KR101678314B1 - Manufacturing Method of Antibacterial Masterbatch Using Ionized Calcium Powder - Google Patents

Abstract

The present invention relates to a manufacturing method of an antibacterial masterbatch using ionized calcium powder and, more specifically, to a manufacturing method of a masterbatch having excellent antibacterial properties, comprising the steps of: manufacturing shells, which have been through foreign substance removing, washing, drying, cooling, and pulverizing processes, into ionized calcium powder; treating the powder with a surfactant; mixing the same; and molding a masterbatch.

Description

{Manufacturing Method of Antibacterial Masterbatch Using Ionized Calcium Powder Using Ionized Calcium Powder}

The present invention relates to an antibacterial masterbatch manufacturing method using an ionized calcium powder. More specifically, the present invention relates to an antibacterial masterbatch manufacturing method using an ionized calcium powder, and more particularly, to a method for manufacturing an antibacterial masterbatch using an ionized calcium powder, A mixing step, and a master batch forming step to produce a master batch having a very high antibacterial property.

Recently, resin compositions having antimicrobial properties, so-called antimicrobial resin compositions, have been widely used for building materials, household appliances, miscellaneous goods, packing materials, food manufacturing facilities, drug manufacturing facilities, medical facilities and the like.

The antibacterial agent contained in such an antimicrobial resin composition is highly suitable as an inorganic antibacterial agent because it has higher safety than the organic antibacterial agent, has an antibacterial effect for a long period of time, and is excellent in heat resistance.

These antimicrobial techniques can be divided into a technology group for forming a coating film that gives antimicrobial activity to the surface of a product and a technology group for forming an antimicrobial product including a material showing antibacterial activity in a raw material.

A technique of forming an antimicrobial coating film on the surface of a product has a problem in that the antimicrobial performance is extinguished when the coating film is damaged and the antibacterial performance itself is not constant. In addition, the technology for molding the product containing the antimicrobial material into the raw material is advantageous in that the antibacterial performance is maintained as compared with the coating technology, but the antibacterial ability is not sufficiently realized or the product is difficult to manufacture.

Korean Patent No. 10-0483075 discloses a method for producing a functional calcium oxide, and more particularly, to a method for producing a functional calcium oxide, comprising the steps of: a) primary calcining a calcium-containing material at a temperature of 1,000 ° C to 1,400 ° C for 2 to 6 hours; b) pulverizing the calcined calcium oxide (CaO) to produce a calcium oxide powder; c) adding inorganic acid and water to the calcium oxide powder to prepare a hydrated lime solution; d) stirring and aging the hydrated lime solution; e) filtering and drying the aged hydrated lime solution; And f) secondary calcination of the dried calcium oxide under the same temperature and time conditions as in the step a). The functional calcium oxide maintains a stable crystalline state and is easy to store , A deodorant for decomposing odorous substances by adding various functional metal substances, and an antibacterial agent for killing various bacteria and fungi. However, it has been reported that a functional substance is added to a functional calcium oxide powder to show functionality, There is a problem that it is not verified that it can be used in a food product with confidence even though it is recognized.

Korean Patent Registration No. 10-0483075 (Apr. 4, 2005)

Accordingly, the technical problem to be solved by the present invention is to provide a method for manufacturing a master batch, which comprises washing the shell with alkaline water and coating the powder with a surfactant to obtain a more excellent antibacterial performance, And a method for producing a master batch having an antibacterial function.

Another object of the present invention is to provide an antimicrobial masterbatch prepared by the above method.

In order to solve the above-mentioned problems and to achieve the object, the present invention provides an antimicrobial masterbatch manufacturing method using ionized calcium powder, comprising the steps of: (S1) preparing an ionized calcium powder to produce an ionized calcium powder using a shell as a raw material; A surfactant treatment step (S2) for lowering the surface polarity of the inorganic powder particles by surface-treating the inorganic powder particles formed in the ionized calcium powder production step (S1) with a cationic surfactant; The powder having been subjected to the surfactant treatment step may be used in an amount of 1 to 50% by weight, and may be any one selected from the group consisting of polyethylene, polypropylene, polyurethane, acrylonitrile-butadiene-styrene resin, silicone rubber and thermoplastic polyurethane (TPU) (S3) in which the synthetic resin or rubber is mixed; And a master batch forming step (S4) of molding the resultant obtained through the mixing step into a spherical or chip form.

 In the ionized calcium powder production step (S1), the rotation speed, the shell input amount and the calcination temperature of the calcination furnace are controlled by using a cylindrical calcination furnace which is installed downwardly inclined and rotated by a driving device and maintains a high temperature state, And a sintering step (S14) for separately preparing an ionizing calcium agent for food and industrial according to the purity of the ionized calcium agent.

The sintering step (S14) is carried out in such a manner that the sintering furnace is thermally insulated by refractory bricks, the length is 18,000 mm and the inside diameter thereof is 900 mm, the rotational speed of the calcining furnace is 35 to 40 rpm, the input amount of shell is 500 kg / And a shell having a purity of 95 to 99% by retaining the shell in the calcining furnace for 30 to 45 minutes at 1,100 to 1,200 ° C.,

When the rotary speed of the calcination furnace is 30 to 35 rpm, the shell amount is 300 kg / hr, and the calcination temperature is 1,200 ° C or more, the shell is kept in the calcination furnace for 45 to 90 minutes to produce an industrial ionized calcium powder having a purity of calcium of 99% .

The cationic surfactant used in the surfactant treatment step (S2) is 99% pure and has 12-20 carbon atoms, and is any one of CTAB (Cetyl trimethylammonium bromide) and CTAC (cetyl trimethylammonium chloride).

The shell is subjected to the foreign substance removing step S11 and the washing step S12 three times and the drying step S13 before the firing step S14 is entered.

A cooling step (S15) in which the shell obtained through the firing step (S14) is quenched to room temperature, and a pulverizing step (S16) in which the particle size is pulverized to a size of 3-8 mu m.

In the cleaning step S12, an ultrasonic cleaning method using a frequency higher than an audible frequency is used, and alkaline water having a pH of 8.5-9.0 is used as cleaning water.

The alkaline water is made by passing the ground water through a filter filled with a fine mesh of clathrate powder.

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The polyethylene is either LLDPE (Linear LDPE), HDPE or LDPE.

The masterbatch prepared by the method of producing the antimicrobial masterbatch using the ionized calcium powder of the present invention was prepared by using a natural material called shell, such as a shell or the like, with a cationic surfactant added thereto to have excellent antibacterial performance, So that it can be safely used as a container for food or the like.

In addition, it is possible to reuse the unprocessed and discarded local special products such as cockles and shells of oysters, thereby helping to use available resources and solve environmental problems.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view illustrating a method of manufacturing an antimicrobial masterbatch using the ionized calcium powder of the present invention. FIG.
2 is a view schematically showing a process for producing an ionized calcium powder.
FIG. 3 is a photograph of a master batch chip produced by the method of manufacturing an antimicrobial master batch using the ionized calcium powder of the present invention.
Figs. 4 to 7 are test results obtained from Korea Conformity Laboratories (KCL) for antibacterial testing of shells and general antibacterial plastics.
8 to 11 are test reports obtained from Korea Conformity Laboratories (KCL) commissioned by Korea Institute of Construction and Environment Testing (KCL) for antimicrobial testing of films prepared from the antimicrobial masterbatch according to the present invention.
12 to 15 are test reports obtained by asking Korea Conformity Laboratories (KCL) for antimicrobial activity of antibacterial silicone rubber prepared from the antibacterial masterbatch prepared by the present invention.
16 to 17 are test reports obtained from Korea Conformity Laboratories (KCL) commissioned for the antibacterial test of a plastic container made from the antimicrobial master batch manufactured by the invention.
FIGS. 18 to 19 are photographs showing experimental results of an additional antibacterial experiment of a film prepared from the antimicrobial masterbatch prepared by the present invention as a raw material. FIG.

The present invention will be described in detail with reference to the "method for manufacturing an antimicrobial master batch using an ionized calcium powder" . Also, the terms defined in the present specification and claims should not be construed as limiting, but may be changed according to the intention or custom of the operator, and interpreted in terms of meaning and concept consistent with the technical idea of the present invention.

In one aspect of the present invention,

FIG. 1 is a view schematically showing a method of manufacturing an antimicrobial masterbatch using the ionized calcium powder of the present invention. FIG. 2 is a view schematically showing a process of producing an ionized calcium powder. FIG. 3 is a cross- 4 to 7 were obtained from Korea Conformity Laboratories (KCL) by requesting shells and antimicrobial tests of general antimicrobial plastics. The results are shown in FIG. 8 to 11 are test reports obtained from Korea Conformity Laboratories (KCL) commissioned for antimicrobial tests on films prepared from the antimicrobial masterbatch prepared by the present invention, 12 to 15 are graphs showing the results of tests conducted by the Korean Institute of Concrete Laboratories (KCL) 16-17 are test results obtained from an antimicrobial masterbatch prepared by the invention in Korea Conformity Laboratories (KCL). The test results are shown in Fig. FIG. 18 to FIG. 19 are photographs showing experimental results on the additional antibacterial experiment of the film made from the antimicrobial masterbatch prepared by the present invention as a raw material. FIG.

1, an antimicrobial masterbatch manufacturing method using an ionized calcium powder comprises: (S1) preparing an ionized calcium powder to produce an ionized calcium powder using a shell as a raw material; A surfactant treatment step (S2) for lowering the surface polarity of the inorganic powder particles by surface-treating the inorganic powder particles formed in the ionized calcium powder production step (S1) with a cationic surfactant; The powder having been subjected to the surfactant treatment step may be used in an amount of 1 to 50% by weight, and may be any one selected from the group consisting of polyethylene, polypropylene, polyurethane, acrylonitrile-butadiene-styrene resin, silicone rubber and thermoplastic polyurethane (TPU) (S3) in which the synthetic resin or rubber is mixed; And a master batch forming step (S4) of molding the resultant obtained through the mixing step into a spherical or chip form.

The cationic surfactant used in the surfactant treatment step (S2) is 99% pure and has 12-20 carbon atoms, and is any one of CTAB (Cetyl trimethylammonium bromide) and CTAC (cetyl trimethylammonium chloride).

The cationic surfactant should be harmless to human body.

The polyethylene is either LLDPE (Linear LDPE), HDPE or LDPE.

Referring to FIG. 2, in the ionized calcium powder production step (S1), the shell is subjected to a foreign matter removal step (S11) and a cleaning step (S12) three times before the firing step (S14) S13).

In the ionized calcium powder production step (S1), the rotation speed, the shell input amount and the calcination temperature of the calcination furnace are controlled by using a cylindrical calcination furnace which is installed downwardly inclined and rotated by a driving device and maintains a high temperature state, And a firing step (S14) for separately preparing an ionizing calcium agent for food and industrial according to the purity of the ionized calcium agent.

The sintering step (S14) is carried out in such a manner that the sintering furnace is thermally insulated by refractory bricks, the length is 18,000 mm and the inside diameter thereof is 900 mm, the rotational speed of the calcining furnace is 35 to 40 rpm, the input amount of shell is 500 kg / And a shell having a purity of 95 to 99% by retaining the shell in the calcining furnace for 30 to 45 minutes at 1,100 to 1,200 ° C.,

When the rotary speed of the calcination furnace is 30 to 35 rpm, the shell amount is 300 kg / hr, and the calcination temperature is 1,200 ° C or more, the shell is kept in the calcination furnace for 45 to 90 minutes to produce an industrial ionized calcium powder having a purity of calcium of 99% .

A cooling step (S15) in which the shell obtained through the firing step (S14) is quenched to room temperature, and a pulverizing step (S16) in which the particle size is pulverized to a size of 3-8 mu m.

In the cleaning step S12, an ultrasonic cleaning method using a frequency higher than an audible frequency is used, and alkaline water having a pH of 8.5-9.0 is used as cleaning water.

The alkaline water is made by passing the ground water through a filter filled with a fine mesh of clathrate powder.

Since the alkaline water contains a large amount of potassium, magnesium, sodium and iron, it plays an important role in naturally naturalizing, and can be sterilized against shells contaminated with various pollution and the like.

On the other hand, the alkaline water-producing powder is a mixture of 98% of the alkaline water-containing powder and the rest of which is filled with shell powder such as mussel shell and oyster shell, wherein 35-50% by weight of diaritic powder, 12-30% by weight of zeolite powder, 2 to 20% by weight of the powder and 1 to 20% by weight of the coral powder can be used.

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Referring to FIG. 3, the master batch chip made by the method of manufacturing an antimicrobial master batch using the ionized calcium powder of the present invention is photographed.

The prepared antimicrobial masterbatches are applicable to various antimicrobial lunches, side dishes, trash cans, water bottles, various life containers, and industrial containers.

The antimicrobial film produced from the master batch chip as a raw material can be allied to produce daily life products such as antimicrobial disposable gloves, wraps, roll bags, zipper bags and rubber gloves, and also to manufacture all kinds of plastic bags such as confectionery bags and ramen bags It is applicable.

- Antibacterial test of shell and general antibacterial plastic.

Inoculated Escherichia coli (strain: Escherichia coli ATCC 8739, initial concentration: 3.4 × 10 ^ 5 CFU / mL) was used as the control. Staphylococcus aureus ATCC 6538P (initial concentration: 2.9 x 10 ^ 5 CFU / mL) was used as an antimicrobial agent, The initial concentration was kept at room temperature and the degree of change after 24 hours was observed.

The results are shown in Table 1 below and the official test report is shown in FIG. 4 to FIG.

Test Items
Test result Initial concentration (CFU / mL) Concentration after 24 hours
(CFU / mL) Bacterial reduction rate (%) Antibacterial test with Escherichia coli Blank 3.4 x 10 ^ 5 4.8 x 10 ^ 5 - Non-treated general antimicrobial plastic 3.4 x 10 ^ 5 4.7 x 10 ^ 5 2.0 Antibacterial test with Pseudomonas aeruginosa Blank 3.6 x 10 ^ 5 5.0 x 10 ^ 5 - Non-treated general antimicrobial plastic 3.6 x 10 ^ 5 4.8 x 10 ^ 5 4.0 Antibacterial test with Staphylococcus aureus Blank 2.9 x 10 ^ 5 4.6 x 10 ^ 5 - Non-treated general antimicrobial plastic 2.9 x 10 ^ 5 4.5 x 10 ^ 5 2.1

It can be confirmed that the antimicrobial effect of the antimicrobial plastic generally distributed from this example was surprisingly small.

- Antimicrobial test of the film made from the antimicrobial masterbatch prepared by the present invention as a raw material.

As a raw material of the antimicrobial masterbatch prepared by the present invention, a specimen containing 1% of ionized calcium powder was used as a test specimen of 5 cm x 5 cm. As a control, untreated stomarker film of the same size was used. Pseudomonas aeruginosa ATCC 15442, initial concentration 3.6 x 10 5 CFU / mL), Staphylococcus aureus (strain used: Escherichia coli ATCC 8739, initial concentration 3.4 x 10 5 CFU / Staphylococcus aureus ATCC 6538P, initial concentration 2.9 x 10 ^ 5 CFU / mL) was used and the initial concentration was maintained at room temperature to see how it changed after 24 hours.

Table 2 below shows the results, and the official test report is shown in Figs. 8 to 11. Fig.

Test Items
Test result Initial concentration (CFU / mL) Concentration after 24 hours
(CFU / mL) Bacterial reduction rate (%) Antibacterial test with Escherichia coli Blank 3.4 x 10 ^ 5 4.8 x 10 ^ 5 - Antimicrobial plastic (containing 1%) 3.4 x 10 ^ 5 <10 99.9 Antibacterial test with Pseudomonas aeruginosa Blank 3.6 x 10 ^ 5 5.0 x 10 ^ 5 - Antimicrobial plastic (containing 1%) 3.6 x 10 ^ 5 <10 99.9 Antibacterial test with Staphylococcus aureus Blank 2.9 x 10 ^ 5 4.6 x 10 ^ 5 - Antimicrobial plastic (containing 1%) 2.9 x 10 ^ 5 <10 99.9

From this example, it can be seen that the antibacterial effect of the film produced from the master batch produced by the present invention as a raw material is very remarkable.

These antimicrobial effects are shown to be higher due to higher alkalinity and OH-action, higher anion and ultraviolet emissivity than other materials, and higher specific surface area due to the nature of the porous particles.

- Antimicrobial activity of antibacterial silicone rubber prepared from the antimicrobial masterbatch prepared by the present invention as a raw material.

As the antimicrobial silicone rubber prepared from the antimicrobial masterbatch prepared by the present invention, a specimen containing 1% of ionized calcium powder was used as a test specimen of 5 cm x 5 cm. The control specimen was an untreated stomarker film of the same size, Was used for the detection of E. coli (strain: Escherichia coli ATCC 8739, initial concentration 3.4 × 10 5 CFU / mL), P. aeruginosa ATCC 15442 (initial concentration: 3.6 × 10 5 CFU / mL) Staphylococcus aureus ATCC 6538P, initial concentration 2.9 x 10 ^ 5 CFU / mL) was used and the initial concentration was kept at room temperature to see how much it changed after 24 hours.

Table 3 below shows the results and the official test report is shown in Figures 12-15.

Test Items
Test result Initial concentration (CFU / mL) Concentration after 24 hours
(CFU / mL) Bacterial reduction rate (%) Antibacterial test with Escherichia coli Blank 3.4 x 10 ^ 5 4.8 x 10 ^ 5 - Antibacterial silicone (containing 2%) 3.4 x 10 ^ 5 <10 99.9 Antibacterial test with Pseudomonas aeruginosa Blank 3.6 x 10 ^ 5 5.0 x 10 ^ 5 - Antibacterial silicone (containing 2%) 3.6 x 10 ^ 5 <10 99.9 Antibacterial test with Staphylococcus aureus Blank 2.9 x 10 ^ 5 4.6 x 10 ^ 5 - Antibacterial silicone (containing 2%) 2.9 x 10 ^ 5 <10 99.9

It can be seen from the present Example that the antimicrobial effect of the silicone rubber produced from the master batch produced by the present invention as a raw material is very remarkable.

- Antibacterial experiment of plastic container made from the antimicrobial masterbatch prepared by the present invention as raw material.

The test piece was a plastic container (containing 2% of the ionic calcium powder produced by the present invention) made of the antimicrobial masterbatch prepared by the present invention, and filled with 1 L of tap water in the container and inoculated with the test strain. The bacterial reduction rate was measured on the general antimicrobial plastics for 1-5 days under the same conditions as above. Escherichia coli ATCC 25922 (initial concentration 4.5 x 10 ^ 4 CFU / mL) was used for inoculation.

Table 4 below shows the results and the official test report is shown in Figs. 16-17.

Test Items
Test result Initial concentration (CFU / mL) After 1 day concentration (CFU / mL) After 2 days the concentration (CFU / mL) After 3 days the concentration (CFU / mL) After 4 days the concentration (CFU / mL) After 5 days concentration (CFU / mL)
Antibacterial test with Escherichia coli
Blank 4.5 x 10 ^ 4 3.9 x 10 ^ 4 3.1 x 10 ^ 4 2.3 x 10 ^ 4 1.8 x 10 ^ 4 1.2 x 10 ^ 4 Plastic containers (2%) 4.5 x 10 ^ 4 3.8 x 10 ^ 4 3.0 x 10 ^ 4 2.2 x 10 ^ 4 1.6 x 10 ^ 4 1.0 x 10 ^ 4 Bacterial reduction rate (%) - 2.5 3.2 4.3 11.1 16.6

It can be confirmed from the present Example that the antibacterial plastic container made from the masterbatch prepared by the present invention as a raw material has a better antimicrobial effect than a general antibacterial plastic container. Further, as compared with Examples 2 to 3, , The antimicrobial effect is actively observed on the surface of the plastic container.

The antimicrobial plastic container made from the masterbatch prepared by the present invention is active only on the surface of the container. Therefore, if kimchi is contained therein, it can prevent overcooking due to excessive fermentation, .

- Further antibacterial experiments of the film made from the antimicrobial masterbatch prepared by the present invention as a raw material.

This experiment was conducted to more clearly demonstrate the results of Example 2. The test group was a zipper bag made of a film containing 1.5% of ionized calcium powder and a zipper bag made of a film containing 2% of ionized calcium powder (Two on the left in the photographs of FIGS. 18 and 19), using a general zipper bag (Lotte product) as a control group (one on the right in the photographs of FIGS. 18 and 19) and putting sesame leaves and lettuce (Yeosu local food product) The changes in the time were observed one time at the same time every day. The temperature was in the range of 26-32 ℃.

Referring to FIGS. 18 and 19, the zipper bag of the test group was not changed over time, whereas the sesame leaf and lettuce contained in the general zipper bag of the control group decayed over time.

The masterbatch prepared by the method of producing an antimicrobial masterbatch using the ionized calcium powder of the present invention is made by using a natural material called a shell of a shell or the like and having a superior antibacterial performance by adding a cationic surfactant, So that the material can be safely used as a container for food or the like.

In addition, it is possible to reuse the unprocessed and discarded local special products such as cockles and shells of oysters, thereby helping to use available resources and solve environmental problems.

S1: Preparation of ionized calcium powder
S10: shell shelling step S11: foreign matter removal step
S12: Cleaning step S13: Drying step
S14: Firing step S15: Cooling step
S16: Crushing process
S2: Surfactant treatment step S3: Mixing step
S4: master batch forming step

Claims (9)

In the master batch manufacturing method,
In the manufacturing method,
A step of preparing an ionized calcium powder to produce an ionized calcium powder using a shell as a raw material;
A surfactant treatment step of lowering the surface polarity of the inorganic powder particles by surface-treating the inorganic powder particles produced in the ionized calcium powder production step with a cationic surfactant;
The powder having been subjected to the surfactant treatment step may be used in an amount of 1 to 50% by weight, and may be any one selected from the group consisting of polyethylene, polypropylene, polyurethane, acrylonitrile-butadiene-styrene resin, silicone rubber and thermoplastic polyurethane (TPU) A synthetic resin or a rubber; And
And a master batch forming step of forming the resultant obtained through the mixing step into a spherical or chip form,
The ionized calcium powder preparation step
Shell filling process; A foreign matter removing process; Cleaning process; Drying process; Firing process; A cooling step of quenching the coarse shell of the sintering step to room temperature; And a pulverizing step of pulverizing the particle size to a size of 3-8 mu m,
In the foreign matter removing process and the cleaning process, the two processes are successively performed three times in succession,
The cleaning process uses an ultrasonic cleaning method using a frequency higher than an audible frequency, and the cleaning water is cleaned using alkaline water having a pH of 8.5-9.0,
The sintering process is controlled by controlling the rotation speed, shell input amount, and sintering temperature of the sintering furnace by using a cylindrical sintering furnace which is installed at a downward slope and rotates by a driving device and maintains a high temperature state, The calcium powder or the industrial ionized calcium powder may be separately prepared,
The food ionized calcium powder has a purity of calcium of 95 to 99%, a sintering furnace which is heat-treated by refractory bricks, a length of 18,000 mm and an inner diameter of 900 mm, a rotational speed of the calcining furnace is 35 to 40 rpm, When the amount of the feed is 500 kg / hr and the firing temperature is 1,100 to 1,200 ° C, the shell is manufactured by staying in the firing furnace for 30 to 45 minutes,
The industrial ionized calcium powder preferably has a purity of calcium of 99% or more, a rotation speed of the calcination furnace of 30 to 35 rpm, a shell input of 300 kg / hr, and a calcination temperature of 1,200 ° C or more. Wherein the antimicrobial masterbatch is produced by a process comprising the steps of: delete The method according to claim 1,
The cationic surfactant used in the surfactant treatment step is any one of CTAB (Cetyl trimethylammonium bromide) and CTAC (cetyl trimethylammonium chloride) having a number of carbon atoms of 12-20, which is 99% purity. Manufacturing method. delete delete delete The method according to claim 1,
Wherein the alkaline water is produced by passing the ground water through a filter filled with a fine mesh of a crucible powder. delete The method according to claim 1,
Wherein the polyethylene is one of LLDPE (Linear LDPE), HDPE and LDPE.

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