KR20220150780A - Preparation method of microplastic material by natural climate environment simulation and device therefor - Google Patents

Abstract

The present invention relates to a method and a device for preparing a microplastic material by using climate environment simulation and, more particularly, to a method and a device for preparing a microplastic material by using climate environment simulation. The method comprises: a plastic specimen preparation step; a weathering environment application step of applying a weathering environment to the plastic specimen; and a microplastic separation step of separating microplastics from the plastic specimen to which the weathering environment is applied. Therefore, the method and the device for preparing a microplastic material by using climate environment simulation can be applied to all kinds of plastics and can prepare and recover a large amount of microplastics in a short time.

Description

Microplastic material manufacturing method and manufacturing device using climate environment simulation {Preparation method of microplastic material by natural climate environment simulation and device therefor}

The present invention relates to a microplastic material manufacturing method and manufacturing apparatus using climate environment simulation.

More specifically, a plastic specimen preparation step; A weathering environment application step of applying a weathering environment to the plastic specimen; and a microplastic separation step of separating microplastics from plastic specimens to which a weathering environment is applied.

Environmental pollution by microplastics is rapidly emerging as an international issue, and in Korea, there is a need to clearly identify the effects on the ecosystem and human body caused by the pollution of microplastics as environmental media.

In general, microplastic refers to small pieces of plastic less than 5 mm, some of which have been decomposed or pulverized into small sizes due to corrosion by ultraviolet rays or various collisions of plastic waste dumped in the sea or rivers, and the rest are exfoliants for skin or face wash. Or, as included in products such as functional toothpaste for scaling (removal of calculus) effect, those made of very small-sized particles from the production stage are leaked into the environment. The resulting microplastics are not filtered out at sewage treatment plants and flow into the sea through streams and rivers.

Microplastics adsorb not only toxic persistent organic pollutants (POPs), such as PCBs (Polychlorinated biphenyls), dioxins, and DDT (Dichloro-diphenyl-trichloroethane), but also endocrine disruptors, such as phthalates and bisphenols, to transport and transport Because it can be released, it is also called a grain of death that seriously affects rivers, marine environments and various ecosystems. They are not only ultimately consumed by humans in the form of food after continuously accumulating in the body of living things along the food chain, but also can be included in tap water that has undergone a purification process, and through this process, microplastics are consumed for a long time. Accordingly, when a large amount of microplastics accumulate in the body, they can become a cause of carcinogenesis or cause health damage by endocrine disruptors. In recent years, several countries have banned the production of products such as cosmetics, face wash and toothpaste containing microplastics.

As described above, the area most concerned about environmental pollution and ecosystem destruction by microplastics is the inland and adjacent coastal waters. ), it is necessary to take samples of seawater containing microplastics and analyze the content and types of microplastics. To this end, a microplastic collecting device capable of filtering and collecting microplastic particles of 1 mm to 5 mm in size from surface water in the process of being towed along the sea surface by the power of the ship while hanging from the stern of the ship. is known and described in Korean Patent Registration No. 10-2100852.

In order to evaluate the harmfulness of these microplastics, a standard or reference material is required, and for this, there is a method of using artificially synthesized micro-sized beads or directly taking samples from the environment. The method of synthesizing microbeads or particles can obtain a large amount of samples relatively easily, but mainly uses emulsion polymerization, so the types of plastics that can be applied are limited, and it is not easy to control the particle size. In particular, it is a round particle shape and shows a big difference in shape and density from microplastics that occur in the actual natural environment. The method of obtaining a sample directly from nature takes a lot of time and money to collect, and it is not easy to separate it because a lot of organic and inorganic substances other than microplastics are mixed.

On the other hand, Korean Patent Publication No. 10-2017-0110482 estimates the failure time through an accelerated photodegradation test and predicts the service life based on this, thereby evaluating long-term durability against photodegradation in a short period of time. It is known about a service life prediction method using a test.

Republic of Korea Patent Registration No. 10-2100852. Republic of Korea Patent Publication No. 10-2017-0110482.

The present invention was developed to solve the above problems, and an object of the present invention is to provide a microplastic material manufacturing method and manufacturing apparatus using climate environment simulation applicable to all types of plastics.

In addition, the present invention is to provide a microplastic reference material that can be used for risk assessment such as ecosystem and human exposure, microplastic pollution monitoring and operating system establishment technology, microplastic measurement and analysis technology and equipment development, and a manufacturing method thereof.

In the present invention, the plastic specimen preparation step to solve the above problems; A weathering environment application step of applying a weathering environment to the plastic specimen; and a microplastic separation step of separating the microplastics from the plastic specimen to which the weathering environment is applied.

In addition, in the present invention, the fixing module 100 for fixing the plastic specimen 300; a microplastic recovery module 200 integrally connected to the lower side of the fixing module 100; a sunlight-simulating light irradiation module 400 configured on the front surface of the fixed module 100; A water injection module 500 configured on the fixed module 100; a steam generating module 600 configured under the fixing module 100; a temperature control module 700 configured behind the fixing module 100; And it provides a microplastic material manufacturing apparatus using climate environment simulation, characterized in that it comprises a housing forming the outside of the above components.

The microplastic material manufacturing method and apparatus using climate environment simulation according to the present invention have the advantage of being applicable to all types of plastics.

Microplastics occurring in nature vary greatly in size, shape, and physical properties. The method according to the present invention can produce microplastics of a size of several micrometers or less or nanometers even from synthetic resins manufactured by methods such as emulsion polymerization and plastics that are difficult to obtain from nature. It is characterized by being able to manufacture microplastics having the same size, shape and physical properties as various microplastics occurring in nature.

In addition, according to the method and apparatus of the present invention, there is a great advantage in that a large amount of microplastics can be produced and recovered in a short time.

The microplastic material manufactured using the method and device of the present invention can be used for risk assessment such as ecosystem and human exposure, microplastic pollution monitoring and operating system establishment technology, and microplastic measurement/analysis technology and equipment development.

The method for manufacturing microplastics according to the present invention not only uses sheet-shaped plastic specimens to generate microplastics, but also can manufacture specimens by adding various additives and plasticizers in the same way as plastics used in real life. While additives and plasticizers contained in plastics have the advantage of being able to manufacture more effective microplastics in the study of harmfulness to the actual ecosystem and human body, when manufacturing microplastics by a separate synthesis method, these additives or There is a disadvantage that it is difficult to use in effective research because it is difficult to include a plasticizer.

1 schematically shows a housing forming a cross section and an exterior of a weathering environmental test equipment according to an embodiment of the present invention.
2 shows a fixing module 100 for fixing a plastic specimen 300 according to an embodiment of the present invention and a microplastic recovery module 200 integrally connected to the lower side of the fixing module 100. .
3 is a schematic diagram showing a microplastic generation mechanism of a plastic specimen according to a weathering environment application according to an embodiment of the present invention.
4 shows the result of observing surface degradation according to the cumulative amount of light of a plastic specimen according to the application of a weathering environment according to an embodiment of the present invention.
5 shows the results of observing micro-cracks on the surface through confocal image analysis of PP, HDPE, Nylon6, and PS specimens according to the weathering environment application according to one embodiment of the present invention.
6 shows a comparison of particle sizes after filtering particles of microplastics prepared from plastic specimens according to a weathering environment application according to an embodiment of the present invention to 100 um.
7 is a graph showing a comparison of particle sizes after filtering particles of microplastics prepared from plastic specimens according to a weathering environment application according to an embodiment of the present invention to 1 μm.
8 shows a comparison of the sizes of micro-cracks formed in plastic specimens according to application of a weathering environment according to an embodiment of the present invention.
FIG. 9 shows the results of SEM observation of ultrafine plastic particles prepared from plastic specimens subjected to a weathering environment according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventors may appropriately define the concept of terms in order to explain their invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The term “microplastic” used throughout this specification refers to microscopic plastics that exist on earth and contaminate the environment in terms of biophysics, and usually refers to plastics having a particle size of 1 μm or less, but In the specification of the present invention, it refers to primary particles having a size of 5 mm or less and secondary particles having a size of 0.5 μm or more as micronized secondary particles by weathering thereof. That is, the microplastics according to the manufacturing method of the present invention may have a size of 0.5 μm or more and 5 mm or less, and the size of the particles can be controlled by adjusting conditions such as the type of plastic and weathering environment. On the other hand, in general, plastic particles having a size of 1 μm or less are also classified as ultra-fine plastics.

In the present invention, the plastic specimen preparation step to solve the above problems; A weathering environment application step of applying a weathering environment to the plastic specimen; and a microplastic separation step of separating microplastics from the plastic specimen to which the weathering environment is applied.

In the manufacturing method according to one embodiment of the present invention, the plastic specimen may be at least one selected from the group consisting of LDPE, HDPE, PP, PS, PVC, PA, and PET. In general, the five most commonly used general-purpose plastics are LDPE, HDPE, PP, PS, and PVC, and the five major engineering plastics are nylon, PC, PPO, POM, and PBT, which are a type of polyamide. PET, etc. is a plastic that is commonly seen around, and according to one embodiment of the present invention, it can be applied to all of various plastic materials that are not limited to specific types such as general-purpose and engineering plastics, and are not limited to the types of materials mentioned above. don't

In the manufacturing method according to one embodiment of the present invention, the weathering environment application step may be an accelerated test through light irradiation amount control, or may be sunlight-simulating light irradiation, and the sunlight-simulating light irradiation uses a UVA/Xenon light source. it could be More preferably, an ultraviolet wavelength generated from a UVA-340 lamp having a wavelength of 290 to 400 nm may be used.

In the manufacturing method according to one embodiment of the present invention, the microplastic separation step may include ultrasonic cleaning of a plastic specimen subjected to a weathering environment. Through such ultrasonic cleaning, it is possible to obtain particles having a shape similar to microplastics found in actual nature. In the actual land environment, microplastics fall from the surface of plastics due to wind or strong rain. In the weather resistance test, there are parts that are difficult to simulate such a phenomenon and the shape of particles formed therefrom. By washing, the microplastics attached to the surface of the specimen are removed, so that they can have a shape similar to the microplastics found in nature.

Hereinafter, implementation examples and embodiments of the present invention will be described in detail so that those with general knowledge in the technical field to which the present application pertains can easily practice, as shown in the accompanying drawings, preferred embodiments of the present invention. In particular, the technical idea of the present invention and its core configuration and operation are not limited by this. In addition, the contents of the present invention can be implemented in various types of equipment, and is not limited to the implementation examples and examples described herein.

1 schematically shows a housing forming a cross section and an exterior of a weathering environmental test equipment according to an embodiment of the present invention. In particular, the present invention relates to the production of microplastics simulating a terrestrial environment and a recovery system for microplastics manufactured therefrom.

An apparatus for manufacturing a microplastic material using climate environment simulation according to an embodiment of the present invention includes a fixing module 100 for fixing a plastic specimen 300; a microplastic recovery module 200 configured below the fixing module 100; a sunlight-simulating light irradiation module 400 configured on the front surface of the fixed module 100; A water injection module 500 configured on the fixed module 100; a steam generating module 600 configured under the fixing module 100; a temperature control module 700 configured behind the fixing module 100; And it provides a microplastic material manufacturing apparatus using climate environment simulation, characterized in that it comprises a housing forming the outside of the above components.

2 shows a fixing module 100 for fixing a plastic specimen 300 according to an embodiment of the present invention and a microplastic recovery module 200 configured under the fixing module 100.

The fixing module 100 for fixing the plastic specimen 300 is preferably in a form capable of fixing the specimen in a sliding manner in the upward and downward direction, and the microplastic recovery module 200 configured at the bottom thereof is located on the upper part of the fixing module. The surface of the plastic specimen 300, such as water drops generated from the water injection module 500 configured to implement a rainfall environment among land environments or the steam generating module 600 configured to implement a humid environment configured under the fixed module It is preferable to implement a detachable type so that the microplastic formed on the surface of the specimen can be recovered from the lower part when it flows down after being condensed in.

According to one embodiment of the present invention, the microplastic generation method and generating device can control the degree of miniaturization by controlling light, heat, and water. More specifically, the type of light irradiation lamp, light irradiation intensity, light irradiation time, It is characterized in that the degree of refinement is controlled by adjusting the test temperature, the water spray method, and the total test time.

That is, the present invention relates to a method for miniaturization of plastics, and more particularly, to a method for generating and recovering micro-sized microplastics using climatic environment simulation, wherein the process for miniaturizing plastics includes (a) generating microplastics, (b) ) It can be composed of a total of three steps: (c) microplastic recovery step (c) microplastic size classification step.

In the miniaturization process of the plastic, the microplastic generation step of step (a) uses a generator that simulates the terrestrial climate environment (see FIG. 1), and controls light, heat, and water conditions, which are deterioration conditions of the climate environment. It is characterized in that it includes a detailed device that can be. In order to simulate the climatic environment of a specific region, information such as annual irradiation light, precipitation, and temperature of the region is required, and the wavelength and amount of light irradiated to the plastic specimen, water control, and temperature are set by reflecting this.

In one embodiment of the present invention, the microplastic recovery module 200 may be detachably implemented under the fixing module. By implementing the recovery module in a detachable manner, it is possible to effectively recover or separate the microplastic material in observing changes in the shape of the microplastic that occur over time in the climatic environment simulation test of the same specimen.

In one embodiment of the present invention, the sunlight-simulating light irradiation module 400 may include a UVA/Xenon light source.

At this time, the wavelength of irradiation light uses a xenon-arc light source to simulate the full range of sunlight or UVA-340 (290-400 nm) and UVB-313 (250-400 nm) light sources with excellent short-wavelength reproducibility of the sunlight spectrum. In this way, the light irradiation time can be adjusted from 6 to 16 hours. In order to simulate the climate of a specific area, the irradiation intensity corresponding to the annual UV irradiation amount of the corresponding area can be set.

Further, in the light irradiation module according to one embodiment of the present invention, it is more preferable that a plurality of lamps are arranged at regular intervals to irradiate the surface of the plastic specimen with the same amount of light. As a specific example, a light source in which long rod-shaped light sources such as a plurality of fluorescent lamps are arranged at regular intervals may be used.

In one embodiment of the present invention, the water spray module 500 may spray water in a spray form. The water spraying module 500 according to one embodiment of the present invention is for realizing a rainfall environment among terrestrial environments, and it is preferable that water is sprayed so that the water dispersed is in the form of rain, and the amount of water to be sprayed It is more preferable that the intensity can be adjusted.

In addition, in one embodiment of the present invention, the steam generating module 600 configured under the fixing module is for realizing a humid environment among land environments, which is preferably a form of generating steam by heating water, but is usually Any configuration that can increase the humidity is possible.

On the other hand, the water spraying or water condensing step using the water spraying module or the steam generating module may select a method of spraying or condensing water in an environment where light is not irradiated, and at this time, the time is adjusted to 8 to 18 hours to simulate simulation. It can be adjusted according to the desired climate.

In the manufacturing method according to one embodiment of the present invention, the temperature control module 700 may adjust the temperature of the specimen in the range of 30 ° C to 80 ° C when light irradiation, water spray or steam is generated.

3 is a schematic diagram showing a microplastic generation mechanism of a plastic specimen according to a weathering environment application according to an embodiment of the present invention.

When ultraviolet rays are irradiated from the light irradiation module, the surface of the plastic specimen is oxidized and degraded by decomposition of polymer chains, and when water is sprayed from the steam generating module or the water injection module and the water is condensed on the plastic surface, when ultraviolet rays are irradiated, this deterioration occurs. is further accelerated, after which cracks occur on the surface of the plastic specimen, and microplastics are formed due to the generation and growth of these cracks. plastic is formed.

<Example> Microplastic manufacturing test

Manufacturing of microplastics was performed under the following conditions using the microplastic material manufacturing apparatus using the weathering environment simulation shown in FIGS. 1 and 2 according to an embodiment of the present invention.

First, after placing the injected plastic specimen on the specimen stand, Cycle 1 (condition: 60 C, UV irradiation amount 0.89 W/m2/nm, 8 hours), and then Cycle 2 (condition: 50 C, no UV irradiation, 4 hours) After that, cycle 1 and cycle 2 are repeated continuously, and the microplastic generated every 100 MJ/m2 of cumulative light is recovered from the collection container, and the plastic specimen is taken out and ultrasonically Microplastics adhered to the surface were recovered by washing.

This cycle test example simulates the high-temperature and high-humidity Florida environment of ASTM G 154-16, and it is possible to simulate the environment in other regions by adjusting the temperature, light amount, and time.

<Analysis Example 1> Analysis of surface deterioration of microplastic specimens

4 shows the result of observing surface degradation according to the cumulative amount of light of a plastic specimen according to the application of a weathering environment according to an embodiment of the present invention. As can be seen from FIG. 4, it can be seen that all specimens change color when irradiated with a cumulative light amount of 100 MJ/m2.

Figure 5 shows the results of observing micro-cracks on the surface through confocal image analysis of PP, HDPE, Nylon6 and PS specimens according to the weathering environment application according to one embodiment of the present invention. From the results of this test, it was found that the formation of microplastics is closely related to the size of cracks formed by deterioration on the plastic surface. did

<Analysis Example 2> Particle size analysis of microplastics

6 is a comparison of particle sizes after filtering microplastic particles prepared from plastic specimens according to a weathering environment application according to an embodiment of the present invention with 100 um, and FIG. 7 shows particles after filtering with 1 um It is shown by comparing the size.

First, the prepared microplastic particles were filtered with 100 um and then measured with a particle size analyzer (PSA), and the particle size of the microplastics obtained by filtering with 1 um was measured with dynamic light scattering (DLS). The graph on the left shows the particle size distribution, and the right graph shows the average size of microplastic particles. In particular, when microplastics filtered to 1 um were measured using DLS equipment, ultrafine plastics of 1 um or less were observed, indicating that particles having a size classified as ultrafine plastics in one embodiment of the present invention can be formed. there was.

8 shows a comparison of the sizes of micro-cracks formed in plastic specimens according to application of a weathering environment according to an embodiment of the present invention.

Comparing the size of the microcracks in FIG. 8 with the particle sizes of the microplastics in FIGS. 6 and 7, in the case of the plastic specimens having large microcrack sizes, the results of the microplastic particles being large were observed.

9 is a result of SEM observation of ultrafine plastic particles prepared from plastic specimens according to weathering environment application according to one embodiment of the present invention. The shape of the particles has an irregular shape similar to that observed in nature, but the emulsion PE microplastics synthesized through polymerization are round in shape, which is different from microplastic particles observed in nature.

100: fixed module
200: microplastic recovery module
300: plastic specimen
400: sunlight simulation light irradiation module
500: water injection module
600: steam generating module
700: temperature control module

Claims (12)

plastic specimen preparation step;
A weathering environment application step of applying a weathering environment to the plastic specimen; and
A method for producing a microplastic material using a climate environment simulation, comprising a microplastic separation step of separating the microplastic from a plastic specimen to which a weathering environment is applied. The method of claim 1,
The plastic specimen is a microplastic material manufacturing method using climate environment simulation, characterized in that at least one selected from the group consisting of LDPE, HDPE, PP, PS, PVC, PA, PET. The method of claim 1,
The method of manufacturing a microplastic material using climate environment simulation, characterized in that the weathering environment application step is an accelerated test through light irradiation control. The method of claim 1,
The method of manufacturing a microplastic material using a climate environment simulation, characterized in that the weathering environment application step is sunlight simulation light irradiation. The method of claim 4,
The method of manufacturing a microplastic material using a climate environment simulation, characterized in that the sunlight simulation light irradiation uses a UVA / Xenon light source. The method of claim 1,
The microplastic separation step is a microplastic material manufacturing method using climate environment simulation, characterized in that ultrasonic cleaning of the plastic specimen to which the weathering environment is applied. a fixing module 100 fixing the plastic specimen 300;
a microplastic collection module 200 configured on a lower side of the fixing module 100;
a sunlight-simulating light irradiation module 400 configured on the front surface of the fixed module 100;
a water injection module 500 configured above the fixing module 100;
a steam generating module 600 configured under the fixing module 100;
a temperature control module 700 configured behind the fixing module 100; and
Microplastic material manufacturing apparatus using climate environment simulation, characterized in that it comprises a housing forming the exterior of the above components. The method of claim 7,
The microplastic recovery module 200 is a microplastic material manufacturing device using climate environment simulation, characterized in that detachably implemented on the lower side of the fixed module. The method of claim 7,
The solar simulation light irradiation module 400 is a microplastic material manufacturing apparatus using a climate environment simulation, characterized in that it includes a UVA / Xenon light source. The method of claim 7,
The water injection module 500 is a microplastic material manufacturing apparatus using climate environment simulation, characterized in that for spraying water in a spray form. The method of claim 7,
Microplastic material manufacturing apparatus using climate environment simulation, characterized in that the water vapor generating module 600 generates water vapor by heating water. The method of claim 7,
The temperature control module 700 is a microplastic material manufacturing apparatus using climate environment simulation, characterized in that it can adjust the temperature of the specimen in the range of 30 ℃ to 80 ℃ when light irradiation, water spray or steam is generated.

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