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CN-120331066-A - Bio-based fluorine-free oil-proof agent for food packaging paper

CN120331066ACN 120331066 ACN120331066 ACN 120331066ACN-120331066-A

Abstract

The invention discloses a bio-based fluorine-free oil-proof agent for food packaging paper, which comprises, by weight, 30-50 parts of modified low-viscosity starch, 5-15 parts of reinforced polymer emulsion, 10-30 parts of 10wt% polyvinyl alcohol aqueous solution, 3-20 parts of 3wt% nano cellulose aqueous solution, 0.5-2 parts of plasticizer and 0.01-0.3 part of preservative. The invention has the advantages of environment-friendly raw materials, no fluorine, high efficiency, oil resistance and the like.

Inventors

  • YAO XIANPING
  • JIANG JIANMEI
  • CHEN HUI
  • YAO XIANGRONG

Assignees

  • ZHEJIANG HANGHUA NEW MATERIAL TECH CO LTD

Dates

Publication Date
20250718
Application Date
20250325
Priority Date
20250325

Claims (10)

  1. 1. The bio-based fluorine-free oil-proof agent for the food packaging paper is characterized by comprising, by weight, 30-50 parts of modified low-viscosity starch, 5-15 parts of reinforced polymer emulsion, 10-30 parts of 10wt% polyvinyl alcohol aqueous solution, 3-20 parts of 3wt% nano cellulose aqueous solution, 0.5-2 parts of plasticizer and 0.01-0.3 part of preservative.
  2. 2. The bio-based fluorine-free oil repellent agent according to claim 1, wherein the modified low-viscosity starch is prepared by the following method: Mixing low-viscosity starch and water to form a mixed solution with the mass concentration of 20-30%, adding alpha-amylase, carrying out enzymolysis for 10min-1h at 40-60 ℃, heating to 90-95 ℃, and carrying out gelatinization and inactivation treatment at the temperature of 0.5-1 h.
  3. 3. The bio-based fluorine-free oil repellent agent according to claim 2, wherein the low-viscosity starch is one or more of cationic starch, anionic starch or amphoteric starch.
  4. 4. The bio-based fluorine-free oil repellent agent according to claim 2, wherein the amount of alpha-amylase is 0.1% -1% of the absolute dry mass of low-viscosity starch.
  5. 5. The bio-based fluorine-free oil-proof agent according to claim 1, wherein the raw materials of the reinforced polymer emulsion comprise, by mass, 30-40 parts of acrylamide, 5-10 parts of methacryloxyethyl trimethyl ammonium chloride, 3-5 parts of itaconic acid, 5-10 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.1-0.5 part of nanocellulose, 3-5 parts of sodium methacrylate, 3-5 parts of an initiator, 5-10 parts of a cross-linking agent N, N-dimethylacrylamide, 3-5 parts of ethylenediamine tetraacetic acid, 1-3 parts of sulfuric acid with the concentration of 98%, 1-3 parts of sodium sulfite, 1-3 parts of a defoaming agent and 1-3 parts of sodium dodecyl sulfate, and water is added to adjust the solid content to 15-25 wt% of ammonium persulfate.
  6. 6. The bio-based fluorine-free oil repellent agent according to claim 5, wherein the reinforced polymer emulsion is prepared by the method of: (1) Pre-emulsification Adding acrylamide, methacryloxyethyl trimethyl ammonium chloride, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, nanocellulose, sodium methacrylate sulfonate, ethylenediamine tetraacetic acid, sulfuric acid with the concentration of 98%, sodium sulfite and sodium dodecyl sulfonate into a reaction kettle, adding water accounting for 30% -50% of the total water consumption, and stirring at a high speed for 30 minutes to form a pre-emulsion; (2) Seed preparation Under the stirring condition, 10-30% of the total weight of the pre-emulsion is heated to 40-50 ℃, the rest water is slowly dripped, the initiator accounting for 20-30% of the total weight of the initiator is added after the dripping is finished, the temperature is raised to 60-70 ℃ and the reaction is carried out for 1-2 hours, so that stable seed latex is formed; (3) Main polymerization stage Adding the residual pre-emulsion, the cross-linking agent N, N-dimethylacrylamide and the residual initiator, controlling the temperature at 70-85 ℃ and continuously stirring for 4-6 hours; (4) Post-treatment Cooling to 40 ℃, adding NaOH to neutralize to pH 7-8, and controlling viscosity at 1000-3000 Pa.
  7. 7. The bio-based fluorine-free oil repellent agent according to claim 1, 2 or 5, wherein the nanocellulose has a diameter of 50nm or less and a length of 1000nm or less.
  8. 8. The bio-based fluorine-free oil repellent agent according to claim 1, 2 or 5, wherein the plasticizer is one or more of glycerin, triethyl citrate, epoxidized soybean oil.
  9. 9. The bio-based fluorine-free oil repellent according to claim 1,2 or 5, wherein the preservative is one or more selected from the group consisting of sodium benzoate, potassium benzoate, sodium sorbate, potassium sorbate, sodium propionate, calcium propionate and natamycin.
  10. 10. The bio-based fluorine-free oil repellent agent according to claim 1,2 or 5, wherein the polymerization degree of the polyvinyl alcohol is 1700 to 1800.

Description

Bio-based fluorine-free oil-proof agent for food packaging paper Technical Field The invention relates to the technical field of oil-proofing agent production, in particular to a bio-based fluorine-free oil-proofing agent for food packaging paper. Background With the continuous development of society and the continuous improvement of the living standard of people, the oil-proof paper is increasingly widely applied and the demand is also increasingly large. The food-grade oil-proof paper in the current market almost uses fluoride as an oil-proof agent, the surface of fluorine atoms contains more negative charges, the atomic volume is larger, a compact thin layer with low surface energy can be formed, the interaction between fibers and liquid is reduced, and the surface of the paper is coated with a layer of fluorine-containing oil-proof agent, so that the paper has good oil-proof performance. However, the research of scientists proves that fluoride has cancerogenic action on the body. Since 2016, the U.S. Food and Drug Administration (FDA) has announced that the use of three perfluorinated compounds in food packaging materials has been prohibited. On month 6 and 14 of 2017, the European Union issued (EU) 2017/1000 on its official gazette, newly added to REACH regulations annex XVII item 68 on the limitation of perfluorooctanoic acid (PFOA), formally incorporating PFOA and its salts and related substances into the REACH regulations limit list. Since 2019, the european union has comprehensively restricted the market of fluorine-containing paper products. Therefore, the novel development of the fluorine-free oil-proof agent coating and the development of the fluorine-free oil-proof paper have important significance. The fluorine-free oil-proofing agent radically eliminates the harm of the fluorine-containing oil-proofing agent or the coating film to the environment or organisms, and accords with the pursuit of people on environmental protection. However, the fluorine-free oil-proofing agent has high viscosity, is inconvenient to operate, has poor oil-proofing effect and is expensive. Patent CN113931005A discloses a preparation method of oil-proof package for food. The method takes paraffin as a raw material, an emulsifying agent and an emulsion assistant are added, uniform and stable fluorine-free oil-proof agent is prepared through high-speed dispersion and emulsification and high-pressure homogenization, the oil-proof agent is used for carrying out surface sizing on paper, and oil-proof paper with oil-proof grease penetration is prepared through drying. But poor mechanical properties and degradability limit the application of the oil-repellent paper. Patent CN110258184a discloses a method for preparing biopolymer type coating from amorphous modified starch and chitosan, then coating the coating on the surface of paper, drying to obtain food oil-proof paper, the oil-proof paper has good green safety, high degradability, but chitosan is expensive and low in concentration, which limits the application of the oil-proof paper in oil-proof paper. Patent CN 118621615A discloses that after a coating layer containing sodium alginate and carboxymethyl cellulose is coated and sized, the mechanical property and barrier property of base paper can be enhanced, and a polydimethylsiloxane solution is applied to the sized dry paper, so that the grease resistance and barrier property of the paper are improved. However, sodium alginate and carboxymethyl cellulose have the problem of high viscosity, sodium alginate is expensive, two layers of coating are needed, and the application of the sodium alginate in oil-proof paper is limited by complex process. Disclosure of Invention The invention aims to provide a bio-based fluorine-free oil-proof agent for food packaging paper, which has the advantages of environment-friendly raw materials, no fluorine, high-efficiency oil proofing and the like. The technical scheme adopted for solving the technical problems is as follows: The bio-based fluorine-free oil-proofing agent for the food packaging paper comprises, by weight, 30-50 parts of modified low-viscosity starch, 5-15 parts of reinforced polymer emulsion, 10-30 parts of 10wt% polyvinyl alcohol aqueous solution, 3-20 parts of 3wt% nano cellulose aqueous solution, 0.5-2 parts of plasticizer and 0.01-0.3 part of preservative. The preparation method of the modified low-viscosity starch comprises the following steps: Mixing low-viscosity starch and water to form a mixed solution with the mass concentration of 20-30%, adding alpha-amylase, carrying out enzymolysis for 10min-1h at 40-60 ℃, heating to 90-95 ℃, and carrying out gelatinization and inactivation treatment at the temperature of 0.5-1 h. The low-viscosity starch adopts one or more of cationic starch, anionic starch or amphoteric starch. The dosage of the alpha-amylase is 0.1% -1% of the absolute dry mass of the low-viscosity starch. The reinforced polymer emulsion comprises, by m