Europe and the United States prefer paper packaging, and fluorine free paper packaging will become a new air outlet

  • 2022-11-08
With the rapid development of economy and the enhancement of environmental protection awareness, China's plastic ban and restriction order will be fully implemented in January 2021. As well as the European Commission's disposable plastic product guide and the forthcoming revision of the packaging and packaging waste directive, it will be more inclined to the paper packaging of plant fiber substrates, including pulp molded product packaging. Paper packaging will become the largest packaging material used in catering, food packaging and other fields

1. Disadvantages of PE coated paper and silicone paper

Due to the contact with oily, fatty and water containing foods, paper packaging must be waterproof, oil proof and impermeable. In order to obtain the effect of water and oil resistance, most food packaging papers are PE coated paper at present, that is, a thin layer of polyethylene plastic is coated on the paper, and some water-based coating materials are polyacrylate, polyvinyl alcohol, carboxymethyl cellulose, etc., forming a continuous and dense organic polymer film, so that oil and water cannot pass through the protective layer, so as to achieve the purpose of water and oil resistance. High end products are also packaged with silicone oil paper. The silicone oil paper has three layers: the first layer of base paper, the second layer of coating, and the third layer of silicone oil.

This kind of polymer film itself is not oil resistant, and the grease can still spread on the surface of the film. Some contain bisphenol a grease, which may release harmful substances when contacting high temperature food. In addition, this kind of polymer material cannot be degraded or degraded very slowly in nature, which is difficult to recycle, high in recovery cost, and has environmental pollution problems.

2. Disadvantages of fluorine-containing waterproof and oil repellent

In addition to the coating, a small amount of water and oil repellent agent is added in the paper making process or a layer of paint with water and oil repellent properties is coated on the paper surface to reduce the paper surface tension, which can give the paper substrate water and oil repellent properties without affecting the recycling of paper products. Although the waterproof and oil proof effect is excellent, this type of waterproof and oil proof agent usually uses long-chain perfluorinated monomers (PFCs) with a carbon atom number greater than 6, usually C8 PFCs (containing 8 carbon perfluorocarbons) with 8 carbon atoms. The longer the chain of carbon atoms in perfluorinated alkyl, the better its waterproof and oil proof performance. This is because fluoropolymers can form a film on paper fibers, The long side chains containing fluorine in the film can be stretched and arranged directionally at the interface. The film can significantly reduce the surface energy of the substrate, which is smaller than that of ordinary liquids, so it has the property of water and oil resistance.

However, in recent years, it has been found through research that these long-chain fluoroalkyl compounds will produce ammonium perfluorooctanoate/perfluorooctane sulfonate (PFOA/S) which is harmful to the environment and human body during use. Low dose of these substances have bioaccumulation, especially in long-term contact with food, which is highly toxic to human body and may cause genetic, reproductive, developmental, liver, cardiovascular and other diseases of biology.

Therefore, the European Union, environmental protection organizations in Canada and the National Environmental Protection Agency of the United States have restricted the use of PFOA/S. Long chain fluoroalkyl compounds (with the carbon atom number greater than 6) are also restricted to be used in waterproof and oil repellent agents for paper products. C8 PFCs are gradually withdrawing from the market.

3. Requirements for Fluorine containing Additives in China

Compared with the old national standard GB 9685-2008, the new version of the national standard GB 9685-2016 Standard for the Use of Additives for Food Contact Materials and Products deletes two perfluorocarbons: diethanolamine mono (1H, 1H, 2H, 2H perfluoroalkyl) phosphate and bi (1H, 1H, 2H, 2H perfluoroalkyl) phosphate, perfluoroalkyl acrylate copolymer (perfluoroalkyl acrylate copolymer).

At present, the toxicological data on C6-PFCs are limited, and studies show that they do not have the same bioaccumulation and potential systemic and developmental toxicity as C8 substances. Animal and epidemiological studies have shown that C6-PFCs will not accumulate in organisms because they can be rapidly excreted. Therefore, short chain C6-PFCs are still allowed to be used as food contact materials in China.

According to GB 9685-2016 Standard for Use of Additives in Food Contact Materials and Products, GB 4806.6-2016 Plastic Resins for Food Contact, GB 4806.10-2016 Coatings and Coatings for Food Contact and other standards in China, some small molecules or polymers containing fluorine can be used in food contact materials and products under certain restrictions. For example, tetrafluoroethylene polymer or copolymer of tetrafluoroethylene and other fluorinated monomers (hexafluoropropylene, perfluoro-n-propyl vinyl ether, etc.) can be used for plastic products or coatings, but the migration limits of tetrafluoroethylene, hexafluoropropylene, perfluoro-n-propyl vinyl ether and other fluorinated compounds must be met (0.05 mg/kg, 0.01 mg/kg and 0.05 mg/kg respectively). Fluorine containing compounds such as difluoro chloromethane, 2,2-ethylidene bis (4,6-di-tert-butylphenyl) fluorophosphazene, bis [ethyl (perfluorooctane) sulfonamidoethyl] ammonium phosphate can be used as additives for food contact plastics or paper products.

4. Fluorine free water and oil repellent

In January 2015, the US FDA announced that food contact substances (FCSs) containing monoethanolamine and diethanolamine, valeric anhydride, and perfluoroalkyl substituted phosphonic acid were prohibited as waterproof and oil repellent agents for paper and paperboard to contact water and oil foods. In January 2021, the US FDA announced that it would require manufacturers to voluntarily phase out the use of food contact packaging materials containing PFAS/PFOA within three years, which would be enforced from January 2024. As of July 2022, 26 states in the United States have introduced legislation restricting the use of PFAS/PFOA, and 11 states have implemented it.

The restrictions on PFAS within the EU are gradually expanding. In Denmark, the ban on the use of paper and paperboard food contact materials containing perfluorinated and polyfluoroalkyl compounds came into force in July 2020. The Netherlands, Germany, Norway, Denmark and Sweden proposed to propose the revision of REACH regulations to comprehensively restrict the manufacture and use of PFAS/PFOA.

Fluorine free waterproof and oil repellent agent has become a research hotspot in the industry. It is safer and more environmentally friendly. Paper packaging, pulp molding and paper mulch products produced with it are the first choice for export to Europe, the United States and Japan. Although surface treatment such as product surface coating and spraying dip coating can achieve the same waterproof and oil proof performance as fluoro products, its high equipment investment and treatment cost are doomed to be unable to be used on a large scale. The advantages of the scheme of fluorine free waterproof and oil proofing agent added in the slurry are no equipment investment and the cost is controllable. The disadvantage is that the oil proofing performance cannot reach the effect of fluorine based products. However, the industry also has different views on the oil control effect of fluoride free additives. For example, the previous test standard for impermeability of 95 ℃ hot oil for 30 minutes for pulp molded products was considered by the industry and the end consumer market to be greatly beyond the actual use scenario. At present, the European and American markets are more rational in accepting the physical test results, or according to the terminal use scenarios and customer needs, select the test standard of 30 minutes impermeability of hot oil at a certain temperature (30 ℃, 40 ℃, 70 ℃). After all, the scheme that can be widely accepted by the market must be feasible and cost controllable at the production end.

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