KR20090045503A - Celite-containing polyethylene film having excellent anti-corrosive properties and manufacturing method thereof - Google Patents

Abstract

The present invention is a celite-containing polyethylene film having excellent antirust properties, wherein the celite is uniformly dispersed in the inside of the polyethylene film, and the inner cavity of the celite is dicyclohexylamine, dicyclohexylamine nitrite And it is provided with a film comprising a rust inhibitor selected from the group consisting of diisopropylamine. The celite powder may be surface coated with cetyltrimethylammonium bromide (CTAB), a cationic surfactant as surface modifier.

In addition, the present invention is a method for producing a celite-containing polyethylene film having excellent anti-corrosion properties, (a) uniformity of the celite powder inside the polyethylene (PE) film by extrusion using a twin screw extruder Dispersing to form a polyethylene / celite master batch having a celite content of 15 to 20% by weight; (b) a celite content of 8 to 12% by weight from a polyethylene / cerite masterbatch having a celite content of 15 to 20% by weight by extrusion using a single screw blown extruder; Producing a containing polyethylene film; And (c) diluting a rust inhibitor selected from the group consisting of dicyclohexylamine, dicyclohexylamine nitrite and diisopropylamine, thereby uniformly dispersing the celite-containing polyethylene film. And filling said rust inhibitor into an internal cavity of powder.

The celite-containing polyethylene film according to the present invention is suitable for packaging products such as iron products, because the production cost is low, but the antirust property is excellent, and the antirust effect can be maintained for a long time due to the sustained release of the rust preventive agent.

Anti-rust, celite, internal cavity, surface modifier, cetyltrimethylammonium bromide (CTAB), polyethylene (PE) film, low density polyethylene (LDPE) film, rust preventive agent, polycyclohexylamine, Dicyclohexylamine nitrite, diisopropylamine, sustained release.

Description

Celite-containing polyethylene film having excellent anti-corrosive properties and a method of manufacturing the same {A CELITE-CONTAINING POLYETHYLENE FILM WITH ENHANCED ANTI-RUST PROPERTY, AND A METHOD FOR PRODUCTION OF THE SAME}

The present invention relates to a celite-containing polyethylene film having excellent antirust properties and a method for producing the same.

In the industry, rust preventive oil has been applied thinly to the surface of products to prevent damage caused by corrosion in the storage and transportation of machinery parts or steel products. However, after opening, the rust preventive oil needs to be wiped off, so if the quantity of the product becomes very cumbersome.

In some imported packaging films that solve these problems, the rust preventive molecules first evaporate from the film surface and settle on the surface of the product, thereby providing a rust preventive effect. It has been in the spotlight recently. However, not only the packaging film price is higher than that of general-purpose polyethylene (PE) film, but also has the disadvantage that the rust-preventing effect cannot last for a long time.

On the other hand, Korean Patent Publication No. 274181 discloses "5-20% by weight of dicyclohexyl ammonium nitrite and an average particle diameter of 0.01-20 in a propylene resin having a melting index of 1-20 (g / 10min) and a melting point of 140-180 占 폚. A polymer film having improved anti-corrosive properties comprising a thickness ratio of 1: 9 to 1: 1 of a first resin layer made of a resin to which 0.1-1 wt% of 1 μm inorganic particles are added and a second resin layer made of a thermoplastic resin Is described. Korean Patent Publication No. 598152 discloses "5 to 7 parts by weight of hydroxyethyl cellulose, 25 to 35 parts by weight of sodium benzoate, 25 to 35 parts by weight of benzotriazole, 5 to 7 parts by weight of sodium metasilicate, and an inorganic salt (e.g., Vaporizable antirust film comprising 25 to 35 parts by weight of a phosphate including ammonium phosphate, or nitrate), and 2 to 4 parts by weight of an additive (such as beta-cyclodextrin). Korean Unexamined Patent Publication No. 1997-0033830 discloses that a vaporizable rust preventive film impregnated with low vapor density rust preventive (VCI) and a low density polyethylene (LDPE) and a vaporized rust preventive gas laminated on the vaporizable rust preventive film to block permeation of the vaporized rust preventive gas from the rust preventive film. Multilayer vaporizable antirust film composed of a barrier film for the purpose of However, the polymer rust preventive films described in these patent documents have a fatal disadvantage that the rust preventive effect cannot last for a long time.

Zeolite, silica, alumina and the like are known as inorganic materials that can be added to the polymer material, but the inventors have focused on the fact that a wide cavity is required for the storage of the rust-preventing material. Attention was paid to.

Celite is a porous mineral composed of silica and alumina, and is used in various fields such as purifiers, feed additives, papermaking, paints, chromatography, catalysts, and the like in the beverage production process. However, celite has a problem of causing a decrease in the physical properties (eg, tensile strength, tear strength, strain at break, tensile modulus, etc.) of a film such as polyethylene film. Celite, on the other hand, may contain a rust preventive material in its interior cavity and may be uniformly dispersed in the interior of the polyethylene film, thereby ensuring a long term sustaining of the rust preventive effect due to the sustained release of the rust preventive material. Accordingly, the inventors have found that the celite-containing polyethylene film can be applied to the field of packaging films that do not require high mechanical properties.

The present invention provides a celite-containing polyethylene film suitable for packaging products such as iron and the like and a method for producing the same, since the production cost is low and the antirust property is excellent, and the antirust effect can be maintained for a long time due to the sustained release property of the rust preventive agent. For the purpose of

The present invention is a celite-containing polyethylene (PE) film excellent in rust prevention properties, the celite is uniformly dispersed in the inside of the polyethylene film, the inner cavity of the celite is dicyclohexylamine, di Provided is a celite-containing polyethylene film comprising a rust inhibitor selected from the group consisting of cyclohexylamine nitrite and diisopropylamine.

The polyethylene film (PE) is preferably a low density polyethylene (LDPE) film, most preferably a linear low density polyethylene (LLDPE) film.

Celite is a porous mineral composed of silica and alumina. As clearly shown in the scanning electron micrograph of FIG. 1, at similar magnifications, celite has much more voids and a larger surface area than zeolites. The size of the celite particles is preferably in the form of a powder having an average particle diameter of 3 to 5㎛. Celite is uniformly dispersed in the polyethylene (PE) film, and the celite content in the celite-containing polyethylene film is preferably 8 to 12% by weight.

Since celite itself is composed of silica and alumina, the surface has a very high polarity, but the polyethylene (PE) film itself has a low polarity, so the dispersion of celite particles due to the difference in polarity between the celite particle and the polyethylene (PE) film interface is difficult. It may not be uniform. In this case, when the celite surface is treated with cetyltrimethylammonium bromide (CTAB), a cationic surfactant as surface modifier, the ammonium group is distributed to the celite surface and the cetyl group is distributed inside the polyethylene (PE) film to provide high polarity on the interface. Overcoming the differences can lead to more uniform dispersion.

Examples of the rust inhibitor included in the internal cavity of celite include, but are not limited to, dicyclohexylamine, dicyclohexylamine nitrite, diisopropylamine, and the like.

It is preferable that the thickness of a celite-containing polyethylene film is 40-50 micrometers.

In addition, the present invention is a method for producing a celite-containing polyethylene film having excellent anti-corrosion properties, (a) uniformity of the celite powder inside the polyethylene (PE) film by extrusion using a twin screw extruder Dispersing to form a polyethylene / celite master batch having a celite content of 15 to 20% by weight; (b) a celite content of 8 to 12% by weight from a polyethylene / cerite masterbatch having a celite content of 15 to 20% by weight by extrusion using a single screw blown extruder; Producing a containing polyethylene film; And (c) diluting a rust inhibitor selected from the group consisting of dicyclohexylamine, dicyclohexylamine nitrite and diisopropylamine, thereby uniformly dispersing the celite-containing polyethylene film. And filling said rust inhibitor into an internal cavity of powder.

The twin screw extruder is preferably operated under the conditions of an extruder temperature of 235 to 265 ° C, a screw torque of 2.5 to 3.5 Nm and a screw speed of 250 to 350 rpm.

The single screw blown extruder is preferably operated under conditions of a die temperature of 200-240 ° C. and room temperature cooling.

The celite-containing or CTAB-cerite-containing polyethylene film according to the present invention has a low production cost and excellent anti-corrosive properties, and is suitable for packaging products such as iron because the anti-corrosive effect can be maintained for a long time due to the sustained release of the anti-corrosive agent. Do.

Through the following examples will be described in more detail the present invention. However, the following examples are only for illustrating the present invention, and the scope of the present invention should not be construed as being limited to the following examples. Therefore, it will be understood by those skilled in the art that various modifications, modifications and applications of the following embodiments are possible within the scope of the technical idea derived from the matters described in the appended claims.

Example

Celite Preparation of Polyethylene Films Containing

3 kg of celite powder was stirred in 50 mmol of cetyltrimethylammonium bromide (CTAB) solution for 24 hours, filtered off under reduced pressure, and dried for 1 week in an oven at 100 ° C. to obtain a white powder. Subsequently, the celite powder filled with the rust inhibitor in the inner cavity was extruded by using a twin screw extruder (extruder temperature: 250 ° C., screw torque: 3.0 Nm, screw speed: 300 rpm). By uniformly dispersing the inside of the film, a polyethylene / cerite master batch having a celite content of 20% by weight was produced. Subsequently, by extruding with a single screw blown extruder (die temperature: 220 ° C., room temperature cooling), the celite content was 10 wt% from a polyethylene / cerite master batch having a 20 wt% celite content. A celite-containing polyethylene film of% was produced. Subsequently, by injecting a diluent of a rust preventive agent (dicyclohexylamine nitrite), the rust preventive agent was added to an internal cavity of the celite powder having an average particle diameter of 4 占 퐉 uniformly dispersed in the celite-containing polyethylene film. Charged.

Mechanical properties

Tensile tests were performed on dumbbell-type specimens with a gauge length of 25 mm, crosshead speed of 100 mm / min and load cell 250 N using a universal testing machine (Lloyd LR 50K) in accordance with ASTM D-638. It was performed at room temperature. Impact strength was measured using an Elmendorf tester from Toyo seoki. Particle size analysis was measured using a Malvern Mastersizer Microplus particle size analyzer. Changes in the concentration of rust preventive materials were carried out by HP 9850 Series II gas chromatography with Hewlett Packard's flame ionization detector (injector temperature: 250 ° C, column temperature: 200 ° C, detector temperature: 350 ° C, column type: HP 1 crosslinked methyl silicon gum) ), And a mixture of nitrogen, air and hydrogen was used as the carrier gas.

In general, deterioration of the physical properties of the film due to the addition of minerals occurs in the existing inorganic addition polymer material, the addition of minerals interferes with the arrangement of the polymer chain, the cohesive force is reduced, thereby reducing the physical properties. This phenomenon has also been observed in Celite-containing polyethylene films.

For tensile strength (maximum stress), the low density polyethylene film was 24.1 MPa in the mechanical direction (MD) and 16.4 MPa in the transverse direction (TD). In contrast, the celite containing low density polyethylene film was 16.4 MPa in MD and 12.8 MPa in TD. That is, the tensile strength was reduced by 30% in MD and 22% in TD. On the other hand, the CTAB-cerite containing low density polyethylene film was 23.2 MPa in MD and 10.6 MPa in TD. That is, the tensile strength was reduced by 3% in MD and 35% in TD (see FIG. 2).

For the strain at break (elongation at break), the low density polyethylene film was 202% in MD and 445% in TD. In contrast, the celite containing low density polyethylene film was 136% in MD and 378% in TD. In other words, the elongation at break decreased by 33% in MD and 15% in TD. On the other hand, CTAB-cerite-containing low-density polyethylene film was 240% in MD, 66% in TD, compared to other films showed excellent elongation at break in MD but very low value in TD (see Fig. 3).

For tear strength, the low density polyethylene film was 660 gf in MD and 345 gf in TD. In contrast, the celite containing low density polyethylene film was 580 gf in MD and 280 gf in TD. That is, the tear strength was reduced by 12% in MD and 19% in TD (see FIG. 4).

For tensile modulus, the low density polyethylene film was 532 MPa in MD and 347 MPa in TD, and the celite containing low density polyethylene film showed 513 MPa in MD and 344 MPa in TD with little change in MD and TD (see FIG. 5). ).

In the case of haze, the low density polyethylene film was 15% while the celite containing low density polyethylene film was 55%. Due to the scattering of light due to the celite particles, the transparency of the celite containing low density polyethylene film was significantly reduced compared to the low density polyethylene film (see FIG. 6).

Due to the addition of celite, the overall mechanical properties were reduced, and the physical reinforcing effect due to CTAB coating was not obvious, but the above-mentioned property degradation was not a problem in the field of packaging films that do not require high mechanical properties.

Antirust properties

The divergence durations of the rust inhibitors were compared between the celite-containing polyethylene film and the CTAB coated celite-containing polyethylene film. First, the film was cut into a size of 10 × 10 cm and placed in a solution of three 10% rust inhibitors (dicyclohexylamine, dicyclohexylamine nitrite, and diisopropylamine) diluted with methanol for 10 days, respectively. Was permeated into the inner cavity of the celite. Methanol on the surface of the film is wiped off with a tissue, nitrogen gas is injected into the surface of the film to completely remove the remaining methanol, and the films are placed in 250 ml three-necked flasks, and the volume of the gas inside the three-necked flasks is periodically fixed (100 μl) for one month. After sampling with a gas tight syringe, the gas concentration was measured using gas chromatography. Two of the three entrances to the three-necked flask were sealed with a polyethylene film to allow the rust inhibitor to freely emanate to the outside, and one attached a rubber septum for internal gas collection. The measured value was repeated three times to select the average value. In addition, as a control experiment, after applying a rust preventive solution to the surface of the celite-containing polyethylene film, by removing the rust preventive solution on the surface by the above method, and put the celite-containing polyethylene film in a three-necked flask to analyze the gas concentration emitted from the film surface It was. Using a polyethylene film filled with the three anti-rust agents and a polyethylene film containing celite, a film bag (30cm × 30cm) is manufactured by using a heat sealer, and the inside is sealed with a nail, a blade, a trivet, and sealed at room temperature. After storage for months, the contents were corroded.

The three rust inhibitors used (dicyclohexylamine, dicyclohexylamine nitrite and diisopropylamine) were immersed in the rust preventive solution to allow the concentration of the cavities to penetrate the internal cavity of the celite. A three-necked flask as shown in FIG. 7 was used to measure the concentration of the anti-rust agent emitted from the film, and the inlet covered with the polyethylene film prevented the internal anti-rust agent molecules from the outside through the polyethylene film to prevent the anti-rust agent molecules from accumulating inside the flask. The inlet was used to sample rust inhibitors for gas chromatography.

As shown in FIG. 8, diisopropylamine peaks were observed at about 1.5 minutes by gas chromatography, and the dicyclohexylamine and dicyclohexylamine nitrite peaks at about 1.5 minutes, although the chromatograms were too similar to be separately shown. Was observed. As shown in FIG. 9, the amount of diisopropylamine released from the film was tracked over time, after 5 days, about 90% of the rust inhibitor was released, and thereafter, little change in concentration of the rust inhibitor occurred. In the case of diisopropylamine, there was no difference in the storage or divergence period of the rust inhibitor in the CTAB-cerite-containing polyethylene film and the celite-containing film. On the other hand, as a result of the control experiment of the anti-rust agent on the surface of the film, it was determined that the anti-rust agent on the surface of the film was mostly removed in the process of wiping the surface because the amount of anti-corrosive agent is small.

Since it was judged that the decrease in mechanical properties and the increase in rust resistance due to CTAB coating were not obvious, the experiment on the rust prevention effect on the iron was performed only for the low density polyethylene film and the celite-containing polyethylene film (see FIG. 12). Nails and blades are made of low density polyethylene film, celite-containing polyethylene film infused with dicyclohexylamine, celite-containing polyethylene film infused with dicyclohexylamine nitrite, celite-containing polyethylene infused with diisopropylamine The film was heat-sealed and sealed on four films such as a film, and the contents were compared after 6 months. In the cerite-containing polyethylene film injected with the rust preventive iron was very good, but in the low-density polyethylene film it was confirmed that the iron is significantly corroded.

On the other hand, in order to test the rust prevention effect in more severe conditions, the experiment was conducted on the steel already corrosion. As shown in FIG. 13, the laboratory iron trivet was not evident in the case of nails and blades after 6 months because the trivets themselves had undergone corrosion. However, when comparing the leg portions in good condition, it was confirmed that the tricycle legs sealed with the celite-containing polyethylene film were relatively less prone to corrosion, while the tricycle legs sealed with the low density polyethylene film were significantly advanced.

Therefore, as a result of the antirust test over 6 months, the antirust effect of the celite-containing polyethylene film was very excellent compared to the general polyethylene (PE) film.

1 is a scanning electron microscope (SEM) image of (a) celite and (b) zeolite.

FIG. 2 is a graph comparing tensile strength (maximum stress) of a low density polyethylene (LDPE) film, a celite containing low density polyethylene film, and a CTAB-cerite containing low density polyethylene film.

FIG. 3 compares the strain at break of a low density polyethylene (LDPE) film, a celite containing low density polyethylene film and a CTAB-cerite containing low density polyethylene film.

4 compares the tear strength of low density polyethylene (LDPE) films, celite containing low density polyethylene films and CTAB-cerite containing low density polyethylene films.

5 compares the tensile modulus of low density polyethylene (LDPE) films, celite containing low density polyethylene films and CTAB-cerite containing low density polyethylene films.

FIG. 6 compares the cloudiness of low density polyethylene (LDPE) films and celite containing low density polyethylene films.

7 shows a three-necked flask used for rust inhibitor evaporation chamber.

8 shows a gas chromatogram of diisopropylamine in a celite-containing (low density) polyethylene film.

FIG. 9 shows the profile of diisopropylamine strength VS time between CTAB-cerite containing (low density) polyethylene film and celite containing (low density) polyethylene film.

FIG. 10 shows the profile of dicyclohexylamine nitrite intensity VS time of CTAB-cerite containing (low density) polyethylene film and celite containing (low density) polyethylene film.

FIG. 11 shows the profile of dicyclohexylamine VS time of CTAB-cerite containing (low density) polyethylene film and celite containing (low density) polyethylene film.

12 includes four different films [(a) low density polyethylene (LPDE) film, (b) dicyclohexylamine, celite containing low density polyethylene film, (c) dicyclolexylamine nitrite for 6 months. To a celite-containing low density polyethylene film, and (d) a celite-containing low density polyethylene film containing diisopropylamine].

FIG. 13 includes four different films [(a) low density polyethylene (LPDE) film, (b) dicyclohexylamine, celite containing low density polyethylene film, (c) dicyclolexylamine nitrite for 6 months. To a celite-containing low density polyethylene film, and (d) a celite-containing low density polyethylene film containing diisopropylamine].

Claims (12)

A celite-containing polyethylene (PE) film having excellent rust preventing properties, The celite is uniformly dispersed in the interior of the polyethylene film, the inner cavity of the celite includes a rust inhibitor selected from the group consisting of dicyclohexylamine, dicyclohexylamine nitrite and diisopropylamine Celite-containing polyethylene film, characterized in that. The method of claim 1, And the polyethylene film is a low density polyethylene (LDPE) film. The method of claim 1, The celite-containing polyethylene film, characterized in that the surface is coated with cetyltrimethylammonium bromide (CTAB), a cationic surfactant as a surface modifier. The method of claim 1, The celite-containing polyethylene film, characterized in that the powder form having an average particle diameter of 3 to 5㎛. The method of claim 1, Celite-containing polyethylene film, characterized in that the celite content in the celite-containing polyethylene film is 8 to 12% by weight. The method according to any one of claims 1 to 5, The celite-containing polyethylene film is characterized in that the thickness of 40-50 ㎛. As a method for producing a celite-containing polyethylene film having excellent antirust properties, (a) Polyethylene / cerite masterbatch having a celite content of 15 to 20% by weight by uniformly dispersing the celite powder inside the polyethylene (PE) film by extrusion using a twin screw extruder. Generating a PE / celite master batch; (b) a celite content of 8 to 12% by weight from a polyethylene / cerite masterbatch having a celite content of 15 to 20% by weight by extrusion using a single screw blown extruder; Producing a containing polyethylene film; And (c) the celite powder uniformly dispersed in the celite-containing polyethylene film by injecting a diluent of a rust inhibitor selected from the group consisting of dicyclohexylamine, dicyclohexylamine nitrite and diisopropylamine. And filling said rust inhibitor in an internal cavity of said. The method of claim 7, wherein And the celite powder is surface coated with cetyltrimethylammonium bromide (CTAB), a cationic surfactant as a surface modifier. The method of claim 7, wherein And said polyethylene (PE) film is a low density polyethylene (LDPE) film. The method of claim 7, wherein Wherein said twin screw extruder is operated under conditions of an extruder temperature of 235-265 ° C., a screw torque of 2.5-3.5 Nm and a screw speed of 250-350 rpm. The method of claim 7, wherein Wherein said single screw blown extruder is operated under conditions of a die temperature of 200-240 ° C. and room temperature cooling. The method according to any one of claims 7 to 12, And the thickness of the celite-containing polyethylene film is 40-50 μm.

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