KR101564328B1

KR101564328B1 - Plastic deposited with copper based compound and method of manufacturing the plastic

Info

Publication number: KR101564328B1
Application number: KR1020140050541A
Authority: KR
Inventors: 백승우
Original assignee: (주)비에스써포트
Priority date: 2014-04-28
Filing date: 2014-04-28
Publication date: 2015-10-29
Also published as: WO2015167095A1

Abstract

A plastic coated with a copper-based compound on which a coating film having a high coating strength is imparted to the surface of a plastic by imparting conductivity and antibacterial property to the surface of the plastic, and a method for producing the same. The plastic and the method deposit a compound on the surface of the plastic base material that has the chemical structure Cu _x M _y (M is any one selected from the group 15 to 17 in the periodic table, x / y = 0.8 to 1.5).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to plastics deposited with a copper-based compound,

TECHNICAL FIELD The present invention relates to a plastic and a method of manufacturing the same, and more particularly, to a plastic which imparts antimicrobial properties to a copper-based compound having conductivity and improves the durability of a deposited film, and a method for producing the same.

Recently, development of a plastic container having excellent electromagnetic shielding property and antistatic property has been demanded due to an increase in the use of high-priced equipment with many electromagnetic waves. A method of forming a conductive coating film on the surface of a plastic is widely used as an electromagnetic shielding method using conductivity. In addition, the use of plastics with antibacterial properties to prevent bacterial infections is increasing. Antimicrobial activity includes preventing bacteria from growing or sterilizing bacteria. Various types of plastics, such as textile articles, tubes, trays, bowls, appliance parts, etc., need to simultaneously achieve conductivity and antibacterial properties. For example, plastic containers used in hospitals should meet the conductivity for electromagnetic shielding and antimicrobial properties to prevent infection by pathogens.

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, in Korean Patent Applications No. 2011-7014670, 2010-0101700, and 2009-0098692, the conductivity of a plastic material is imparted by using an organic salt having a fluorine 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, the phosphate salt, the fluorine group and the organic salt having a sulfonyl group and the like can easily be applied to plastics and can easily improve the conductivity, but the drawback is that the conductivity of the plastic container is drastically lowered when hot water is used . 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. A method of imparting antimicrobial properties has not been specifically implemented.

A problem to be solved by the present invention is to provide a plastic on which a copper-based compound is deposited on which a coating film having a high coating strength is imparted to the surface of a plastic, and a method for producing the same.

The plastics deposited with the copper based compound for solving the problems of the present invention include a plastic base material and a copper based compound deposited film deposited on the surface of the plastic base material. In this case, the chemical structure of the compound is Cu _x M _y (M is any one selected from Groups 15 to 17 in the periodic table, x / y = 0.8 to 1.5).

In the plastic of the present invention, M may be any one selected from S, F and Cl. The compound may be copper sulfide.

In order to solve the problems of the present invention, a method of manufacturing a plastic on which a copper compound is deposited includes first preparing a plastic base material. Thereafter, a copper-based compound is deposited on the surface of the plastic base material. In this case, the chemical structure of the compound is Cu _x M _y (M is any one selected from Groups 15 to 17 in the periodic table, x / y = 0.8 to 1.5).

In the production method of the present invention, the surface of the plastic can be treated with a conductive polymer emulsion solution containing a transition metal before the deposition step. 0.01 to 3.0% by weight of colloidal transition metal fine particles and 0.01 to 5.0% by weight of at least one emulsion selected from water-soluble polyester, water-soluble urethane and water-soluble acrylic on the surface of the plastic.

According to the plastics deposited with the copper-based compound of the present invention and the method of producing the same, the surface of the plastics has high conductivity, antibacterial properties and film strength by depositing a compound containing copper sulfide. The copper-based compound formed by the vapor deposition is excellent in antimicrobial activity, so that the antibacterial property of the plastic can be improved by applying it.

1 is an XRD graph showing the crystal structure of copper sulfide produced by the present invention.
2 is a photograph of copper sulfide deposited on the plastic produced by the present invention.

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.

The copper-based compound to be applied to the embodiment of the present invention is preferably copper sulfide (CuS). Copper sulfide was synthesized by reacting copper sulfate (CuSO ₄ ) with a salt selected from the group consisting of a sulfur flame, a fluoride salt, and a chloride flame in a 1: 1 molar ratio at a temperature of 10 to 80 ° C in an aqueous solution. At this time, the chemical structure of the synthesized copper sulfide nanoparticles is in the form of Cu _x S _y , and the synthesis conditions are limited so that the ratio x / y is 0.8 to 1.5. 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, the copper sulfide synthesized by using sodium sulfide and copper sulfate was the best.

When the reaction temperature is lower than 10 캜, the reactivity between the copper sulfate and the salt is poor when the copper nanoparticles are synthesized, but the antibacterial property is good. However, the yield for producing copper sulfide is low. When the reaction temperature is 80 ° C or higher, the reaction rate becomes excessively high, and the density of the crystals on the surface of the copper sulfide increases and the antibacterial property decreases as the copper concentration increases. Further, when the binding ratio of x / y of the copper-based nanoparticles is 0.8 or less, the concentration of sulfur (S) becomes excessively high and the antibacterial property is good. However, the chemical stability of copper sulfide drops. If it is more than 1.5, the copper concentration increases and the antibacterial property is lowered.

After depositing the deposition target using the copper sulfide produced by the above method, it is physically deposited on the surface of the plastic. In order to increase the film strength in the deposition, it is preferable to treat the surface of the plastic with the conductive polymer emulsion solution containing the transition metal before the deposition. 0.01 to 3.0 wt% of colloidal transition metal fine particles and 0.01 to 5.0 wt% of at least one emulsion selected from water-soluble polyester, water-soluble urethane and water-soluble acrylic are applied to the surface of the plastic. The water dispersion coating liquid can increase the vapor deposition strength. The residual solids in the water-dispersed coating liquid are adjusted to be 0.001 to 0.1 g / m ² . The deposition is carried out under a vacuum of 10 ^-5 to 10 ^-3 torr so that the vapor pressure of the metal is maintained at 10 ^-2 to 10 ^-1 , and copper sulfide is deposited on the plastic surface to a thickness of 300 to 600 Å. The deposition strength of the deposition layer is preferably at least 60 g / 25 mm or more.
The plastic can be a thermoplastic resin and a thermosetting resin, and thermoplastic resins advantageous for molding are more preferable. The thermoplastic resin mainly includes polyethylene terephthalate, polylactic acid, polyethylene, polypropylene, polycarbonate, polymethylmethacrylate, polyvinyl chloride, polyurethane, silicone, and the like. The thermosetting resin is preferably an epoxy resin or the like. Polyurethane is more preferable because it is flexible, nontoxic and has good chemical resistance.

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 of the plastics prepared in the examples and comparative examples of the present invention was evaluated in the following manner. Hereinafter, among the above compounds, copper sulfide will be mainly described.

(1) Surface state of coating film

The surface state of the coating film was observed by a microscope to evaluate the presence or absence of protrusions on the surface of the coating film and the state of the non-deposited state. The protrusions and the non-deposited water observed per 10 cm × 10 cm were observed and evaluated.

○: 1 or less

?: 2 to 4

×: 5 or more

(2) Coating film thickness

The thickness of the coated film was measured using SEM (sanning electron microscopy, JSM-6390A, JEOL, USA).

(3) Coating film strength

The coating strength of the coating film was controlled by the adhesion of the coating film, and the adhesion strength of the coating film measured when pulling with a load of 90 kg / sec was measured using a pull-down break point tester (Phto Teohnioa, USA).

?: 300 kg / cm ² or more

?: 100 to 300 kg / cm ²

X: 100 kg / cm ² or less

(4) Antimicrobial activity

Escherichia coli (ATCC 25922) was used as a strain to bring the test bacteria into contact with the specimens. The specimens were incubated at 25 ° C for 24 hours, and the bacterial counts of the specimens were evaluated. The antimicrobial activity was excellent when the number of bacteria was less than 10 < ⁷ > Escherichia coli (ATCC 25922) was labeled ^{10 if the} number of bacteria was more than 10 ¹⁰ per mL and measurement was impossible.

(5) 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.

O: 10 ² Ω × cm or more

×: 10 ² Ω × cm or less

&Lt; Example 1 >

CuSO ₄ and Na ₂ S were added to distilled water in an amount of 1 mol each, stirred for 30 minutes, and placed in an isothermal reactor at 50 ° C for 30 minutes to synthesize copper sulfide microparticles. A water-dispersion coating liquid containing 0.5 wt% of colloidal transition metal fine particles and 1.0 wt% of emulsion of water-soluble polyester was applied to the surface of LDPE plastic having a diameter of 1 cm and a length of 10 cm. The residual solids in the water-dispersed coating liquid were adjusted to 0.05 g / m ² . Thereafter, the vapor deposition target was physically evaporated to form a coating film on the plastic surface. The thickness of the deposited copper sulfide was 400 Å.

The crystal structure of the deposited copper sulfide had the inherent structure of copper sulfide as shown in Fig. According to Fig. 1, 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 for observation of the fine particles. The coating film formed on the LDPE plastic was as shown in Fig. The antimicrobial properties, conductivity, surface condition and film strength of the thus-produced plastics were measured as described above.

&Lt; Example 2 >

Copper sulphide was deposited on the surface of PP plastic of 1 cm in diameter and 10 cm in length as in Example 1 to form a coating film. The antimicrobial properties, conductivity, surface condition and film strength of the thus-produced plastics were measured as described above.

&Lt; Example 3 >

As in Example 1, copper sulfide was deposited on the surface of PET plastic having a diameter of 1 cm and a length of 10 cm to form a coating film. The antimicrobial properties, conductivity, surface condition and film strength of the thus-produced plastics were measured as described above.

&Lt; Comparative Example 1 &

0.1wt% of copper sulfide was mixed with IPA (isopropyl alcohol) and stirred at room temperature for 1 hour to prepare a coating solution. Using this coating solution, dip coating was performed on LDPE plastic having a diameter of 1 cm and a length of 10 cm. The coated LDPE plastic was first dried at 50 ° C for 1 hour and then subjected to a secondary heat treatment at 400 ° C for 30 minutes. At this time, the thickness of the coating film was approximately 500 angstroms. The antimicrobial properties, conductivity, surface condition and film strength of the thus-produced plastics were measured as described above.

&Lt; Comparative Example 2 &

The antimicrobial activity, the conductivity, the surface condition and the film strength of the surface of LDPE having a diameter of 1 cm and a length of 10 cm without a copper sulfide coating film were measured as described above.

Table 1 compares the antibacterial properties (dog / mL), the conductivity (Ωcm), the surface state (pieces / 100 cm 2) and the film strength (kg / cm 2) of the plastics of Examples 1 to 3 and Comparative Examples 1 and 2 of the present invention It is.

division

Fla
stick
Copper sulfide
Presence
coating
Way Properties Antimicrobial activity Conductivity Surface condition Film strength room
city
Yes One LDPE ○ deposition ○ ○ ○ ○ 2 PP ○ deposition ○ ○ ○ ○ 3 PET ○ deposition ○ ○ ○ ○ ratio
School
Yes One LDPE ○ Wet
apply ○ × × × 2 LDPE / / × × × ×

According to Table 1, Examples 1 to 3 and Comparative Example 1 in which a copper sulfide coating film was formed by a vapor deposition method, a wet coating method and a vapor deposition method were excellent in antimicrobial activity and conductivity. It was found that the copper sulfide coating film showed high antibacterial activity and conductivity regardless of the coating method. On the other hand, in Comparative Example 2 in which the copper sulfide coating film was not present, the antibacterial properties were remarkably deteriorated to such an extent that measurement was impossible. However, when the coating was performed by wet coating instead of the vapor deposition method, the film strength was 100 kg / cm ² or less, and the film strength of the vapor deposition system was larger than 300 kg / cm ² . When the film strength is less than 300 kg / cm ² , it is difficult to apply the plastic to the plastic according to the embodiment of the present invention. In addition, the surface state of the deposited film by the vapor deposition method was superior to the wet coating method.

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

Plastic base material;
A copper based compound deposition film deposited on the surface of the plastic base material; And
And a coating layer disposed between the surface of the plastic base material and the deposition layer and treated with a water dispersion coating liquid containing a conductive polymer emulsion containing a transition metal,
Wherein the chemical structure of the compound is 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 1.5).

The plastic according to claim 1, wherein M is any one selected from S, F and Cl.

The plastic according to claim 1, wherein the compound is copper sulfide.

delete

Preparing a plastic base material;
Applying a surface of the plastic base material with a water dispersion coating liquid containing a conductive polymer emulsion containing a transition metal; And
And depositing a copper-based compound on the surface of the plastic base material,
Wherein the chemical structure of the compound is Cu _x M _y (wherein M is any one selected from the group consisting of groups 15 to 17 in the periodic table, x / y = 0.8 to 1.5).

delete

The aqueous dispersion liquid according to claim 5, wherein the aqueous dispersion liquid contains 0.01 to 3.0 wt% of colloidal transition metal fine particles and 0.01 to 5.0 wt% of at least one emulsion selected from water-soluble polyesters, water-soluble urethane, Wherein the copper-based compound is deposited on the substrate.

The method for producing a plastic deposited with a copper-based compound according to claim 5, wherein the plastic base material is made of a polyurethane resin or a silicone resin.