WO2015167095A1

WO2015167095A1 - Plastic having copper-based compound deposited thereon and preparation method for same

Info

Publication number: WO2015167095A1
Application number: PCT/KR2014/010940
Authority: WO
Inventors: 백승우
Original assignee: (주)비에스써포트
Priority date: 2014-04-28
Filing date: 2014-11-14
Publication date: 2015-11-05
Also published as: KR101564328B1

Abstract

Provided is plastic having copper-based compound deposited thereon and a preparation method for same, the plastic having formed on the surface thereof a coating film that provides conductivity and antibacterial properties and has great film strength. Plastic has a compound deposited on the surface of plastic based material, the compound having the chemical structure of Cu_xM_y (M is any one selected from groups 15-17 in the periodic table, and x/y=0.8-1.5).

Description

Copper-deposited plastics and its manufacturing method

The present invention relates to a plastic and a method for manufacturing the same, and more particularly, to a plastic and a method for manufacturing the same, which provides antimicrobial properties by a conductive copper-based compound and enhances the durability of the deposited film.

Recently, the development of plastic containers having excellent electromagnetic shielding and antistatic properties has been required due to the increased use of expensive equipment that generates a lot of electromagnetic waves. Electromagnetic shielding method using the conductivity is a method of forming a conductive coating film on the surface of the plastic is used a lot. In addition, the use of plastics equipped with antimicrobial activity to prevent bacterial infection is increasing. Antimicrobial activity includes preventing germs from growing or sterilizing them. Various types of plastics, such as textile articles, tubes, trays, bowls, and machine parts, need to simultaneously implement conductivity and antibacterial properties. For example, plastic containers used in hospitals must meet the conductivity for shielding electromagnetic waves and the antibacterial properties for preventing infection of pathogens.

In order to improve the conductivity of plastics, Korean Application No. 2012-7022202 improves the antistatic properties by applying a divalent cation and a phosphate ester salt of a Group 2 element metal. In addition, the Republic of Korea Application Nos. 2011-7014670, 2010-0101700, 2009-0098692 used organic salts having a fluorine group and a sulfonyl group to impart the conductivity of the plastic material. In Korean application No. 2009-7006733, a polymer compound having a PEO chain as a conductive base structure is added to increase the conductivity of a plastic material. However, as in the literature, organic salts having a phosphate ester salt, a fluorine group, and a sulfonyl group can be easily applied to plastics and can easily improve conductivity. However, when hot water is used, the conductivity of the plastic container drops sharply. There is this. In addition, in the case of manufacturing a plastic container by kneading a conductive polymer having a PEO chain, container deformation occurs due to uneven crystallinity and crystal size for each part.

Looking at the prior literature on plastic antimicrobial properties, Korean Patent Registration No. 10-0559405 No. 10-20 parts by weight of sulfur powder having a particle size of 1 ~ 3㎛ kneaded with resin, and Korean Patent Registration No. 10-0766418 No. 1 ~ A 600 nm silver nano powder and titanium dioxide were kneaded with a resin to prepare a plastic product having excellent antibacterial properties. In Korean Patent Registration No. 10-0987728, silver was deposited on the resin surface by sputtering or ion plating, and then the deposited silver was mixed to make antimicrobial yarn. In Korean Patent Registration No. 10-1180117, antimicrobial yarns were prepared by dyeing zinc sulfide nanoparticles and organic antibacterial agents.

However, although it is known that the antibacterial properties of the silver and sulfur components used in the prior literature are excellent, there are many limitations in practical use. In the case of silver, although it has high antibacterial property and convenience, supply price is too high. In the case of sulfur, environmental hazards and processing difficulties have not been solved yet. How to give antimicrobial has not been specifically implemented.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a plastic and a method of manufacturing the same, in which a copper-based compound on which a coating film is formed, which provides conductivity and antimicrobial properties to a surface of the plastic and has a high coating film strength.

Plastics deposited with a copper-based compound for solving the problems of the present invention includes a plastic base material and a copper-based compound deposition 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 group 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 problem of the present invention, a method of manufacturing a plastic on which a copper-based compound is deposited first prepares a plastic base material. Thereafter, a copper 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 group 15 to 17 in the periodic table, x / y = 0.8 to 1.5).

In the manufacturing method of the present invention, the surface of the plastic may be treated with a conductive polymer emulsion solution containing a transition metal before the depositing step. An aqueous dispersion coating liquid containing 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 a water-soluble polyester, a water-soluble urethane, and a water-soluble acrylic may be applied to the surface of the plastic.

According to the plastic on which the copper-based compound of the present invention is deposited and its manufacturing method, by depositing a compound containing copper sulfide on the surface of the plastic, it has high conductivity, antimicrobial activity and coating film strength. Copper-based compound formed by the deposition is excellent in antibacterial, it can be applied to improve the antimicrobial properties of plastics.

1 is an XRD graph showing the crystal structure of copper sulfide prepared by the present invention.

Figure 2 is a photograph of copper sulfide deposited on the plastic produced by the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments described below may be modified in 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 more completely explain the present invention to those skilled in the art.

The copper compound applied to the embodiment of the present invention is preferably copper sulfide (CuS). Copper sulfide was synthesized by reacting copper sulfide (CuSO ₄ ) with a salt selected from sulfide salts, fluoride salts, and chloride salts in an aqueous solution at a temperature of 10 to 80 ° C. in a molar ratio of 1: 1. 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 were limited so that the ratio of x / y is 0.8 ~ 1.5. Examples of the sulfide salts that can be used in the present invention include sodium sulfide, iron sulfide, potassium sulfide, zinc sulfide, and the like, and examples of the fluoride salt include sodium fluoride, iron fluoride, potassium fluoride, and zinc fluoride. Examples of the chloride salt include sodium chloride, iron chloride, potassium chloride, and zinc chloride. At this time, the antibacterial activity of the copper sulfide synthesized using sodium sulfide and copper sulfate was the best.

When the reaction temperature is 10 ° C. or less, when synthesizing the copper-based nanoparticles, the reactivity of copper sulfate and salt is decreased, but the antibacterial property is good. However, the yield of producing copper sulfide is poor. When the reaction temperature is 80 ° C. or higher, the reaction rate is too high, the density of crystals on the surface of the copper sulfide increases, and the concentration of copper increases, and the antimicrobial activity decreases. In addition, when the bonding ratio of x / y of the copper-based nanoparticles is 0.8 or less, the concentration of sulfur (S) becomes too high and the antibacterial property is good. However, the copper sulfide has poor chemical stability. When it is 1.5 or more, the concentration of copper increases and the antimicrobial activity decreases.

After making a deposition target using the copper sulfide prepared in the above manner, it is physically deposited on the surface of the plastic. In order to increase the coating strength in the deposition, it is preferable to treat the surface of the plastic with a conductive polymer emulsion solution containing a transition metal before deposition. An aqueous dispersion coating solution containing 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 a water-soluble polyester, a water-soluble urethane, and a water-soluble acryl is applied to the surface of the plastic. The dispersion coating liquid can increase the deposition strength. Adjust so that the residual solid of the aqueous dispersion coating solution is 0.001 ~ 0.1g / m ² . The deposition is heated to maintain the vapor pressure of the metal 10 ^-2 ~ 10 ^-1 in a vacuum condition of 10 ^-5 ~ 10 ^-3 torr and copper sulfide is deposited to a thickness of 300 ~ 600Å on the plastic surface. The deposition intensity of the deposition layer is preferably maintained at least 60g / 25mm or more.

Plastics can be both thermoplastic resins and thermosetting resins, of which thermoplastic resins which are advantageous for molding are more preferred. The thermoplastic resin may mainly be polyethylene terephthalate, polylactic acid, polyethylene, polypropylene, polycarbonate, polymethyl methacrylate, polyvinyl chloride, polyurethane, silicone, or the like. The thermosetting resin is preferably an epoxy resin or the like. Polyurethanes are more preferred because they are flexible, nontoxic, and have 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 the invention and are not limited thereto. Performance evaluation of the plastic produced in Examples and Comparative Examples of the present invention was carried out by the following method. Hereinafter, the copper sulfide will be mainly described among the compounds.

(1) Surface condition of coating film

The surface state of the coating film was observed under a microscope and the number of protrusions and undeposited films per 10 cm × 10 cm was evaluated to evaluate the presence or absence of protrusions on the surface of the coating film.

○: 1 or less

△: 2 to 4

×: 5 or more

(2) Coating thickness of coating film

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

(3) Coating film strength of coating film

The coating film strength of the coating film was controlled by the film adhesion, and the adhesion strength was measured by using a pull down breaking tester (Pull Down Breaking Point Tester, Phpto Teohnioa, USA) with a load of 90 kg / sec.

○: 300 kg / cm ² or more

△: 100-300 kg / cm ²

×: 100 kg / cm ² or less

(4) antibacterial

Using the Escherichia coli (ATCC 25922) as a strain, the test bacteria were contacted with the specimens, and then allowed to stand and incubated at 25 ° C for 24 hours. The antimicrobial activity is excellent when the number of bacteria is less than 10 ⁷ , and is indicated by ○. If the number of Escherichia coli (ATCC 25922) bacteria was more than 10 ¹⁰ per mL and measurement was impossible, it was indicated as a side payment.

(5) conductivity

The conductivity of the plastic container was evaluated by measuring the surface resistance using an insulation resistance meter of Hewlett-Packard Co., Ltd. at 23 ° C., 60% relative humidity, and 500 V applied voltage.

○: 10 ² Ω × cm or more

×: 10 ² Ω × cm or less

1 mol each of CuSO ₄ and Na ₂ S was added to distilled water, stirred for 30 minutes, and then placed in an isothermal reactor at 50 ° C. for 30 minutes to synthesize copper sulfide fine particles, thereby preparing a deposition target. An aqueous dispersion coating liquid containing 0.5 wt% of colloidal transition metal fine particles and 1.0 wt% of an emulsion of water-soluble polyester was applied to the surface of an LDPE plastic having a diameter of 1 cm and a length of 10 cm. The residual solids of the aqueous dispersion coating solution were adjusted to 0.05 g / m ² . Thereafter, the deposition target was physically evaporated to form a coating film on the plastic surface. The thickness of the deposited copper sulfide was 400 mm 3.

The crystal structure of the deposited copper sulfide had a unique structure of copper sulfide as shown in FIG. 1. According to FIG. 1, sulfur did not have a crystal structure, and thus peaks did not appear, but copper showed peaks at 55 degrees, 65 degrees, 99 degrees, 125 degrees, and 137 degrees. The fine particles were observed by X-ray powder diffraction (XRD, XD-3A, Shimadzu, Japan). In addition, the coating film formed on the LDPE plastic was as shown in FIG. The antimicrobial, electrical conductivity, surface state and coating strength of the plastics thus prepared were measured as set forth above.

As in Example 1, copper sulfide was deposited on the surface of PP plastic having a diameter of 1 cm and a length of 10 cm to form a coating film. The antimicrobial, electrical conductivity, surface state and coating strength of the plastics thus prepared were measured as set forth above.

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, electrical conductivity, surface state and coating strength of the plastics thus prepared were measured as set forth above.

Comparative Example 1

Copper sulfide 0.1wt% was mixed with IPA (isopropyl alcohol), and stirred at room temperature for 1 hour to prepare a coating solution. The coating solution was dip coated onto LDPE plastics 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 secondary annealing at 400 ° C. for 30 minutes. At this time, the thickness of the coating film was about 500 kPa. The antimicrobial, electrical conductivity, surface state and coating strength of the plastics thus prepared were measured as set forth above.

Comparative Example 2

The antimicrobial, conductivity, surface state, and coating 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 antimicrobial (dog / mL), conductivity (Ωcm), surface state (dog / 100cm2) and coating strength (kg / cm2) of the plastics of Examples 1 to 3 and Comparative Examples 1 and 2 of the present invention. It is.

Table 1

division		plastic	Copper sulfide presence	Coating method	Properties
division		plastic	Copper sulfide presence	Coating method	Antimicrobial activity	Conductivity	Surface condition	Coating strength
Example	One	LDPE	○	deposition	○	○	○	○
	2	PP	○	deposition	○	○	○	○
	3	PET	○	deposition	○	○	○	○
Comparative example	One	LDPE	○	Wet coating	○	×	×	×
Comparative example	2	LDPE	Of	Of	×	×	×	×

According to Table 1, Examples 1-3 and Comparative Example 1 which formed the copper sulfide coating film by the vapor deposition method, the wet coating method, and the vapor deposition method were excellent in antimicrobial activity and electroconductivity. The copper sulfide coating film was found to exhibit high antimicrobial activity and conductivity regardless of the coating method. On the contrary, Comparative Example 2 without the copper sulfide coating film deteriorated antimicrobial so much that measurement was impossible. However, when coated with a wet coating rather than a deposition method, the coating film strength was 100 kg / cm ² or less, and the coating film strength of the deposition method was greater than 300 kg / cm ² . If the coating film strength is less than 300 kg / cm ² , it is difficult to apply 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.

As mentioned above, although the present invention has been described in detail with reference to preferred embodiments, the present invention is not limited to the above embodiments, and various modifications may be made by those skilled in the art within the scope of the technical idea of the present invention. It is possible.

Claims

Plastic base material; And

It includes a copper-based compound deposition film deposited on the surface of the plastic base material,

The chemical structure of the compound is Cu x M y (M is any one selected from group 15 to 17 in the periodic table, x / y = 0.8 to 1.5) a plastic on which a copper-based compound is deposited.
The method of claim 1, wherein the copper is a copper-based compound deposited plastic, characterized in that any one selected from S, F, Cl.
The plastic of claim 1, wherein the compound is copper sulfide.
Preparing a plastic base material; And

Depositing a copper compound on the surface of the plastic base material;

The chemical structure of the compound is Cu x M y (M is any one selected from group 15 to 17 in the periodic table, x / y = 0.8 to 1.5) A method for producing a plastic on which a copper-based compound is deposited.
The method of claim 4, wherein the surface of the plastic is treated with a conductive polymer emulsion solution containing a transition metal before the depositing step.
The aqueous dispersion coating liquid according to claim 4, wherein the surface of the plastic 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 a water-soluble polyester, a water-soluble urethane, and a water-soluble acryl. Method for producing a plastic on which a copper-based compound is deposited, characterized in that the coating.
The method of claim 4, wherein the plastic base material is made of a polyurethane resin or a silicone resin.