KR20150006767A - Thermoplastic resin wares having fine particle of copper compound and method of manufacturing the same - Google Patents

Abstract

Disclosed are a thermoplastic resin container having fine particles of a copper compound which has relative low costs, is easy to be processed, and has economic feasibility and production efficiency, and a manufacturing method thereof. The container and the method comprise a thermoplastic resin in which a copper sulfur compound, Cu_xM_y (M is one selected among 15-17th columns of periodic table, x/y=0.8-1.2) is diffused. The thermoplastic resin container is manufactured by a sheet made by diffusing metal fine particle which is at least one selected from chrome, manganese, iron, cobalt, nickel, or zinc into the thermoplastic resin, and mulling the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin container containing copper-based compound fine particles and a method of manufacturing the same.

The present invention relates to a thermoplastic resin container containing copper-based compound fine particles and a method of manufacturing the same. More particularly, the present invention relates to a copper-based nano-sized copper nano- The present invention relates to a thermoplastic resin container containing particles and a method of manufacturing the same.

Recently, in hospitals, it is necessary to develop a plastic container improved in conductivity, which is excellent in electromagnetic wave shielding property and antistatic property due to an increase in use of high-priced medical equipment with many electromagnetic waves. In addition, indoor air pollution in hospitals is known to be the main cause of hospital infection, and the influence of newborn infants, elderly patients, low immune patients and pathogens on weak general inorganic atoms is very serious. In general, 10 to 20% of hospital infections are caused by airborne infections and the remainder are indirect infections caused by items and containers used in hospitals.

Among the products that can cause infections are bedding of patients, patient clothes, working clothes of hospital workers, and thermoplastic resin containers. The incidence of such infections in hospitals is 2.8 ~ 15.0% of those hospitalized. Social problems caused by infections in hospitals are being raised, and infection cases with disposable plastic containers such as tubes, trays, bowls, and parts should be removed at the same time as the fiber products. Accordingly, development of a plastic material excellent in antibacterial properties is required. In other words, plastic containers used in hospitals must meet the conductivity for electromagnetic shielding and antimicrobial properties to prevent hospital infection.

In order to improve the conductivity of plastics, Korean Patent Application No. 2012-7022202 improves the antistatic property by applying a divalent cation of a Group 2 element metal and a phosphoric acid ester salt. In addition, Korean Patent Applications No. 2011-7014670, No. 2010-0101700, and No. 2009-0098692 have imparted the conductivity of a plastic material using an organic salt having a fluoro group and a sulfonyl group. Korean Patent Application No. 2009-7006733 improves the conductivity of plastic materials by adding a polymer compound having a conductive base structure of PEO chain. However, as in the prior art, it is easy to apply plastics and improve the conductivity easily, such as phosphoric acid ester salts, fluoro groups and sulfonyl group-containing organic salts. However, when hot water is used, There are disadvantages. In addition, when a plastic container is produced by kneading a conductive polymer having a PEO chain, deformation of the container occurs due to non-uniform crystal and crystal size at each site.

In the prior literature on plastic antibacterial properties, Korean Patent Registration No. 10-0559405 discloses that 10 to 20 parts by weight of sulfur powder having a particle size of 1 to 3 占 퐉 is kneaded with a resin. In Korean Patent No. 10-0766418, 600nm silver nano powder and titanium dioxide were kneaded with a resin to produce a plastic product having excellent antimicrobial properties. In Korean Patent Registration No. 10-0987728, silver was deposited on a resin surface by sputtering or ion plating method, and then the silver deposited was mixed to make an antimicrobial yarn. In Korean Patent Registration No. 10-1180117, antimicrobial yarns were prepared by dyeing zinc sulfide nano-particles and organic antibacterial agent.

However, although it is known that the antimicrobial properties of the silver and sulfur components used in the prior art are excellent, there are many limitations in practical use. In the case of silver, despite the high antibacterial and convenience, the supply price is too high. In case of sulfur, environmental hazard and machinability are not yet solved. Even in the method of imparting antimicrobial properties, deposition and coating have disadvantages such as poor economical efficiency and efficiency.

A problem to be solved by the present invention is to provide a thermoplastic resin container containing copper-based compound fine particles having relatively low cost, easy processing, economical efficiency and production efficiency, and a manufacturing method thereof.

The thermoplastic resin container containing the copper-based compound fine particles for solving the problems of the present invention is a copper-based sulfur compound having Cu _x M _y (M is any one selected from the groups 15 to 17 in the periodic table, x / y = 0.8 to 1.2) Is dispersed in the thermoplastic resin.

In the container of the present invention, M may be any one selected from S, F and Cl. The sulfur compound is preferably copper sulfide. The sulfur compound may be greater than 0 wt% and less than 50 wt% with respect to the entire vessel. , Preferably from 0.1 wt% to 40 wt%, and more preferably from 5 wt% to 30 wt%. The sulfur compound may have an average particle diameter of 5 to 150 nm and a sulfur concentration of 10 to 60 mol%.

In the preferred container of the present invention, the thermoplastic resin may be at least one selected from the group consisting of polyethylene terephthalate, polylactic acid, polyethylene, polypropylene, polycarbonate, polymethylmethacrylate, and polyvinyl chloride. The thermoplastic resin may be applied in the order of an olefin resin, polyethylene terephthalate and polycarbonate as the size of the container increases.

In the preferred container of the present invention, the thermoplastic resin may include fine metal particles of at least one selected from the group consisting of chromium, manganese, iron, cobalt, nickel and zinc. The metal fine particles may be contained in an amount of 0.1 to 2 wt% with respect to the entire container, and the average particle size may be 10 to 30 nm. The average particle diameter of the metal fine particles may be smaller than the average particle diameter of the copper sulfide fine particles.

In order to solve the above problems, the present invention provides a method for producing a thermoplastic resin container containing copper-based compound microparticles, which comprises mixing copper sulfate and at least one selected from the group consisting of a sulfide, a fluoride salt and a chloride salt in a molar ratio of 1: 80 ° C to synthesize copper sulfide microparticles having an average particle size of 5 to 150 nm and a sulfur concentration of 10 to 60 mole%. Thereafter, a sheet in which the copper sulfide fine particles larger than 0 wt% and not more than 50 wt% are dispersed in the thermoplastic resin is formed. A thermoplastic resin container is produced using the sheet.

In the production method of the present invention, the sulfur flame may be any one selected from sodium sulfide, iron sulfide, potassium sulfide and zinc sulfide. At this time, the sulfur flame may be sodium sulfide. The fluorinated salt may be any one selected from among sodium fluoride, iron fluoride, potassium fluoride, and zinc fluoride. The salt flame may be any one selected from sodium chloride, iron chloride, potassium chloride, and zinc chloride. 0.1 to 2 wt% of fine metal particles of at least one selected from chromium, manganese, iron, cobalt, nickel and zinc having an average particle diameter of 10 to 30 nm can be dispersed in the thermoplastic resin. The sheet is formed by extrusion, and the formed sheet can be made into a thermoplastic resin container through primary cooling, heat treatment and secondary cooling. The extrusion pressure for forming the sheet may be 0.05 to 1 kg / mm ² h h.

According to the thermoplastic resin container containing the copper-based compound fine particles and the method for producing the same, the thermoplastic resin container in which the copper-based sulfur compound fine particles including copper sulfide and the transition metal fine particles are dispersed in the thermoplastic resin is manufactured , The price is relatively inexpensive, the processing is easy, and the economy and the production efficiency can be sufficiently provided. In particular, by adding at least one selected from chromium, manganese, iron, cobalt, nickel, and zinc which are transition metals in the four cycles of the periodic table, it is possible to reduce the extrusion pressure .

1 is a photograph showing copper sulfide nanoparticles produced according to an embodiment of the present invention.
2 is an XRD graph showing the crystal structure of copper sulfide produced according to an embodiment of the present invention.
FIG. 3 is a micrograph of copper sulfide produced according to an embodiment of the present invention at a magnification of 30,000 times. FIG.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments described below can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

An embodiment of the present invention is to provide a thermoplastic resin container in which copper-based sulfur compound fine particles including copper sulfide and transition metal fine particles are dispersed in a thermoplastic resin to produce a thermoplastic resin container having a relatively low cost and easy processing, Based thermoplastic resin particles and a method for producing the same. To this end, a method for producing a thermoplastic resin container by dispersing copper compound fine particles including copper sulfide and metal fine particles in a thermoplastic resin will be described in detail, and the antibacterial property and conductivity of the thermoplastic resin container will be described in detail. On the other hand, in consideration of economical efficiency and production efficiency, the production of a plastic container having improved antibacterial and conductivity is not a surface coating such as deposition or dyeing, but a method of dispersing a substance having high antibacterial and high conductivity therein and kneading with a resin To be applied.

The material of the thermoplastic resin container is mainly composed of a thermoplastic resin composed of polyethylene terephthalate, polylactic acid, polyethylene, polypropylene, polycarbonate, polymethylmethacrylate, polyvinyl chloride and the like. Polyvinyl chloride (PVC) has excellent processability and is widely used as a disposable thermoplastic resin container until recently. However, recently, environmental regulations are serious because of the problem of harmful substances generated by incineration, and its usage is gradually decreasing. The use of olefin resins such as low density polyethylene (LDPE), high density polyethylene (HDPE), and polypropylene (PP) is relatively increasing. In this case, the container includes not only a container for storing articles but also a consumable for hospital such as tubes and other parts.

The resin used in the embodiment of the present invention varies depending on the size of the container. That is, owing to the viscosity characteristics of the resin, relatively small containers are preferable for olefin resins such as PP and PE, and medium-sized containers are mainly useful for polyethylene terephthalate (PET). Polycarbonate (PC) is preferred for relatively large capacity containers. Polymethylmethacrylate (PMMA) and polyvinyl chloride (PVC) are mainly used as hospital consumables such as tubes and other parts. In recent years, polylactic acid (PLA), which is a biomaterial made from corn or potato, is used as an injection product.

The thermoplastic resin container according to an embodiment of the present invention includes copper-based sulfur compound fine particles and metal fine particles. The sulfur compound fine particles may be contained in an amount greater than 0 wt% and less than or equal to 50 wt% with respect to the container. , Preferably from 0.1 wt% to 40 wt%, and more preferably from 5 wt% to 30 wt%. The sulfur compound fine particles may have an average particle diameter of 5 to 150 nm. The metal fine particles may be at least one selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and zinc. The metal fine particles have an average particle diameter of 10 to 30 nm and may contain 0.1 to 2 wt% of the metal fine particles. At this time, the sulfur content of the synthesized copper-based sulfur compound fine particles is preferably 10 to 60 mol%. When the sulfur content of the fine particles is less than 10 mol%, the antimicrobial activity becomes poor. When the sulfur content is more than 60 mol%, the conductivity is deteriorated.

The copper-based sulfur compound fine particles to be applied to the embodiment of the present invention are preferably copper sulfide (CuS). Copper sulphide was synthesized in the form of nanoparticles of 20 to 100 nm by reacting copper sulfate (CuSO ₄ ) with a salt selected from a sulphate, a fluoride salt and a chloride sulphate in a molar ratio of 1: 1 at a temperature of 50 to 80 ° C . At this time, the chemical structure of the synthesized copper sulfide nanoparticles was Cu _x S _y , and the synthesis conditions were limited so that the ratio x / y was 0.8 to 1.2. Examples of the sulfur flame that can be used in the present invention include sodium sulfide, iron sulfide, potassium sulfide, and zinc sulfide, and examples of the fluoride salt include sodium fluoride, fluoride iron, potassium fluoride, and zinc fluoride. Examples of the chloride salt include sodium chloride, iron chloride, potassium chloride, and zinc chloride. At this time, copper sulfide synthesized using sodium sulfide and copper sulfate showed the best antimicrobial activity and deodorization.

On the other hand, when the reaction temperature is lower than 50 캜, when copper-based nanoparticles are synthesized, reactivity between the copper sulfate and the salt is decreased, and the average particle size becomes smaller, and the antibacterial property is good but the deodorizing property is poor. When the reaction temperature is 80 ° C or higher, the reaction rate becomes excessively high, the crystal density of the surface of the copper sulfide increases, and the copper concentration increases. However, the deodorizing property is good but the antibacterial property is deteriorated. Also, when the binding ratio of x / y of the copper-based nanoparticles is less than 0.8, the concentration of sulfur (S) becomes too high, so that the antibacterial property is good but the deodorizing property is poor. The antibacterial property is lowered.

On the other hand, if the sulfur compound fine particles such as copper sulfide are dispersed in a thermoplastic resin alone to form a fiber, it is sufficient for use as a thermoplastic resin fiber having improved antibacterial properties and conductivity. However, when it is made into a sheet form for use in a thermoplastic resin container, the dispersibility becomes poor, and the pressure (extrusion pressure) during extrusion may increase. In other words, in the case of a sheet having a relatively small size, sufficient antibacterial properties and conductivity can be obtained by the sulfur compound fine particles. However, a sheet of larger size should take into consideration the above-mentioned extrusion pressure.

In order to prevent the extrusion pressure from rising, in the embodiment of the present invention, at least one metal selected from the group consisting of chromium, manganese, iron, cobalt, nickel and zinc, which is a transition metal selected in four cycles of the periodic table having an average particle size of 10 to 30 nm 0.1 to 2 wt% of metal fine particles may be added to the container. When the transition metal is mixed with a copper-based compound, the transition metal is excellent in dispersibility as well as antimicrobial activity and conductivity compared to a typical metal such as Al.

On the other hand, in order to reduce the extrusion pressure, the average particle diameter of the metal fine particles is preferably smaller than the particle diameter of the copper-based sulfur compound fine particles. Further, when kneaded with the thermoplastic resin, the mixing pressure of the metal fine particles was higher than 0.1 wt% or higher than 2 wt%, the extrusion pressure was rather increased. As described above, the metal microparticles are added to control the extrusion pressure, and the antimicrobial property and the conductivity required in the thermoplastic resin container can be obtained by only copper-based sulfur compounds. Accordingly, the thermoplastic resin container can be produced without metal fine particles within the scope of the present invention. At this time, the added metal fine particles were selected so as not to impair the antimicrobial activity and conductivity required for the thermoplastic resin container of the present invention.

In the present invention, kneading was used to increase the dispersibility between the resin and the fine particles, and kneading was performed at a barrel temperature 30 to 50 ° C higher than the melting temperature of the resin. The kneading was carried out in a kneader equipped with a biaxial co-directional screw having excellent dispersibility rather than a uniaxial screw. The L / D ratio range of the kneader is preferably 30 to 40. The kneaded resin was stored in a bunker in the form of chips and then extruded at an extrusion temperature of 30 to 50 DEG C higher than the melting temperature of the plastic resin used. It was then produced in the form of thermoplastic resin containers required through molding, primary cooling, heat treatment, and secondary cooling.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are intended to illustrate but not limit the invention. The performance evaluation of the containers prepared in the examples and the comparative examples of the present invention was carried out as follows.

(1) average particle diameter

The average particle size of copper sulfide and fine metal particles was measured using a particle size analyzer (ELS-Z2, Otsuka Electronics Co., Japan).

(2) Antimicrobial activity

 Escherichia coli (ATCC 25922) was used as a strain to bring the test strain into contact with the specimen. The specimen was then incubated at 25 ° C for 24 hours, and the bacterial count was counted to evaluate the antibacterial activity of the specimen.

(3) Conductivity

 The conductivity of the plastic container was evaluated by measuring the surface resistance using an insulation resistance meter of Hewlett-Packard Company under the conditions of 23 캜, 60% relative humidity, and an applied voltage of 500 V.

(4) Sulfur component

 An inductively coupled plasma mass spectrometer (Agilent 7500, Aglient Technologies Inc., USA) was used to calculate the sulfur mole ratio of the copper sulfide microparticles.

(5) Extrusion pressure

The dispersibility of the copper sulfide and the metal fine particles added in the resin was evaluated by the change value of the extrusion pressure applied to the filter. When the resin was extruded at a rate of 30 kg per hour using a pilot extruder, the change in filter pressure (0.1 kg / (mm ² × h) = ΔP / h) applied to the 350 mesh filter per a fixed time was measured, The better the dispersion of copper sulfide and metal fine particles was.

≪ Example 1 >

CuSO ₄ and Na ₂ S were added to distilled water in an amount of 1 mole each, and the mixture was stirred for 30 minutes. The mixture was then placed in an isothermal reactor at 50 ° C. for 30 minutes to synthesize copper sulfide microparticles as shown in FIG. At this time, the synthesized copper sulfide had an average particle diameter of 55 nm and sulfur was 25 mol%. The crystal structure of the synthesized copper sulfide had a native structure of copper sulfide as shown in FIG. 2, and the shape of the particles observed at a magnification of 30,000 was as shown in FIG. According to Fig. 3, no peak was observed due to the absence of a crystal structure of sulfur, but peaks at 55 degrees, 65 degrees, 99 degrees, 125 degrees and 137 degrees of copper. X-ray powder diffraction (XRD, XD-3A, Shimadzu, Japan) was used to observe the nanoparticles.

Thereafter, 0.01wt% of the synthesized copper sulfide was added to low density polyethylene (LDPE, specific gravity 0.92), and 1 wt% of zinc (Zn) fine particles having an average particle diameter of 15 nm was added to improve the extrusion pressure. I made chips. The prepared chip was extruded at an extrusion pressure of 0.1 kg / (mm ² × h) at a temperature of 130 ° C. by using an extruder to produce a sheet, and the sheet thus prepared was molded into a thermoplastic resin container by a known method such as injection molding. At this time, the mechanical properties of the vessel were improved through two cooling and heat treatment processes. The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

≪ Example 2 >

Copper sulfide having an average particle diameter of 55 nm, an average particle diameter of 55 nm, a sulfur concentration of 0.1 wt% and an average particle diameter of 15 nm and zinc (Zn) having a concentration of 1 wt% were put into low density polyethylene in the same manner as in Example 1 to prepare a thermoplastic resin container. At this time, the extrusion pressure was 0.1 kg / (mm ² × h). The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

≪ Example 3 >

Copper sulfide having an average particle diameter of 55 nm, sulfur 10 mol% and concentration 5 wt%, zinc (Zn) having an average particle diameter of 10 nm and a concentration of 0.2 wt% was put into low density polyethylene in the same manner as in Example 1 to prepare a thermoplastic resin container. At this time, the extrusion pressure was 0.1 kg / (mm ² × h). The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

<Example 4>

Copper sulphide having an average particle diameter of 55 nm, sulfur 10 mol% and concentration 5 wt% and manganese (Mn) having an average particle diameter of 10 nm and a concentration of 0.2 wt% were put into low density polyethylene in the same manner as in Example 1 to prepare a thermoplastic resin container. At this time, the extrusion pressure was 0.05 kg / (mm ² × h). The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

&Lt; Example 5 &gt;

Copper sulfide having an average particle diameter of 45 nm, sulfur 36 mol% and concentration 20 wt% and iron (Fe) having an average particle diameter of 25 nm and a concentration of 0.6 wt% were put into high-density polyethylene (HDPE) in the same manner as in Example 1 to prepare a thermoplastic resin container . At this time, the extrusion pressure was 0.2 kg / (mm ² × h). The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

&Lt; Example 6 &gt;

Copper sulphide having an average particle diameter of 85 nm, sulfur 42% by mole and a concentration of 30% by weight and cobalt (Co) having an average particle diameter of 30 nm and a concentration of 0.7% by weight were placed in polypropylene (PP) in the same manner as in Example 1 to prepare a thermoplastic resin container . At this time, the extrusion pressure was 0.3 kg / (mm ² × h). The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

&Lt; Example 7 &gt;

Copper sulphide having an average particle diameter of 100 nm, sulfur 60 mol% and a concentration of 40 wt% and chromium (Cr) having an average particle diameter of 30 nm and a concentration of 2 wt% were placed in polyethylene terephthalate (PET) in the same manner as in Example 1 to prepare a thermoplastic resin container . At this time, the extrusion pressure was 0.5 kg / (mm ² × h). The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

&Lt; Comparative Example 1 &

Copper sulfide having an average particle diameter of 55 nm, sulfur 65 mol%, concentration 10 wt%, zinc (Zn) having an average particle diameter of 15 nm and a concentration of 1 wt% was put into low density polyethylene (LDPE) in the same manner as in Example 1 to prepare a thermoplastic resin container. At this time, the extrusion pressure was 0.2 kg / (mm ² × h). The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

&Lt; Comparative Example 2 &

Copper sulphide having an average particle diameter of 55 nm, a sulfur concentration of 5 mol% and a concentration of 10 wt%, and zinc (Zn) having an average particle diameter of 15 nm and a concentration of 1 wt% were put into low density polyethylene (LDPE) in the same manner as in Example 1 to prepare a thermoplastic resin container. At this time, the extrusion pressure was 0.2 kg / (mm ² × h). The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

&Lt; Comparative Example 3 &

Copper sulfide with an average particle diameter of 45 nm, 36 mol% of sulfur and 20 wt% of concentration and iron (Fe) having an average particle diameter of 25 nm and a concentration of 0.01 wt% were put into high-density polyethylene (HDPE) in the same manner as in Example 1 to prepare a thermoplastic resin container . At this time, the extrusion pressure was 5 kg / (mm ² × h). The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

&Lt; Comparative Example 4 &

Copper sulphide having an average particle diameter of 85 nm, sulfur 42% by mole and a concentration of 30% by weight and cobalt (Co) having an average particle diameter of 85 nm and a concentration of 40% by weight were put into polypropylene (PP) in the same manner as in Example 1 to prepare a thermoplastic resin container. At this time, the extrusion pressure was 15 kg / (mm ² × h). The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

&Lt; Comparative Example 5 &

Copper sulphide having an average particle diameter of 100 nm, sulfur 60 mol% and a concentration of 40 wt% and aluminum (Al) having an average particle diameter of 30 nm and a concentration of 2 wt% were placed in polyethylene terephthalate (PET) in the same manner as in Example 1 to prepare a thermoplastic resin container . At this time, the extrusion pressure was 12 kg / (mm ² × h). The antimicrobial activity and the conductivity of the thus prepared container were measured as described above.

Table 1 shows the average particle diameter (nm), the sulfur mole% and the concentration (wt%) of the copper sulfide microparticles of Examples 1 to 5 and Comparative Examples 1 to 5, the average particle diameter (nm) %) And the conductivity (Ωcm) of the thermoplastic resin container made of the thermoplastic resin contained in the thermoplastic resin container.

division
Polymer
Suzy
Conductor particle Container sheet Copper sulfide microparticles Metal fine particles Extrusion pressure
(? P / h)
Antimicrobial activity
(Dogs / mL)
Conductivity
(Ω cm)
Particle size
(nm) Sulfur concentration
(mole%) density
(wt%) metal
Kinds Particle size
(nm) density
(wt%)

room
city
Yes

One LDPE 55 25 0.01 Zn 15 One 0.1 2.1 × 10 ⁷ 10 ⁶ 2 LDPE 55 25 0.1 Zn 15 One 0.1 8.0 × 10 ⁶ 10 ⁶ 3 LDPE 55 25 10 Zn 15 One 0.1 3.2 × 10 ⁶ 105 4 LDPE 20 10 5 Mn 10 0.2 0.05 6.5 × 10 ⁶ 10 ⁵ 5 HDPE 45 36 20 Fe 25 0.6 0.2 2.2 x 10 ⁵ 10 ⁴ 6 PP 85 42 30 Co 30 0.7 0.3 1.2 × 10 ⁵ 10 ⁴ 7 PET 100 60 40 Cr 30 2 0.5 1.3 x 10 ⁵ 10 ³
ratio
School
Yes

One LDPE 55 65 10 Zn 15 One 0.2 3.2 x 10 ⁸ 10 ¹⁰ 2 LDPE 55 5 10 Zn 15 One 0.2 3.2 × 10 ¹⁰ 10 ⁵ 3 HDPE 45 36 20 Fe 25 0.01 5 7.2 x 10 ⁵ 10 ⁶ 4 PP 85 42 30 Co 85 40 15 5.2 × 10 ¹⁰ 10 ⁶ 5 PET 100 60 40 Al 30 2 12 6.2 × 10 ¹⁰ 10 ⁸

According to Table 1, the thermoplastic resin containers of Examples 1 to 7 of the present invention had a molar percentage of sulfur of 10 to 60 mol%, an average particle diameter of 20 to 100 nm, and a concentration of 0.01 to 40 wt% with respect to the whole container. Further, the added metal fine particles are at least one selected from chromium, manganese, iron, cobalt, nickel and zinc, and have an average particle diameter of 10 to 30 nm and a concentration of 0.1 to 2 wt% in the whole vessel. At this time, the antimicrobial activity was 1.2 × 10 ⁵ to 2.1 × 10 ⁷ (number / ml), and the conductivity was measured from 10 ³ Ωcm to 10 ⁶ Ωcm. Also, the extruded pressure showed a value within the range of 0.05 to 0.5 kg / (mm ² × h).

In the case of Example 2 in which the copper sulfide microparticles were 0.1 wt%, the antimicrobial activity was not significantly different from that of Example 3, which was 5 wt%, by 8.0 × 10 ⁶ and 3.2 × 10 ⁶ , respectively. However, the conductivity was 10 ⁶ ? Cm and 10 ⁵ ? Cm, which was relatively excellent in Example 3. From the viewpoint of antibacterial activity, Example 2 was also preferable. The antibacterial properties and conductivity of Example 6 having 30 wt% of sulfide fine particles and Example 7 of 40 wt% were almost similar. Accordingly, in the resin container according to the embodiment of the present invention, 0.1wt% to 40wt% of copper sulfide is preferable from the viewpoint of antibacterial activity. In consideration of both antibacterial property and conductivity, 5 wt% to 30 wt% is more preferable.

On the other hand, in Comparative Examples 1 and 2, the sulfur concentration was 65 mol% and 5 mol%, respectively, which were deviated from 10 to 60 mol% of the examples of the present invention. At this time, the antibacterial property and the conductivity were 3.2 × 10 ⁸ (dog / mL), 10 ¹⁰ Ωcm and 3.2 × 10 ¹⁰ (dog / mL) and 10 ⁵ Ωcm, respectively. That is, when the sulfur concentration exceeds 60 mol%, the conductivity deteriorates. When the sulfur concentration is less than 10 mol%, the antimicrobial activity becomes poor. Accordingly, the sulfur concentration of the thermoplastic resin container of the present invention is preferably 10 to 60 mol%.

Comparative Example 3 is a case where the concentration of iron (Fe) is fine, and Comparative Example 4 is a case where the average particle diameter and concentration of cobalt (Co) which is a metal fine particle do not satisfy 10 to 30 nm and 0.1 to 2 wt% . At this time, the antibacterial property and the conductivity were 7.2 × 10 ⁵ (pcs / mL), 10 ⁶ Ωcm, 5.2 × 10 ¹⁰ (pcs / mL) and 10 ⁶ Ωcm, respectively. Specifically, Comparative Example 3 in which the concentration of the metal fine particles deviated from the examples of the present invention did not deteriorate antimicrobiality and conductivity significantly, but was unsuitable for extruding the extruded pressure at 5 kg / (mm ² × h). In Comparative Example 4 in which the average particle diameter and the concentration were out of the range, the extrusion pressure was not able to be extruded at 15 kg / (mm ² × h), and the antibacterial property tended to be much worse.

Comparative Example 5 is a case in which aluminum (Al) other than chromium, manganese, iron, cobalt, nickel and zinc, which are metal fine particles proposed by the present invention, is added. At this time, the antimicrobial activity and the conductivity were 6.2 × 10 ¹⁰ (dogs / mL) and 10 ⁸ Ωcm, respectively, and the extrusion pressure was 12 kg / (mm ² × h). Aluminum is a typical metal in three cycles of the periodic table. This is different from transition metals in the four cycles of the periodic table of the present invention. When aluminum is added, antimicrobial activity and conductivity are deteriorated, and the extrusion pressure is high, which lowers production efficiency. Accordingly, the metal fine particles of the present invention are preferably chromium, manganese, iron, cobalt, nickel and zinc, which are transition metals in four cycles of the periodic table.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but many variations and modifications may be made without departing from the spirit and scope of the invention. It is possible.

Claims (20)

Wherein the copper-based compound particles are dispersed in a copper-based sulfur compound in which Cu _x M _y (M is any one selected from the group consisting of groups 15 to 17 in the periodic table, x / y = 0.8 to 1.2) is dispersed in the thermoplastic resin. The thermoplastic resin container according to claim 1, wherein M is any one selected from S, F, and Cl. The thermoplastic resin container according to claim 1, wherein the sulfur compound is copper sulfide. The thermoplastic resin container according to claim 1, wherein the sulfur compound is contained in an amount greater than 0 wt% and less than 50 wt% with respect to the entire container. The thermoplastic resin container according to claim 1, wherein the sulfur compound is contained in an amount of greater than 0.1 wt% and less than 40 wt% with respect to the entire container. The thermoplastic resin container according to claim 1, wherein the sulfur compound is contained in an amount greater than 5 wt% and less than 30 wt% with respect to the entire container. The thermoplastic resin container according to claim 1, wherein the sulfur compound has an average particle diameter of 5 to 150 nm and a sulfur concentration of 10 to 60 mol%. The copper-based microparticle according to claim 1, wherein the thermoplastic resin is at least one selected from the group consisting of polyethylene terephthalate, polylactic acid, polyethylene, polypropylene, polycarbonate, polymethylmethacrylate and polyvinyl chloride. Containing thermoplastic resin containers. The thermoplastic resin container according to claim 1, wherein the thermoplastic resin is applied in the order of an olefin resin, a polyethylene terephthalate, and a polycarbonate as the size of the container increases. The thermoplastic resin container according to claim 1, wherein the thermoplastic resin comprises copper-based compound fine particles containing fine metal particles of at least one selected from the group consisting of chromium, manganese, iron, cobalt, nickel and zinc. The thermoplastic resin container according to claim 10, wherein the fine metal particles are contained in an amount of 0.1 to 2 wt% with respect to the entire container, and the average particle diameter is 10 to 30 nm. The thermoplastic resin container according to claim 10, wherein the average particle diameter of the metal fine particles is smaller than the average particle diameter of the copper sulfide fine particles. A method of reacting copper sulfate and a salt of any one selected from the group consisting of sulfur, fluoride and chloride in an aqueous solution at a molar ratio of 1: 1 at a temperature ranging from 50 to 80 ° C to obtain an aqueous solution having an average particle size of 5 to 150 nm and a sulfur concentration of 10 to 60 moles % Copper sulfide fine particles;
Forming a sheet in which the copper sulfide microparticles are dispersed in a thermoplastic resin; And
And a step of preparing a thermoplastic resin container using the sheet. The method for producing a thermoplastic resin container according to claim 1, 14. The method according to claim 13, wherein the sulfur flame is any one selected from the group consisting of sodium sulfide, iron sulfide, potassium sulfide, and zinc sulfide. 14. The method for producing a thermoplastic resin container according to claim 13, wherein the sulfur flame is sodium sulfide. 14. The method according to claim 13, wherein the fluorinated flame is any one selected from the group consisting of sodium fluoride, iron fluoride, potassium fluoride, and zinc fluoride. 14. The method for producing a thermoplastic resin container according to claim 13, wherein the salt flame is any one selected from the group consisting of sodium chloride, iron chloride, potassium chloride and zinc chloride. The method of claim 13, further comprising the step of forming a sheet in which 0.1 to 2 wt% of fine metal particles of at least one selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and zinc having an average particle size of 10 to 30 nm is dispersed in the thermoplastic resin Based on the weight of the copper-based compound fine particles. The thermoplastic resin composition according to claim 13, wherein the sheet is formed by extrusion and the formed sheet is made into a thermoplastic resin container through primary cooling, heat treatment and secondary cooling. &Lt; / RTI &gt; The method for producing a thermoplastic resin container according to claim 19, wherein the extrusion pressure for forming the sheet is 0.05 to 1 kg / mm ² h h.

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