KR101705604B1 - Deodorizing functional masterbatch and its film and container manufacturing method - Google Patents

Abstract

The present invention relates to a process for preparing a masterbatch for deodorization and a process for producing a film or a container using the same, and more particularly to a process for producing a masterbatch using a deodorizing masterbatch composition comprising sodium hydrogencarbonate and polyethylene And a method of making a film or container using the masterbatch.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0002] The present invention relates to a master batch having deodorizing capability and a method for manufacturing a film and a container using the master batch,

The present invention relates to a method for producing a masterbatch to which deodorizing ability is imparted, a method for producing a film and a container using the same, and more particularly, to a method for producing a masterbatch using a composition capable of removing odorous substances, A film produced using such a master batch and a container thereof.

Kimchi causes various physicochemical changes during the fermentation and aging process, resulting in various volatile substances that cause odors. For example, the main volatile substances of kimchi include sulfur containing components such as methyl allylsulfide, dimethyl disulfide, diallyl disulfide, methyl allyl trisulde, methyl 2 - propenyldisulde and di - propenyldisulde, ethanol, acetic acid, allyl mercaptan, diisocyanato - 1 - methylbenzene, 2 - phenylethyl isothiocyanate, and 1,2 - benzenedicarboxlyic acid (Ha 2002).

Due to such volatile substances, the overcooked kimchi is not only sour, but also has a strong smell due to a remarkable increase of volatile substances, so that foreigners who usually like kimchi may be reluctant. In addition, the plastic container or the plastic container containing the kimchi is difficult to wash due to the permeation of various odor components as described above, and even after washing the container, the odor still remains and it is difficult to use it for other purposes.

Methods of using a masking material or a binding material to reduce the odor as described above are known.

The reduction by the double masking agent means to reduce the existing odor by adding a stronger substance than the substance causing the odor. Examples of such a masking agent include herbs such as rosemary, lavender, peppermint, garlic, , Pine needles, and other food materials such as phosphoric acid.

Unlike the masking agent which reduces the odor by using strong fragrance, the method of using the binder which reduces the odor by combining with the odor inducing substance means a method of reducing the odor by reducing the volatility of the odor by reacting with the odorless substance . An example of a binder is a method in which, when activated carbon or char is used to adsorb a deodorant, the deodorant is bound through a gauging such as carrageenan.

However, most of the above masking agents and binders are difficult to add to foods because they can change the sensory aspects related to securing stability to the human body, taste, aroma, and the physical properties of the food itself.

On the other hand, conventional food packaging has only served to protect food from external harmful factors, to store food, and to raise information on nutrients and raw materials to consumers. However, in order to maintain the quality and freshness of food, various functional materials for controlling humidity, generating gas, antibacterial and deodorizing are increasingly added.

In Korean Patent Laid-Open Publication No. 2013-0127038, an odor removing substance consisting of sodium bicarbonate (NaHCO ₃ ), maltose, sodium carbonate (Na ₂ CO ₃ ) and live bacteria is prepared in order to remove the odor of food waste, Discloses a food wastes deodorizing substance that removes odors by mixing a substance with food wastes.

According to the above-mentioned prior art, odor generated from food waste can be removed, but there is a limitation in that sodium hydrogen carbonate, fumarole, etc. can not be added to foods. Thus, a new concept Deodorization technology development is urgent.

Korean Patent Publication No. 10-2013-0127038

Accordingly, it is an object of the present invention to provide a masterbatch composition for deodorization capable of reducing odor-causing substances.

It is another object of the present invention to provide a method for producing a film for deodorization using a masterbatch composition for deodorization.

It is also an object of the present invention to provide a packaging container using a masterbatch composition for deodorization.

The master batch composition of the present invention for solving the above problems is characterized by containing sodium hydrogen carbonate and polyethylene.

Here, the polyethylene is preferably low density polyethylene.

The method for producing a film according to the present invention is characterized by comprising the steps of: preparing a master batch from the master batch composition; and extruding the master batch to produce a film.

Preferably, the masterbatch comprises less than 20% by weight of sodium hydrogen carbonate and less than 80 to 100% by weight of low density polyethylene.

Further, in the extrusion molding step, extrusion molding is preferably performed with a twin screw extruder, and it is more preferable that the twin screw extruder is operated at 95 ° C to 200 ° C.

In addition, the present invention provides a film produced by the film production method.

Here, the deodorizing film may contain 0.2 to 2% by weight of sodium hydrogencarbonate.

In addition, the container manufacturing method of the present invention is characterized in that it comprises the steps of manufacturing a master batch with a master batch composition and molding the master batch to manufacture a container. Here, the container may be a kimchi storage container.

The master batch for deodorization of the present invention contains sodium hydrogencarbonate, so that there is an effect that odorous substances generated in foods such as kimchi can be removed.

The master batch for deodorization according to the present invention contains sodium hydrogencarbonate, so that it is possible to produce a film or a container from which odorous substances can be removed. In particular, It is possible to remarkably reduce the odorous substances of the gas discharged to the outside of the container.

Further, according to the method for producing a film or a container of the present invention, since a composition containing a deodorizing material is used in the extrusion molding, a separate step for imparting a deodorizing function is not required, .

Fig. 1 is a graph showing pyrolysis characteristics of sodium hydrogen carbonate.
Fig. 2 is a diagram comparing the transparency of the film with the blending ratio of the master batch.
3 shows the chemical structure of the film according to the blending ratio of the master batch.

Hereinafter, preferred embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.

The process for producing a film according to the present invention comprises the steps of preparing a master batch with a film composition for deodorization, mixing the master batch with low density polyethylene, and extruding the mixture to produce a film .

First, the film composition for deodorization will be described in detail with reference to a film composition for deodorization. The film composition for deodorization may include sodium hydrogencarbonate and polyethylene.

Known as baking soda, sodium hydrogencarbonate (NaHCO ₃ ) is one of the most widely used deodorants as a weakly alkaline natural substance and is known to neutralize odor molecules and effectively remove volatile substances and toxic compounds.

That is, sodium bicarbonate (NaHCO ₃ ) reacts with acetic acid, a volatile organic acid component generated during the aging process of kimchi through the following reaction, thereby generating sodium acetate, water and carbon dioxide, Is expected to be removed.

Reaction 1) NaHCO ₃ + CH ₃ COOH → CH ₃ COONa + H ₂ O + CO ₂

In particular, when sodium hydrogencarbonate is heat-treated at 90 ° C to 200 ° C, more preferably 100 ° C to 180 ° C, the deodorizing effect is more effective because it can react with acetic acid more.

That is, as shown in Reaction Scheme 2 below, sodium bicarbonate is decomposed into sodium carbonate, water and carbon dioxide by pyrolysis, and the resulting 1 mol of sodium carbonate reacts with 2 mol of acetic acid as shown in Scheme 3.

Reaction 2) 2NaHCO ₃ ? Na ₂ CO ₃ + H ₂ O + CO ₂

Reaction formula 3) Na ₂ CO ₃ + 2 CH ₃ COOH? 2 CH ₃ COONa + H ₂ O + CO ₂

On the other hand, the film for deodorization of the present invention preferably includes polyethylene, and is preferably low density polyethylene, although it is not particularly limited as long as it has excellent processability and flexibility.

In particular, low density polyethylene is known as a relatively safe material because it is resistant to heat and excellent in workability and is used as a main ingredient of kitchen utensils and various containers and hardly discolored even when exposed to sunlight for a long time.

In the present invention, in order to improve the dispersibility of sodium hydrogencarbonate, which is a deodorant, and prevent scattering, a master batch in the shape of a small sphere or chip is prepared by mixing with polyethylene.

Here, the master batch preferably contains more than 0 to 20% by weight of sodium hydrogen carbonate and less than 80 to 100% by weight of low density polyethylene.

If the sodium hydrogencarbonate is not contained at all, the prepared film has no deodorizing function. When the content exceeds 20% by weight, the mechanical strength such as tensile strength and elongation of the produced film is lowered. Do.

Meanwhile, since the master batch manufacturing method corresponds to a known technique, a detailed description thereof will be omitted.

Next, the prepared master batch is mixed with low density polyethylene, and then extrusion molding is performed to produce a film.

Preferably, the mixture comprises 0 to 10 wt.% Masterbatch and 90 to less than 100 wt.% Low density polyethylene.

When the content of the masterbatch is 0 wt%, the produced film has no deodorizing function. When the content of the masterbatch exceeds 10 wt%, the mechanical strength such as tensile strength and elongation of the produced film is lowered. .

In addition, various additives such as a stabilizer, a dispersing agent and a lubricant which can be additionally incorporated in the extrusion molding may be added to the mixture.

In the extrusion molding step, an apparatus capable of extrusion molding using a thermoplastic resin or the like is not particularly limited, but extrusion molding is preferably performed with a twin screw extruder.

In the case of extrusion molding with a twin screw extruder, it is preferable to operate at a temperature of 95 ° C to 200 ° C, more preferably 100 ° C to 180 ° C. As described above, in order for sodium bicarbonate to react with acetic acid more, it is necessary to decompose sodium hydrogencarbonate.

Therefore, when the operating temperature of the twin screw extruder is less than 95 캜, it is difficult to thermally decompose sodium hydrogencarbonate. When the operating temperature exceeds 200 캜, the power ratio is unnecessarily wasted. Therefore, the twin screw extruder the twin screw extruder is preferably operated in the temperature range described above.

In the meantime, although only the case where the master batch prepared and the low density polyethylene are mixed and extruded has been described, the master batch may be subjected to extrusion molding by adjusting the low density polyethylene content of the master batch, It is also possible to manufacture. However, it is more preferable to mix low density polyethylene after preparing a high concentration master batch, because it is easy to control the blending ratio.

The deodorizing film produced by the above-described method can be manufactured into various packaging containers for storing food in which the offensive odor is generated, and can be preferably a packaging container for storing kimchi.

Here, the thickness of the film is not particularly limited, but is preferably 60 to 80 占 퐉 in consideration of mechanical strength and transparency. The film preferably contains sodium hydrogen carbonate in an amount of 0.2 wt% to 2 wt%.

When the content of sodium hydrogencarbonate is less than 0.2% by weight, the deodorizing effect is insignificant. When the content exceeds 2% by weight, the deodorizing effect is improved. However, since the mechanical strength is lowered and it is difficult to use the film as a film or a container, It is preferable that the above range is included.

On the other hand, a master batch alone or a mixture of a master batch and a low density polyethylene may be prepared as a container having a predetermined shape. Here, the method of manufacturing the container using the master batch corresponds to a known technique, so a detailed method will be omitted.

Hereinafter, the present invention will be described in more detail with reference to examples. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Example 1: Pyrolysis characteristics and deodorization ability of sodium hydrogencarbonate

Baking soda consisting of 99% sodium hydrogencarbonate and 1% alum was purchased from Feng Enbi Co., Ltd.

FT-IR (Fourier Transform Infrared Spectrometry) analysis was performed on sodium bicarbonate which was heat-treated at 180 ° C for 10 minutes and sodium bicarbonate which was not heat-treated as a control in order to confirm that sodium hydrogencarbonate was pyrolyzed to produce sodium carbonate , And the results are shown in Fig.

As it can be seen from the results of 1, sodium bicarbonate (baking soda) in the 3425, 3042, 2900, 2500, 2045, 1900, 1669, 1606, 1410, 1240, 1016, 1000, 979, 838, 653, 642 cm 1 A unique peak was found. On the other hand, in the heat treated sodium hydrogencarbonate, peaks were observed at 2500, 1770, 1413, 878, 851 and 700 cm ¹ , which are intrinsic peaks of sodium carbonate. From these results, it can be seen that sodium carbonate is produced by heat treatment of sodium hydrogencarbonate .

Lactic acid and acetic acid were increased during fermentation of kimchi, and the smell of kimchi leaking from the container was attributed to the volatile acetic acid. Table 1 below shows the results of investigation of deodorizing effect on acetic acid using heat treated sodium hydrogencarbonate with the above control group.

Here, the control group and the heat treated sodium hydrogencarbonate were each 1.0 g, and the deodorization ratio was calculated by injecting 3 L of 50 ppm acetic acid into a gas bag of 5 L capacity.

division Deodorization rate (%) 0 minutes 30 minutes 60 minutes 90 minutes 120 minutes 150 minutes Control group 0 31.3 ± 1.3 61.3 ± 3.8 70.0 + - 5.0 81.3 ± 1.3 86.3 ± 1.3 Heat-treated
Hydrogen carbonate
salt 0 95.0 ± 0.0 97.5 ± 2.9 > 99.9 ± 0.0 > 99.9 ± 0.0 > 99.9 ± 0.0

As can be seen from the above Table 1, both the control group and the heat-treated sodium hydrogencarbonate were found to increase the deodorization rate as the contact time elapsed.

In particular, in the case of heat treated sodium hydrogencarbonate, 95% of acetic acid was removed after 30 minutes of contact, and most of the acetic acid was removed after 150 minutes.

Example 2: Master batch and film properties produced

First, a master batch was prepared by mixing 2: 8 by weight of sodium hydrogencarbonate and low density polyethylene (LDPE) in a weight ratio. Then, a master batch and low density polyethylene (LDPE) Respectively. The prepared film mixture was prepared by using a twin screw extruder to prepare a deodorizing film having a thickness of 70 ± 2 μm.

Here, SKY GREEN PN200 was purchased from SK Chemicals for LDPE, and MFI (melt flow index) 3.0 g / 10 min was used. The pressure of the twin screw extruder barrel at the master batch and the production of the composite film is 29.0 kgf / cm 2, the temperature is 175 ° C, the metering and compression zone is 140-175 ° C, and the feed zone is 100 ° C. .

Master batch
(Sodium hydrogencarbonate + LDPE) LDPE (g) Gross weight (g) Formulation ratio (%) Weight (g) Formulation ratio (%) Weight (g) 0 0 100 400 400 One 4 99 396 400 3 12 97 388 400 4 20 95 380 400 10 40 90 360 400

To confirm the transparency and color of the prepared film, the film was cut into 5 × 5 cm ² and placed on printed paper. The prepared film was made entirely transparent, and the transparency tended to decrease somewhat as the content of the masterbatch increased (FIG. 2).

FT-IR analysis was performed to confirm the bonding between LDPE and sodium hydrogencarbonate, and the results are shown in FIG.

If the LDPE _{^{is, 2847cm -1 (-CH 3 symmetric stretching}} ), 2913cm -1 (-CH 2 anti symmetric deformation), 1604cm -1 (-CH 3 symmetric deformation), 1470cm -1 (-CH 2 symmetric deformation), _{^{1376cm -1 (-CH 3 anti symmetric deformation}} ), 729cm -1 (-CH 3 Rocking vibration) peak generally appears as. In contrast, in the deodorizing film made according to the present invention is sodium carbonate inherent peak is not present in the pure LDPE was found in ^{1413 cm -1, 878 cm -1,} 700cm -1.

From the above results, it can be predicted that pyrolysis of sodium hydrogencarbonate occurs in the process of producing a film for deodorization.

Table 3 below shows the deodorizing effect of acetic acid using the produced film.

Here, the deodorization ratio was calculated by injecting 1.0 g of each of the control group (0% masterbatch) and the experimental group (masterbatch 1% ~ 20%) together with 3 liters of 50 ppm of acetic acid into a 5 liter gas bag.

division Deodorization rate (%) 0 minutes 30 minutes 60 minutes 90 minutes 120 minutes 150 minutes  Master batch 0% 0 14.2 ± 4 11.2 ± 7 2.0 ± 2 6.1 ± 2 12.2 ± 4  Master batch 1% 0 12.3 ± 4 9.2 ± 3 17.4 ± 3 18.4 ± 4 30.8 ± 5  Master batch 3% 0 8.0 ± 4 7.0 ± 1 20.0 ± 2 22.0 ± 2 36.0 ± 4  Master batch 5% 0 20.8 ± 1 16.8 ± 3 22.8 ± 1 28.7 ± 5 41.6 ± 2  Master batch 10% 0 9.0 ± 1 22.0 ± 0 35.0 ± 1 41.0 ± 1 45.0 ± 1  Master batch 20% 0 18.5 ± 2 35.1 ± 1 45.3 ± 1 50.5 ± 1 57.7 ± 0

Analysis of deodorization effect on acetic acid showed that the deodorization rate increases as the blending ratio of the master batch increases and the reaction time becomes longer.

The transparency, the clarity of color, the plastic smell, the roughness of the surface, the degree of hardness of the film and the overall acceptability were evaluated as the sensory evaluation representing the consumer's preference for the deodorization film of the present invention.

Item Master batch
0% Master batch
One% Master batch
3% Master batch
5% Master batch
10% transparency 8.76 ± 0.4 6.12 ± 1.3 5.76 ± 1.3 4.76 ± 1.6 3.29 ± 1.3 Clarity of color
(White degree) 1.71 ± 1.4 4.94 ± 1.6 4.94 + 1.7 6.00 ± 1.5 6.94 ± 1.5 Plastic (additive) odor 6.94 ± 1.8 5.18 ± 1.6 5.59 ± 1.6 4.88 ± 1.2 4.18 ± 1.5 Roughness of surface 1.53 ± 1.2 4.59 ± 2.2 5.06 ± 2.2 5.47 ± 2.4 7.06 + 1.7 Hardness of Film 3.82 ± 2.7 5.29 ± 1.8 5.41 ± 1.5 5.47 ± 1.6 5.88 ± 2.0 Overall likelihood 6.18 ± 1.5 5.12 ± 1.1 5.12 ± 1.3 5.29 ± 1.6 5.00 ± 1.5

As can be seen from Table 4, the transparency showed a tendency to decrease as the content of the masterbatch increased, and the clarity of the color (whiteness), roughness of the surface and hardness of the film increased in proportion to the content of the masterbatch Respectively.

Meanwhile, regarding the deodorization which is the biggest feature of the present invention, as the content of the masterbatch is increased, the smell of the plastic is also reduced, and it can be confirmed that the use of sodium hydrogencarbonate can reduce the conventional plastic odor.

Having described specific portions of the present invention in detail, those skilled in the art will appreciate that these specific descriptions are only for the preferred embodiment and that the scope of the present invention is not limited thereby. It will be obvious. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (13)

delete delete delete delete delete delete delete delete delete delete Mixing 10 to 20% by weight of sodium hydrogencarbonate with 80 to 90% by weight of polyethylene to obtain a master batch mixture;
Extruding the master batch mixture while maintaining the temperature at 100 캜 to 180 캜 to obtain a master batch;
Mixing the master batch in an amount of more than 10% by weight and less than 90% by weight and polyethylene in an amount of less than 100% by weight;
Extruding the mixture for film while maintaining the temperature at 100 캜 to 180 캜 to produce a film having a thickness of 60 to 80 탆; And
And molding the film into a container,
Wherein the step of preparing the mixture for film comprises adjusting the sodium hydrogencarbonate to be in the range of 0.2 wt% to 2.0 wt%.

delete delete

Images