TWI598389B - Novel low carbon bio-degradable film and application thereof - Google Patents

Description

New low carbon row degradable sheet and its products

A degradable sheet, in particular a degradable sheet having a low carbon content after degradation.

Although petrochemical-derived plastic materials are widely used in daily necessities, with the gradual reduction of petroleum raw materials, the enhancement of the greenhouse effect, and the environmental pollution caused by the inability of plastic materials to decompose, the use of petrochemical plastics is reduced or degradable. Plastics have become an emerging trend in plastics, and bioplastics have emerged. At present, bioplastics can be divided into two categories, one is bio-based plastics, and the other is biodegradable plastics. The bio-based plastics are those in which some or all of the plastics are obtained from renewable biological sources. Or reduce the use of petrochemical-derived plastics and reduce the production of carbon dioxide (CO ₂ ), which is a biodegradable and degradable material from non-petrochemical sources such as corn starch and pea starch, which is intended to reduce Pollution of plastic waste. In addition, because biodegradable plastics can be decomposed, their mechanical strength decays rapidly after being left for a period of time. Generally, film bags are recommended to be used within one year. Therefore, some manufacturers have begun to develop biodegradable materials that can promote the decomposition of petrochemical plastics. Auxiliaries make petrochemical plastics meet biodegradable targets. Currently, biodegradable auxiliaries are commercially available as photo-oxidation auxiliaries and new enzyme-regulating auxiliaries. Manufacturers of photo-oxidation auxiliaries such as EPI's TDPA As well as Symphony's d2w...etc., it is currently the mainstream additive, but due to the heavy metal content and the failure to pass the compostable test, some regions or countries have begun to ban. The new enzyme-regulated auxiliaries will have considerable development in the future due to the absence of heavy metal residues. Currently, major manufacturers such as Earth Nurture (ENA® additive), ECM BioFilms, Bio-Tec Environmental (Ecopure®), Enso Plastics , IQON Ecozyme...etc., the public information of the enzyme-controlled auxiliary agent is as follows: http://agbio.coa.gov.tw/information detail.aspx? Dno=34347&ito=87 ; http://technews.tw/2016/03/13/bacteria-eat-plastic/ ;http://www.bioindustry.cn/info/view/26856.

Enzyme-regulated auxiliaries can react with plastics due to the inclusion of special enzymes, which can reduce the bond energy between carbon-carbon bonds (CC) and carbon-hydrogen bonds (CH) of plastic molecules, which makes it easier for microorganisms to decompose the petrochemical plastics. Organic can be used as a crop compost.

Although enzyme-regulating auxiliaries decompose plastics in a natural way, if they are used alone in petrochemical plastics such as polyethylene (PE) or polypropylene (PP), the disadvantage is that the decomposition rate is too slow, even in the initial stage. The mechanical strength of the material can only be slightly reduced, and there is still a distance from the general cognitive decomposition. In addition, the speed and ability of the petrochemical plastics to degrade depends on the amount of additives, which is reflected in the final cost of the product, which is not easy to promote.

In order to solve the problems of environmental pollution caused by the increasingly reduced petroleum source of petrochemical plastics and the inability to decompose, and the high cost of the enzyme-controlled auxiliary agent, the present invention provides a novel low-carbon degradable sheet with a thickness between between 0.01 ~ 0.15mm, a density of between 0.6 ~ 1g / cm ³ between which a plastic material comprising 20 ~ 80wt%, a bio-based material 10 ~ 70wt%, and an enzyme-regulated aid 1 ~ 10wt%, wherein The plastic material is a petrochemical-derived plastic material; the bio-based material comprises a combination of starch, plant fiber powder or starch, and plant fiber powder; the enzyme-regulated auxiliary agent comprises a polyolefin resin, an enzyme, a microorganism, and a nutrient source; The new low carbon row degradable sheet has a degradation rate of at least 90%.

Wherein, the plastic material comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride, ethylene-vinyl acetate copolymer or polyethylene terephthalate; the polyolefin resin is polyethylene, polypropylene Or an ethylene-vinyl acetate copolymer; and the bio-based material further comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride, ethylene-vinyl acetate copolymer or polyethylene terephthalate.

Wherein, the plant fiber powder comprises bamboo powder, rice bran powder, straw powder, wood flour or coffee powder.

Wherein, it further comprises 1-20% by weight of a functional additive material of a colorant, a filler, a toughening agent, a processing aid or a nano-inorganic material.

Wherein, the toughening agent comprises a thermoplastic polyolefin, a thermoplastic elastomer, and a vulcanized thermoplastic polyolefin-based elastomer-based elastomer, and the processing aid comprises a paraffin wax such as a dispersing agent and a slip agent, a polyethylene wax, an oxidized polyethylene wax, a fatty acid or a fatty guanamine; and the nano inorganic material comprises nano-scale talc, mica, and high territory.

Among them, it is manufactured by extrusion or blow molding.

The present invention further provides a container, a bag product and a bottle made of the novel low carbon row degradable sheet.

The invention combines the bio-based material containing the plant-derived powder with the existing enzyme-regulating auxiliary agent and then extrudes or blows the molding process to form a film, a bag, a plate, a sheet and the like, and the advantages thereof are as follows:

1. The trace amount of water contained in the bio-based material containing the plant-derived powder has a foaming effect in the manufacturing process, and a film, a bag, a plate having a density of 0.6 to 1 g/cm ³ can be obtained without adding a foaming agent. Products such as sheets cause a certain amount of micropores in the product, which makes the product lighter, and the contact area between starch and enzymes and bacteria becomes larger due to the generation of micropores, thus contributing to the decomposition of starch or plastic materials. In addition to the good and rapid degradation characteristics of the plant source powder, it can provide more nutrient sources for microorganisms, accelerate the rapid proliferation of microorganisms, accelerate the disintegration and degradation rate of petrochemical plastics, and further decompose the plant source powder. Helps increase the surface area of the enzyme in the enzyme-regulated auxiliaries, again accelerating the rate of decomposition of the overall material.

2. The invention has the advantages of being highly degradable or fully decomposable, and can pass ISO14855, Composting tests such as EN13432.

3. The chemical formula of the plastic material, such as polyethylene (CH ₂ )n, the chemical formula of the bio-based material, such as starch (C ₆ H ₁₂ O ₅ )n, the carbon dioxide produced by the degradation or combustion of the two is plastic The amount produced is large, so the invention contains a large amount of renewable bio-based materials, which replaces the addition amount of the plastic material, and can greatly reduce the carbon dioxide emissions generated after degradation or incineration, in order to meet the low carbon discharge effect of the present invention. .

The invention can reduce the use amount of the enzyme-regulated auxiliary agent by indirectly reducing the use amount of the enzyme-regulated auxiliary agent by adding a low-cost plant-derived powder bio-based material such as starch or vegetable fiber. In addition to reducing the cost and maintaining the effect of high decomposition or total decomposition, it is also possible to reduce the amount of plastic used in petrochemical sources, and to combine and decompose other types of plastic materials without restriction; and then degrade by Table 1 of the present invention. The rate comparison table confirms that the addition of bio-based materials can further accelerate the decomposition rate of petrochemical plastics. Table 2. Comparison of physical properties of polyethylene plastic film, bio-based plastic film and bio-based enzyme-decomposable film. It can be found that a film with an enzyme-regulated auxiliary agent is added, and no enzyme-regulated auxiliary agent is added or added. In the control group, the physical properties were not affected.

Biomass powders, protein and bacterial components in bio-based plastics and enzyme-regulated auxiliaries are easily agglomerated by hydrogen bonds and van der Waals, and agglomeration tends to cause weakening of products and poor printability. Therefore, the dispersion and refinement of these bio-based materials in plastics will affect the quality of the products. In addition, enzymes and strains in bio-based materials or enzyme-regulated auxiliaries can affect product function and mechanical strength due to excessive temperature, so it is also important to reduce process temperature during product production. The invention increases the dispersibility of the bio-based material in the plastic by adding processing aids and nano-inorganic materials together with suitable equipment planning, and produces high-quality sheets with better product strength or printability. The processing aid comprises paraffin, PE wax, OPE wax, fatty acid or fatty decylamine such as a dispersing agent or a slip agent. Nano inorganics include nano-sized silicates such as talc, mica, high territories, and the like. The bio-based material and the enzyme auxiliary agent containing the plant source powder of the invention can be obtained by using the nano inorganic substance and processing aid With the assistance of the screw, it is evenly dispersed in the screw. The screw of the machine needs a long diameter ratio of more than 25 and has a certain shear force design.

A novel low carbon row degradable sheet having a thickness of between 0.01 and 0.15 mm and a density of between 0.6 and 1 g/cm ³ , comprising a plastic material of 20 to 80 wt %, a bio-based material of 10 to 70 wt %, and An enzyme-regulated additive is 1 to 10% by weight, and the biodegradation rate of the novel low-carbon degradable sheet is at least 90%.

The sheet according to the present invention can be generally classified according to the thickness: a sheet having a thin thickness can be referred to as a film, and a sheet having a thick thickness can be referred to as a sheet, but none of the present invention Reveal the spirit.

Wherein, the plastic material is a general petrochemical or plant-derived plastic material, such as polyethylene (Polyethylene, PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride, ethylene-vinyl acetate. Polyethylene-co-vinyl acetate (EVA) or Polyethylene Terephthalate (PET). The plastic material cannot be used in the environment before adding other degradable components. degradation.

The bio-based material comprises starch or one or more mixtures of plant fiber powder such as bamboo powder, wood flour, rice bran powder, straw powder, coffee powder, etc., and further the bio-based material may be starch or vegetable fiber and a base plastic (polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer or polyethylene terephthalate, etc.), after mixing to form plastic pellets, and then mixing with other components of the present invention, preferably, the plastic pellets are contained The starch or plant fiber content is 60-80% by weight.

The enzyme-regulated additive used in the present invention contains a special enzyme, and the specific reactivity of the special enzyme to a specific chemical structure enables the plastic material to be plasticized by bacteria and bacteria in a soil environment. The rubber material is decomposed. In addition to the special enzyme, the enzyme-regulating additive may further contain a polyolefin resin (PE, PP, EVA, etc.), a microbial and a microbial nutrient source, which can add the added polyethylene (PE). Highly degradable or fully decomposed. The so-called highly degraded or fully decomposed in the present invention means that the plastic material can achieve a degradation rate of 90% or more.

In the composition of the present invention, a functional additive material may be added in an amount of 1 to 20% by weight, such as a colorant, a filler, a toughening agent, a processing aid or a nano-inorganic, depending on process requirements or end product requirements. The filler comprises inorganic substances such as calcium carbonate, talc, etc., and the toughening agent comprises thermoplastic polyolefin (TPO), thermoplastic elastomer (TPE), and sulfurized thermoplastic polyolefin elastomer (Thermoplastic vulcanizate). , TPV)-based elastomers, etc., processing aids include paraffin waxes such as dispersants, slip agents, polyethylene waxes (PE waxes), oxidized polyethylene waxes (OPE waxes), fatty acids or fatty guanamines. Nano inorganics include nanoscale silicates such as nanoscale talc, mica, high territories, and the like.

The formulation composition provided by the present invention can be formed into a sheet by a general plastic processing method, and is not limited thereto. For example, a plastic material, a bio-based material, and an enzyme-regulating auxiliary agent are melted and kneaded together, and then blown and extruded. According to the thickness requirement, it is processed into a plate, a sheet or a film, and the plate, sheet or film can be further formed into a plastic bowl, a tray, a cup or the like into a container or other film bag by means of plastic forming. The formulations of the plastic materials, bio-based materials and enzyme-regulated auxiliaries mentioned in the present invention can also be prepared into bottles or cans by a blowing method.

In general, when a bio-based plastic and an enzyme-regulating auxiliary agent of a plant-derived powder are added, since the bio-source powder is easily produced due to moisture absorption during production or storage, the product is easily deformed, the quality is unstable, and the physical property is low. Poor, therefore, in the present invention, before the bio-based material is blended with the enzyme-regulated auxiliary agent and the petrochemical plastic, the bio-based material and the enzyme-regulated auxiliary agent need to be dried to a moisture content of less than 0.5% to reduce the subsequent process. Lieutenant's question. However, if the plant fiber powder is selected as the bio-based material in the present invention, the physical properties and wear resistance of the product can be increased, so that depending on the characteristics of the end product, Use any combination of starch and plant fiber powder to achieve the physical properties and quality requirements of the product.

The invention can further increase the dispersibility of the bio-based material in the plastic by adding a processing aid and a nano-inorganic material together with a suitable equipment plan to produce a high-quality sheet with better product strength or printability. The bio-based material and the enzyme auxiliary agent containing the plant-derived powder of the invention can be uniformly dispersed in the screw by the aid of the nano-inorganic material and the processing aid, and the screw of the machine machine needs to have an aspect ratio of more than 25, and has a certain Shear force design.

Please refer to Table 1 to prove that the present invention can further accelerate the decomposition rate of the plastic material through the combination of the bio-based material containing the plant-derived powder and the enzyme-regulated auxiliary agent, and only the enzyme-regulated auxiliary agent is added by the control group 1. Polyethylene (PE) thickness of 0.03mm film, control group 2 only starch-added polyethylene (PE) thickness of 0.03mm film material, compared with the bio-based material containing plant-derived powder and enzyme-regulated auxiliary agent of the present invention The polyethylene was made to have a thickness of 0.03 mm and the degradation rate was compared at 90 days, 150 days, 180 days, and 300 days.

It can be seen from Table 1 that the control group 2 with pure PE plus starch no longer degraded after 150 days, indicating that the PE which can be decomposed in the control group 2 is decomposed, and the PE which cannot be decomposed will remain in the environment forever. create pollution.

The group containing the PE, the starch and the enzyme-regulated auxiliary agent of the present invention is also dissolved in 40 days after the dissolution of the starch added in 150 days, and within 30 days from 150 days to 180 days, 7 wt% of the enzyme-regulated type. The additive can completely or highly decompose 53% by weight of PE, because the addition of bio-based materials such as starch can cause a certain amount of micropores in the product, in addition to the light weight effect of the product, and also the generation of micropores. The contact area between starch and enzymes and bacteria becomes larger, which contributes to the accelerated decomposition of plastic materials by enzyme-regulated additives. In addition, starch has good and rapid degradation characteristics, which can provide more nutrient sources for microorganisms, accelerate the rapid proliferation of microorganisms, accelerate the disintegration and degradation rate of petrochemical plastics, and further help to increase enzymes after starch is first decomposed. The surface area of the enzyme in the auxiliaries aids again accelerates the rate of decomposition of the overall material.

In contrast, control group 1 containing only PE and enzyme-regulated auxiliary agent, because no bio-based materials such as starch were added to form micropores which increased the surface area of the reaction, the decomposition rate of PE was rather slow or even decomposed before 150 days. Even if half of the amount of PE (about 50% by weight, which is equivalent to the amount of PE added in the group of the present invention) is to be decomposed, it takes at least 180 days, and within 30 days (150 days to 180 days) with respect to the present invention. The 53% by weight of PE can be decomposed, and the invention can accelerate the decomposition rate of the plastic material by at least 5-6 times.

Please refer to the following Table 2, which is a comparison table of physical properties of polyethylene plastic film, bio-based plastic film and bio-based enzyme decomposable film made by the experimental group in Table 1 above, and it can be found that an enzyme-regulated auxiliary agent is added. The film had little effect on the physical properties of the control group without or with the addition of an enzyme-regulated adjuvant. (film thickness 0.06mm)

The above-mentioned Tables 1 and 2 are only the preferred embodiments of the present invention, and are not intended to limit the scope of the claims of the present invention, and other equivalent changes or modifications made without departing from the spirit of the present invention. All should be included in the scope of the claims of the present invention.

Claims (9)

A novel low carbon row degradable sheet having a thickness of between 0.01 and 0.15 mm and a density of between 0.6 and 1 g/cm ³ , which is made of a low carbon row degradable material, the low carbon row The degradable material comprises a plastic material 20~90wt%, a bio-based material and an enzyme-regulated auxiliary agent 10~80wt% blended, wherein: the bio-based material and the enzyme-regulated auxiliary agent regulate the enzyme The type of auxiliary agent accounts for 10~12wt%; the plastic material is a petrochemical-derived plastic material; the bio-based material comprises starch, plant fiber powder or a combination thereof, and the bio-based material is firstly mixed with polyethylene, polypropylene and polyphenylene. Ethylene, polyvinyl chloride, ethylene-vinyl acetate copolymer or polyethylene terephthalate is mixed into a plastic granule containing the bio-based material, and then blended with the plastic material and the enzyme-regulated auxiliary agent; the enzyme The modulating additive comprises a polyolefin resin, an enzyme, a microorganism, and a nutrient source; and the degradation rate of the novel low carbon row degradable sheet is at least 90%. For example, the novel low carbon row degradable sheet of claim 1 is: wherein the plastic material comprises polyethylene, polypropylene, polystyrene, polyvinyl chloride, ethylene-vinyl acetate copolymer or polyethylene terephthalic acid. The acid ester; and the polyolefin resin is a polyethylene, polypropylene or ethylene-vinyl acetate copolymer. The novel low carbon row degradable sheet according to item 1 of the application scope, the plant fiber powder comprises bamboo powder, rice bran powder, straw powder, wood powder or coffee powder. For example, the novel low carbon row degradable sheet of claim 1 further comprises 1-20% by weight of a functional additive material of a colorant, a filler, a toughening agent, a processing aid or a nano inorganic substance, and is involved in blending, At this time, the low carbon row degradable material is 80 to 99 wt%. A novel low carbon row degradable sheet according to claim 4, wherein the toughening agent comprises a thermoplastic polyolefin, a thermoplastic elastomer, a vulcanized thermoplastic polyolefin elastomer elastomer, and the addition The auxiliary agent comprises a dispersing agent selected from the group consisting of paraffin wax, polyethylene wax, oxidized polyethylene wax, fatty acid or fatty decylamine; and the nano inorganic material comprises nano talc, mica, and high territory. For example, the novel low carbon row degradable sheet of claim 1 is manufactured by extrusion or blow molding. A novel low-carbon row degradable sheet container, which is made of a novel low-carbon row degradable sheet of the patent application scopes 1 to 6. The invention relates to a bag product of a novel low carbon row degradable sheet, which is made of a novel low carbon row degradable sheet of the patent application scopes 1 to 6. A novel low carbon row degradable sheet bottle made of a novel low carbon row degradable sheet of the patent application scopes 1 to 6.