Left below) Table 5 The bacteria used in this test were tested using the shake flask method.
phylococcus aureus,■Klebs
iella pneumOnlae @, Penicillium funicu losu in mold resistance test
It is m.

Example 3 A predetermined amount of antibacterial clay mineral is added to an aqueous solution of antibacterial PVF sponge polyvinyl alcohol, and starch is added as a foam forming agent. Formaldehyde was bonded using hydrochloric acid as a catalyst, and a porous elastic body of polyvinyl; The evaluation results are shown in Table-6.

In the shake flask method, the test bacteria are ■5 taphylo
coccus aureul■Escherichia
Asperg.coli was used in the mold resistance test.
Illus niger was used.

Table 7 shows the results of washing 50 times in the same manner as in Example 1 and conducting the same test as above.

Table 7 As described above, it is confirmed that the polymer containing the antibacterial metal-containing clay mineral according to the present invention has strong antibacterial properties, and that the antibacterial properties persist even after washing.

Example 4 6 Nylon dry chips (relative viscosity 2.3/95% sulfuric acid)
A predetermined amount of antibacterial metal-containing clay mineral was added and mixed, and the antibacterial activity was evaluated after melt spinning according to a conventional method. However, in the shake flask method, Klebsiella was used as the test bacterium.
P. pneumoniae in the mold resistance test.
enicillium funiculosum was used. The antibacterial activity results are shown in Table 8.

Table 8 Example 5 Laponite containing no metal (Laborte), 0
．． 5 parts of urethane foam was foamed. 10 g of the above urethane foam was taken, immersed in a solution of 0.1 g of silver nitrate dissolved in 100 g of deionized water, and kept at room temperature with stirring for 20 hours to perform cation exchange. After cation exchange treatment, the urethane foam is thoroughly washed with water, and after drying,
Antibacterial activity was evaluated. The results are shown in Table-9. The test bacteria were the same as in Example 1.

Table 9 As mentioned above, the site where antibacterial metal ions are added to the clay mineral retains its antibacterial activity even after the clay mineral is blended into the polymer, and the antibacterial metal ion in the present invention The part added to the clay mineral has good antibacterial activity even in the production method shown in the second method.

Patent applicant: Shiseido Co., Ltd.

Claims (2)

[Claims] (1) A polymer characterized by containing a clay mineral that retains one or more metal ions having a bactericidal effect. (2) The polymer according to claim 1, wherein the metal ion having a bactericidal action is silver, copper or zinc.