WO2007100172A1

WO2007100172A1 - Functional master batch and method of preparing the same

Info

Publication number: WO2007100172A1
Application number: PCT/KR2006/001537
Authority: WO
Inventors: Ji-Chan Hwang
Original assignee: Gnc Glotech Co., Ltd.
Priority date: 2006-02-28
Filing date: 2006-04-24
Publication date: 2007-09-07

Abstract

Disclosed are a functional master batch and a method of preparing the same. The present invention provides the functional master batch including an antimicrobial agent and a polymer resin, wherein the antimicrobial agent includes a carrier composed of titanium dioxide (TiO2 ) and zinc oxide (ZnO); and silver (Ag) and magnesium oxide (MgO) supported in the carrier. The functional master batch according to the present invention can prevent the deterioration of silver and magnesium oxide and the detachment and loss of silver caused by use of other fiber processing materials such as various surfactants which are added in the fiber processing process, and the functional master batch containing a small amount of silver can also exhibit remarkable antibiotic and antibacterial activities and a deodorant activity since the zinc oxide, the titanium dioxide and the magnesium oxide serve to assist activity of the silver.

Description

FUNCTIONAL MASTER BATCH AND METHOD OF PREPARING THE SAME

Technical Field

[1] The present invention relates to a functional master batch and a method of preparing the same, and more particularly to a functional master batch having remarkable antibiotic and antibacterial activities and a deodorant activity and being able to be manufactured at a low cost, and a method of preparing the same.

[2]

Background Art

[3] The term "master batch" is referred to as a blend of additives prepared by mixing a high concentration of compounding agents such as an antimicrobial agent with polymer resins, the master batch being used to improve dispensity of the compounding agents and prevent their scattering, and the compounding agents being added to chemical fibers or petrochemical products in producing them in order to provide certain activities to them.

[4] In order to exhibit antibiotic and antibacterial activities and a deodorant activity, master batches containing antibiotic inorganic materials such as metal or ceramic were mainly used to manufacture chemical fibers or petrochemical products. As one of the most representative antibiotic inorganic materials, silver (Ag) has been mainly used because of its excellent antibiosis.

[5] As the representative method for preparing a silver-containing master batch, there are a method for preparing a master batch by incorporating nano silver powder into polymer resin, followed by undergoing stirring, extrusion, cooling and cutting processes; and a method for preparing a master batch by adding colloid silver to a polymer resin, followed by undergoing stirring, extrusion, cooling and cutting processes while drying the resultant mixture.

[6] However, the master batch containing nano silver powder should have desired performances in consideration of endowment with functionality, good dispersion, low deterioration and easiness in use. For this purpose, problems such as homogeneity, color and dispersity of the master batch should be solved in the case of the method using silver powder so as to prevent broken warp yarns in the production process of yarns. In the case of the method using silver colloid, the master batch requires a perfect reduction method to solve problems such as yellowing, and process problems should be solved to remove moisture completely while stirring by mixing a liquid colloid with polymer resin. [7] If silver is used as the antibiotic material, the silver may be oxidized or deteriorated by use of a fiber processing material such as various surfactants which are added to process the fiber in the conventional methods. Actually, a low denier thread has high antibiosis, but the silver may be oxidized, detached and lost by a large amount of acid or basic solvent in a dyeing process of thread, which is prepared by knitting or weaving the low-denier thread. Therefore, the manufactured products do not maintain antibiotic and antibacterial activities.

[8] For the above reasons, although nano silver has remarkable antibiotic and antibacterial activities, the conventional master batches containing nano silver did not have sufficient antibiosis. Therefore, a master batch having remarkable antibiosis remains to be developed.

[9]

Disclosure of Invention Technical Problem

[10] Accordingly, the present invention is designed to solve the problems of the prior art, and therefore it is an object of the present invention to provide a functional master batch having remarkable antibiotic and antibacterial activities and a deodorant activity and being able to be manufactured at a low cost.

[11] It is another object of the present invention to provide a method of preparing a functional master batch having remarkable antibiotic and antibacterial activities and a deodorant activity, wherein the functional master batch may be manufactured in a simple and economic manner.

[12]

Technical Solution

[13] In order to accomplish the above objects, the present invention provides a functional master batch including an antimicrobial agent and a polymer resin, wherein the antimicrobial agent includes a carrier composed of titanium dioxide (TiO ) and zinc oxide (ZnO); and silver (Ag) and magnesium oxide (MgO) supported in the carrier.

[14] The functional master batch according to the present invention has remarkable antibiotic and antibacterial activities and a deodorant activity, and may be manufactured at a low cost.

[15] In the functional master batch of the present invention, the titanium dioxide and the zinc oxide preferably have a particle diameter of 0.15 to 0.25 D, and the silver and the magnesium oxide preferably have a particle diameter of 1 to 200 nm. Also, the antimicrobial agent includes titanium dioxide, zinc oxide, silver and magnesium oxide, wherein the titanium dioxide preferably has a content of 50 to 60 parts by weight; the zinc oxide preferably has a content of 30 to 40 parts by weight; the silver preferably has a content of 10 to 15 parts by weight; and the magnesium oxide preferably has a content of 1 to 5 parts by weight, based on the total content of the antimicrobial agent. In addition, a content ratio of the antimicrobial agent preferably ranges from 3 to 10 % by weight, based on the total weight of the functional master batch.

[16] And, the method of preparing a functional master batch according to the present invention includes (Sl) preparing a mixed powder by mixing titanium dioxide powder with zinc oxide powder while stirring; (S2) mixing magnesium oxide in sol state with the mixed powder and conducting a drying process thereto, and then mixing silver in sol state with the mixed powder and conducting a drying process thereto to prepare a powder of an antimicrobial agent; (S3) melting a polymer resin and mixing the powder of the antimicrobial agent with the melted polymer resin while stirring to prepare a melted polymer resin containing the antimicrobial agent; and (S4) conducting an extruding process, an injection molding process, a cooling process and a cutting process with melted polymer resin containing the antimicrobial agent.

[17] According to the method of preparing a functional master batch according to the present invention, the functional master batch having remarkable antibiotic and antibacterial activities and a deodorant activity may be easily manufactured at a low cost.

[18]

[19] Hereinafter, preferred embodiments of the functional master batch according to the present invention will be described in detail. Prior to the description, it should be understood that the terms used in the specification and appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Therefore, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.

[20] The conventional master batches containing nano silver as an antimicrobial agent has shortcomings such discoloration, oxidation and loss of silver, but the functional master batch according to the present invention has remarkable antibiotic and antibacterial activities and a deodorant activity by solving the shortcomings. The functional master batch according to the present invention includes a polymer resin and an antimicrobial agent.

[21] The polymer resin used for industrial application may be used without any limitation. Representative examples of the polymer resin includes, but is not limited to, nylon, polyethylene (PE), polypropylene (PP), polyester, polyethylene terephthalate (PET), polyamide (PA), polycarbonate (PC), polyurethane (PU), acrylonitrile butadien styrene (ABS), high impact polystyrene (HIPS), polystyrene (PS), high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyvinyl chloride (PVC), polypropylene oxide (PPO), and polybutylene terephthalate (PBT).

[22] The antimicrobial agent includes silver (Ag), magnesium oxide (MgO), titanium dioxide (TiO ) and zinc oxide (ZnO). The silver has remarkable antibiotic and antibacterial activities and a deodorant activity, and the magnesium oxide, the titanium dioxide and the zinc oxide serve to assist the activities of the silver, thereby to maximize the activities of silver due to their synergic effect with the silver.

[23] In particular, if the silver and the magnesium oxide are supported in the titanium dioxide and the zinc oxide, they are not deteriorated by use of other fiber processing materials such as various surfactants which are added in the fiber processing process, and the detachment and loss of the silver and the magnesium oxide may be prevented in a dyeing process because they are fixed in the carrier. Also, if the zinc oxide and the titanium dioxide are used together as the carrier, particle sizes of the final powder of the antimicrobial agent may be more easily adjusted in the mass production of the antimicrobial agent, their photocatalyst function may more strongly assisted and their agitation and dispersion may be made more easily in mixing the polymer resin with the antimicrobial agent than if the titanium dioxide is used alone as the carrier. In addition, the magnesium oxide may function as a catalyst which enhances photoactivity and activates a function of the silver so as to further improve antimicrobial activity, etc.

[24] Moreover, the master batch according to the present invention has an ivory color since the silver tinged with dark brown and grey tones is supported in whitish titanium dioxide, and therefore the master batch containing the antimicrobial agent may be widely used in the field of apparel industry since it has a good esthetic effect .

[25] There is no particular limitation on particle diameters of the titanium dioxide and the zinc oxide in the antimicrobial agent, but the particle diameters preferably range from 0.15 to 0.25 D in order to enhance an antimicrobial activity/unit area by increasing dispersity and a specific surface area. Also, there is no particular limitation on particle diameters of the silver and the magnesium oxide, but the particle diameters preferably range from 1 to 200 nm in order to enhance an antimicrobial activity/unit area by increasing dispersity and a specific surface area.

[26] There is no particular limitation on contents of the titanium dioxide, the zinc oxide, the silver and the magnesium oxide in the antimicrobial agent, but the contents may be suitably adjusted within the scope and spirit of the present invention without departing from the object of the present invention. In order to maximize antibiotic, antibacterial and deodorant activities, the titanium dioxide preferably has a content of 50 to 60 parts by weight, the zinc oxide preferably has a content of 30 to 40 parts by weight, the silver preferably has a content of 10 to 15 parts by weight, and the magnesium oxide preferably has a content of 1 to 5 parts by weight. In the meantime, a dispersing agent may be added to the master batch, if necessary. In this case, a content of the dispersing agent is preferably very low at less than 0.01 %, based on the total amount of the antimicrobial agent.

[27] In the functional master batch according to the present invention, there in no particular limitation on a content of the antimicrobial agent, but the content preferably ranges from 3 to 10 % by weight on the basis of the total weight of the master batch, considering its dispersity. In the meantime, a dispersing agent may be further added to the master batch to disperse the antimicrobial agent homogeneously. In this case, a content of the dispersing agent is preferably low at less than 0.01 %, based on the total amount of the antimicrobial agent.

[28] As described above, in order to improve significantly antibiotic, antibacterial and deodorant activities, the functional master batch according to the present invention may be widely used to manufacture chemical fibers or petrochemical products with various polymer resins. The polymer resins includes, but is not limited to, nylon, polyethylene (PE), polypropylene (PP), polyester, polyethylene terephthalate (PET), poly amide (PA), polycarbonate (PC), polyurethane (PU), acrylonitrile butadien styrene (ABS), high impact polystyrene (HIPS), polystyrene (PS), high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyvinyl chloride (PVC), polypropylene oxide (PPO), and polybutylene terephthalate (PBT).

[29] Hereinafter, the above-mentioned method of preparing a functional master batch according to the present invention will be described in detail. However, the preparation method, as described later, is just a preferable example for the purpose of preparation of the functional master batch according to the present invention, not intended to limit the scope of the present invention.

[30] At first, a titanium dioxide powder is mixed with a zinc oxide powder, and the resultant mixture is stirred to prepare a mixed powder. There is no particular limitation on particle diameters of the titanium dioxide powder and zinc oxide powder, but the particle diameters preferably range from 0.15 to 0.25 D in order to enhance an antimicrobial activity/unit area by increasing dispersity and specific surface area.

[31] Next, the mixed powder is replaced with magnesium oxid a sol state and a drying process is conducted, and then the dried mixture powder is replaced with silver in a sol state and a drying process is conducted to prepare a powder of an antimicrobial agent. Here, the replacement process of magnesium oxide may be carried out by mixing the mixed powder with magnesium oxide in a sol state, followed by stirring and aging the resultant mixture, and the replacement process of silver may be carried out in the same manner as in the replacement process of magnesium oxide. In the above replacement processes, there is no particular limitation on particle diameters of the silver and th magnesium oxide, but the particle diameters preferably range from 1 to 200 nm in order to enhance an antimicrobial activity/unit area by increasing dispersity and specific surface area.

[32] There is no particular limitation on contents of the titanium dioxide, the zinc oxide, the silver and the magnesium oxide which are all added in the two replacement processes, but the titanium dioxide is preferably present at a content of 50 to 60 parts by weight, the zinc oxide is preferably present at a content of 30 to 40 parts by weight, the silver is preferably present at a content of 10 to 15 parts by weight, and the magnesium oxide is preferably present at a content of 1 to 5 parts by weight in order to maximize antibiotic, antibacterial and deodorant activities.

[33] After the powder of the antimicrobial agent is prepared, a polymer resin is melted, and the powder of the antimicrobial agent is then mixed with the melted polymer resin while stirring to prepare a melted polymer resin containing the antimicrobial agent. Representative examples of the polymer resin includes, but is not limited to, nylon, polyethylene (PE), polypropylene (PP), polyester, polyethylene terephthalate (PET), poly amide (PA), polycarbonate (PC), polyurethane (PU), acrylonitrile butadien styrene (ABS), high impact polystyrene (HIPS), polystyrene (PS), high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyvinyl chloride (PVC), polypropylene oxide (PPO) and polybutylene terephthalate (PBT). And, all industrially used polymer resins may be used herein. When the powder of the antimicrobial agent is added to the melted polymer resin, a dispersing agent may be further added thereto to disperse the antimicrobial agent homogeneously. In this case, a content of the dispersing agent is preferably low at less than 0.01 %, based on the total amount of the antimicrobial agent.

[34] Finally, the melted polymer resin containing the antimicrobial agent, prepared through the above process, is extruded, injected, cooled and cut to prepare a functional master batch according to the present invention.

[35]

Advantageous Effects

[36] The functional master batch according to the present invention has remarkable antibiotic and antibacterial activities and a deodorant activity since it includes magnesium oxide, titanium dioxide and zinc oxide, as well as an antimicrobial agent. In particular, the functional master batch according to the present invention may be useful to prevent the deterioration, detachment and loss of silver by use of other fiber processing materials such as various surfactants, which are added in the fiber processing process, by supporting silver and magnesium oxide in titanium dioxide and zinc oxide. Also, the antibiotic, antibacterial and deodorant activities of chemical fibers and plastic products, manufactured with the master batch of the present invention, may be highly improved by enhancing antimicrobial activity of magnesium oxide, zinc oxide and titanium dioxide by themselves and antimicrobial activity by activation of sliver ions.

[37] According to the method of preparing a functional master batch according to the present invention, the functional master batch having remarkable antimicrobial activity may also be easily manufactured at a low cost.

[38]

Best Mode for Carrying Out the Invention

[39] Hereinafter, preferred embodiments of the present invention will be described in detail. However, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention. The preferred embodiments of the present invention will be described in detail for the purpose of better understandings, as apparent to those skilled in the art.

[40]

[41] Example 1

[42] Titanium dioxide powder (a mean particle diameter: 0.2 D) and zinc oxide (a mean particle diameter: 0.2 D) were mixed with each other to prepare a mixed powder. Then, the prepared mixed powder was mixed with magnesium oxide in a sol state (a mean particle diameter: 100 nm), and the resultant mixture was then dried and aged at 80 ⁰C to replace the magnesium oxide. Then, the replaced mixture was mixed with silver in a sol state (a mean particle diameter: 100 nm), and the resultant mixture was dried and aged at 80 ⁰C to replace the silver, thereby to prepare a powder of an antimicrobial agent. In the preparation of the antimicrobial agent, the titanium dioxide, the zinc oxide, the silver and the magnesium oxide were used at contents of 40 % by weight, 45 % by weight, 10 % by weight and 5 % by weight, respectively, based on the total weight of the powder of the antimicrobial agent. The powder of the antimicrobial agent prepared thus were measured for a mean particle diameter, and the measured mean particle diameter was about 250 D.

[43] Next, nylon resin was melted at 150 ⁰C in a mixing agitator, and the previously prepared powder of the antimicrobial agent was added to the mixing agitator, and then mixed with the melted polymer resin for 20 minutes while stirring. Then, the resultant mixture was heated to 180 ⁰C, and a wax dispersing agent was added to the mixing agitator and stirred for 30 minutes. And, an injection product to be extruded through nozzles was quenched and cut to prepare a functional master batch. In the above production process of the master batch, the contents of the polymer resin, the antibiotic powder and the dispersing agent were 96.99 % by weight, 3 % by weight and 0.01 % by weight, respectively.

[44] Finally, a thread having a thickness of 3 deniers was made by adding the master batch prepared thus to a nylon resin (a major resin). In the thread, the content of the master batch was 3 % by weight, based on the total weight of the thread.

[45]

[46] Example 2

[47] A master batch was produced in the same manner as in Example 1, except that a polyester resin was used at a content of 3 % by weight in stead of the nylon resin. Then, a thread having a thickness of 1 denier was made by adding the master batch to the polyester resin. In the thread, the content of the master batch was 3 % by weight, based on the total weight of the thread.

[48]

[49] Measurement of Antimicrobial activity

[50] The threads prepared in Examples 1 and 2 were tested for antimicrobial activity at the FITI Testing & Research Institute in Korea. As a result, the two threads showed the decreased number of the bacteria by 99.9 % or more. Also, two fabrics were woven with the two threads and dyed, and the dyed fabrics were tested for antimicrobial activity again. As a result, it was revealed that the two fabrics showed the decreased number of the bacteria by 99.9 % or more.

[51]

Industrial Applicability

[52] The functional master batch according to the present invention has remarkable antibiotic and antibacterial activities and a deodorant activity since it includes magnesium oxide, titanium dioxide and zinc oxide, as well as an antimicrobial agent. In particular, the functional master batch according to the present invention may be useful to prevent the deterioration, detachment and loss of silver by use of other fiber processing materials such as various surfactants, which are added in the fiber processing process, by supporting silver and magnesium oxide in titanium dioxide and zinc oxide. Also, the antibiotic, antibacterial and deodorant activities of chemical fibers and plastic products, manufactured with the master batch of the present invention, may be highly improved by enhancing antimicrobial activity of magnesium oxide, zinc oxide and titanium dioxide by themselves and antimicrobial activity by activation of sliver ions.

[53] According to the method of preparing a functional master batch according to the present invention, the functional master batch having remarkable antimicrobial activity may also be easily manufactured at a low cost.

Claims

[1] A functional master batch including an antimicrobial agent and a polymer resin, wherein the antimicrobial agent comprises: a carrier composed of titanium dioxide (TiO ) and zinc oxide (ZnO); and silver (Ag) and magnesium oxide (MgO) supported in the carrier. [2] The functional master batch according to claim 1, wherein the titanium dioxide and the zinc oxide have a particle diameter of 0.15 to 0.25 D. [3] The functional master batch according to claim 1, wherein the silver and the magnesium oxide have a particle diameter of 1 to 200 nm. [4] The functional master batch according to claim 1, wherein the titanium dioxide is present at an amount of 50 to 60 parts by weight, the zinc oxide is present at an amount of 30 to 40 parts by weight, the silver is present at an amount of 10 to 15 parts by weight, and the magnesium oxide is present at an amount of 1 to 5 parts by weight, based on the total content of the antimicrobial agent. [5] The functional master batch according to claim 1, wherein the antimicrobial agent has a content of 3 to 10 % by weight, based on the total weight of the functional master batch. [6] A method of preparing a functional master batch, the method comprising:

(51) preparing a mixed powder by mixing titanium dioxide powder with zinc oxide powder while stirring;

(52) mixing magnesium oxide in sol state with the mixed powder and conducting a drying process thereto, and then mixing silver in sol state with the mixed powder and conducting a drying process thereto to prepare a powder of an antimicrobial agent;

(53) melting a polymer resin and mixing the powder of the antimicrobial agent with the melted polymer resin while stirring to prepare a melted polymer resin containing the antimicrobial agent; and

(54) conducting an extruding process, an injection molding process, a cooling process and a cutting process with melted polymer resin containing the antimicrobial agent.