CN114889298B - Aluminum-free high-barrier degradable composite paper for food and preparation method thereof - Google Patents

Aluminum-free high-barrier degradable composite paper for food and preparation method thereof Download PDF

Info

Publication number
CN114889298B
CN114889298B CN202210586166.0A CN202210586166A CN114889298B CN 114889298 B CN114889298 B CN 114889298B CN 202210586166 A CN202210586166 A CN 202210586166A CN 114889298 B CN114889298 B CN 114889298B
Authority
CN
China
Prior art keywords
barrier
stirring
agent coating
paper
deionized water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210586166.0A
Other languages
Chinese (zh)
Other versions
CN114889298A (en
Inventor
林冬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shantou Qiangyu Packaging Materials Co ltd
Original Assignee
Shantou Qiangyu Packaging Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shantou Qiangyu Packaging Materials Co ltd filed Critical Shantou Qiangyu Packaging Materials Co ltd
Priority to CN202210586166.0A priority Critical patent/CN114889298B/en
Publication of CN114889298A publication Critical patent/CN114889298A/en
Application granted granted Critical
Publication of CN114889298B publication Critical patent/CN114889298B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • B32B38/145—Printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/428—Lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/837—Chemically modified polymers by silicon containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/84—Paper comprising more than one coating on both sides of the substrate
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/12—Coating on the layer surface on paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses an aluminum-free high-barrier degradable composite paper for food and a preparation method thereof, wherein the composite paper sequentially comprises a barrier agent coating layer, base paper, an adhesive layer, a barrier agent coating layer and base paper from top to bottom; the barrier agent coating comprises the following raw materials in parts by weight: 50-60 parts of reinforced emulsion, 5-10 parts of barrier filler, 1-3 parts of sodium dodecyl benzene sulfonate and 3-5 parts of polyacrylic acid; the lining paper is free of metal aluminum, the molecular main chain in the blocking agent coating is polylactic acid, the adhesive layer is made of starch-based adhesive, the prepared composite paper can be degraded, the pollution to the environment is reduced, the long-chain halothane on the surface of the blocking agent coating has a good hydrophobic effect, the composite paper can effectively separate oxygen, water and steam, and the main material of the blocking agent coating is polyurethane material, so that the composite paper has a heat sealing effect.

Description

Aluminum-free high-barrier degradable composite paper for food and preparation method thereof
Technical Field
The invention relates to the technical field of food packaging bag processing, in particular to aluminum-free high-barrier degradable composite paper for food and a preparation method thereof.
Background
With the acceleration of pace of life, the food package of convenience, hygienization develops gradually, products such as disposable foam plastic lunch-box, plastic packaging bag and plastic articles for daily use have frequently entered daily life, because the plastic products are difficult to degrade after abandoning, cause the phenomenon of serious pollution of the environment, the plastic food packaging bag is regarded as the body of the food package, have also become one of the important pollution sources in the white pollution, some food packages adopt the inner liner paper, the existing inner liner paper contains metal aluminium, the inner liner paper of metal aluminium has the nondegradable problem too; therefore, the inner lining paper which is degradable, can be thermally sealed and can insulate oxygen, water and steam is urgently needed.
Disclosure of Invention
The invention aims to provide aluminum-free high-barrier degradable composite paper for foods and a preparation method thereof, and solves the problem that the composite paper for foods at the present stage contains metallic aluminum and cannot be degraded.
The purpose of the invention can be realized by the following technical scheme: the aluminum-free high-barrier degradable food composite paper comprises a barrier agent coating layer, base paper, an adhesive layer, the barrier agent coating layer and the base paper from top to bottom in sequence.
The barrier agent coating comprises the following raw materials in parts by weight: 50-60 parts of reinforced emulsion, 5-10 parts of barrier filler, 1-3 parts of sodium dodecyl benzene sulfonate and 3-5 parts of polyacrylic acid; the barrier agent coating is prepared by the following steps: adding the barrier filler into the reinforced emulsion, stirring and adjusting the pH value of the reaction solution to 4-5 under the conditions of the rotation speed of 150-200r/min and the temperature of 60-70 ℃, adjusting the pH value to 7 after stirring for 10-15h, adding sodium dodecyl benzene sulfonate and polypropylene, and stirring for 20-30min under the condition of the rotation speed of 800-1000r/min to prepare the barrier agent coating.
The reaction principle is as follows: the siloxane on the side chain of the molecule of the reinforced emulsion is hydrolyzed to form silanol which is grafted with active hydroxyl on the surface of the blocking filler, so that the dispersibility of the blocking filler and the reinforced emulsion is improved.
Further, the solid content of the barrier agent coating is 40-50%, and the wet coating amount of the barrier agent coating is 6-12g/m 2 The dry coating amount of the barrier agent coating is 3 to 5g/m 2 。
Furthermore, the adhesive layer is a starch-based adhesive.
Further, the reinforced emulsion is prepared by the following steps:
step A1: dissolving polylactic acid in toluene, adding 2, 2-dimethylolpropionic acid and p-toluenesulfonic acid under the conditions of the rotation speed of 150-200r/min and the temperature of 90-100 ℃, heating to 120-130 ℃ after the addition is finished, reacting for 4-6h, distilling to remove toluene to obtain an intermediate 1, uniformly mixing the intermediate 1, 4' -diphenylmethane diisocyanate and PPG-1000, and reacting for 1.5-2.5h under the conditions of the rotation speed of 200-300r/min and the temperature of 80-85 ℃ to obtain a prepolymer;
the reaction principle is as follows:
carrying out esterification reaction on polylactic acid and 2, 2-dimethylolpropionic acid to ensure that carboxyl at one end of a polylactic acid molecule and hydroxyl on the 2, 2-dimethylolpropionic acid are subjected to esterification reaction to form hydroxyl-terminated polylactic acid to prepare an intermediate 1, and carrying out primary reaction on the intermediate 1, 4 '-diphenylmethane diisocyanate and PPG-1000 to ensure that the hydroxyl on the intermediate 1 and the PPG-1000 and isocyanate on the 4,4' -diphenylmethane diisocyanate react to prepare a prepolymer.
The reaction process is as follows:
Figure 265896DEST_PATH_IMAGE001
step A2: uniformly mixing the prepolymer, dibutyltin dilaurate and acetone, stirring for 1-2h at the rotation speed of 150-200r/min and the temperature of 80 ℃, cooling to the temperature of 40-50 ℃, adding triethylamine, stirring for 15-30min, continuously cooling to the temperature of 0-5 ℃, adding deionized water, continuously stirring for 15-20min, and distilling to remove the acetone to obtain a polyurethane emulsion;
the reaction process is as follows:
Figure 323982DEST_PATH_IMAGE002
step A3: uniformly mixing the polyurethane emulsion, 2-amino-1, 3-propylene glycol and zinc chloride, carrying out reflux reaction for 8-10h at the rotation speed of 150-200r/min and the temperature of 130-140 ℃, filtering to remove filtrate, dispersing a substrate in deionized water, dropwise adding KH560, adjusting the pH value of a reaction solution to 8, and carrying out reaction for 4-6h at the rotation speed of 200-300r/min and the temperature of 25-30 ℃ to obtain the reinforced emulsion.
The reaction principle is as follows:
and (2) carrying out esterification reaction on the polyurethane emulsion and 2-amino-1, 3-propylene glycol to ensure that carboxyl of a polyurethane side chain is reacted with alcoholic hydroxyl on the 2-amino-1, 3-propylene glycol to ensure that polyurethane molecules are crosslinked, and then adding KH560 to ensure that epoxy groups on the KH560 are reacted with amino groups on the 2-amino-1, 3-propylene glycol to prepare the reinforced emulsion.
Further, the molar ratio of the polylactic acid and the 2, 2-dihydroxypropionic acid in the step A1 is 3.
Furthermore, the using ratio of the prepolymer in the step A2, dibutyltin dilaurate, acetone, triethylamine and deionized water is 5 g.
Further, the amount by mass ratio of the polyurethane emulsion described in the step A3 to the 2-amino-1, 3-propanediol is: 5, the adding amount of KH560 is 3 to 5 mass parts of the substrate, and the viscosity of the enhanced emulsion is 48.5 to 50.0 mPa.s.
Further, the barrier filler is prepared by the following steps:
step B1: mixing graphite powder, concentrated sulfuric acid and phosphorus pentoxide, stirring for 30-40min at the rotation speed of 150-200r/min and at the temperature of 0-3 ℃, adding potassium permanganate, continuously stirring for 1.5-2.5h, heating to 30-40 ℃, stirring for 1.5-2.5h, heating to 80-90 ℃, adding deionized water, adding hydrogen peroxide until the color of the reaction liquid is yellow and bright, cooling to room temperature, centrifuging to remove supernatant, dispersing a substrate in the deionized water, ultrasonically stripping, and centrifuging again to obtain graphene oxide;
and step B2: dispersing graphene oxide in deionized water, adding 2-perfluoroalkyl ethyl alcohol and p-toluenesulfonic acid, performing reflux reaction for 8-10h at the rotation speed of 200-300r/min and the temperature of 110-120 ℃, filtering to remove filtrate, drying a filter cake to prepare modified graphene, adding montmorillonite into deionized water, stirring for 2-3h at the rotation speed of 600-800r/min and the temperature of 20-25 ℃ to prepare montmorillonite dispersion, dissolving chitosan in an acetic acid solution, and adjusting the pH value to 4.5 to prepare a chitosan solution;
and step B3: adding modified graphene into montmorillonite dispersion liquid, carrying out ultrasonic treatment for 10-15min under the condition of frequency of 20-30kHz, adding chitosan solution, stirring for 5-7h under the conditions of rotation speed of 800-1000r/min and temperature of 60-70 ℃, centrifuging to remove supernatant, washing a substrate with deionized water until washing liquid is neutral, drying and grinding to 200 meshes to obtain the blocking filler.
Further, the use ratio of the graphite powder, concentrated sulfuric acid, phosphorus pentoxide, potassium permanganate and deionized water in the step B1 is 2g 46ml.
Further, the dosage of the 2-perfluoroalkyl ethyl alcohol in the step B2 is 10% of the mass of the graphene oxide, the dosage ratio of the montmorillonite to the ionized water is 1g.
Further, the dosage ratio of the modified graphene, the montmorillonite and the chitosan solution in the step B3 is 1g.
A preparation method of aluminum-free high-barrier degradable composite paper for food specifically comprises the following steps:
the method comprises the following steps: uniformly coating the barrier agent coating on the base paper to form a composite form of the barrier agent coating and the base paper, wherein an upper composite surface and a lower composite surface are arranged;
step two: the adhesive layer is coated between the upper layer composite surface and the lower layer composite surface in a gravure printing mode from top to bottom according to the composite form of the barrier agent coating, the base paper, the adhesive layer, the barrier agent coating and the base paper, and various patterns can be printed on the base paper in the gravure printing mode, so that the paper is more practical;
step three: drying and cutting to obtain the composite paper.
Further, the barrier agent coating can be coated on two sides of the base paper, and the barrier agent coating can also be multi-layer lamination according to the requirements of the actual packaging place.
Further, the coating mode of the barrier agent coating can be gravure coating, rubber roll coating or film transfer.
The invention has the following beneficial effects: the composite paper for the aluminum-free high-barrier degradable food is prepared by sequentially forming a barrier agent coating, base paper, an adhesive layer, a barrier agent coating and the base paper from top to bottom, wherein the lining paper is free of metal aluminum, polylactic acid is used as a molecular main chain in the barrier agent coating, a starch-based adhesive is used as the adhesive layer, the prepared composite paper can be degraded, and the pollution to the environment is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An aluminum-free high-barrier degradable composite paper for food is composed of a barrier agent coating layer, base paper, an adhesive layer, a barrier agent coating layer and base paper from top to bottom in sequence; the barrier agent coating comprises the following raw materials in parts by weight: 50 parts of reinforced emulsion, 5 parts of barrier filler, 1 part of sodium dodecyl benzene sulfonate and 3 parts of polyacrylic acid.
Wherein, the barrier agent coating is prepared by the following steps: adding the blocking filler into the reinforced emulsion, stirring at the rotation speed of 150r/min and at the temperature of 60 ℃, adjusting the pH value of the reaction solution to 4, stirring for 10 hours, adjusting the pH value to 7, adding sodium dodecyl benzene sulfonate and polypropylene, and stirring at the rotation speed of 800r/min for 20 minutes to obtain the blocking agent coating.
The solid content of the barrier agent coating is 40 percent, and the wet coating content of the barrier agent coating is 7.5g/m 2 The dry coating amount of the barrier agent coating is 3g/m 2 。
And the adhesive layer is a starch-based adhesive.
Wherein, the reinforced emulsion is prepared by the following steps:
step A1: dissolving polylactic acid in toluene, adding 2, 2-dimethylolpropionic acid and p-toluenesulfonic acid under the conditions of the rotating speed of 150r/min and the temperature of 90 ℃, heating to 120 ℃ after the addition is finished, reacting for 4 hours, distilling to remove toluene to obtain an intermediate 1, uniformly mixing the intermediate 1, 4' -diphenylmethane diisocyanate and PPG-1000, and reacting for 1.5 hours under the conditions of the rotating speed of 200r/min and the temperature of 80 ℃ to obtain a prepolymer;
step A2: uniformly mixing the prepolymer, dibutyltin dilaurate and acetone, stirring for 1h at the rotation speed of 150r/min and the temperature of 80 ℃, cooling to the temperature of 40 ℃, adding triethylamine, stirring for 15min, continuously cooling to the temperature of 0 ℃, adding deionized water, continuously stirring for 15min, and distilling to remove acetone to obtain a polyurethane emulsion;
step A3: uniformly mixing polyurethane emulsion, 2-amino-1, 3-propylene glycol and zinc chloride, carrying out reflux reaction for 8 hours at the rotation speed of 150r/min and the temperature of 130 ℃, filtering to remove filtrate, dispersing a substrate in deionized water, dropwise adding KH560, adjusting the pH value of a reaction solution to 8, and carrying out reaction for 4 hours at the rotation speed of 200r/min and the temperature of 25 ℃ to obtain the enhanced emulsion.
The molar ratio of the polylactic acid and the 2, 2-dihydroxypropionic acid in the step A1 is 3;
the using ratio of the prepolymer in the step A2 to dibutyltin dilaurate, acetone, triethylamine and deionized water is 5 g;
the dosage mass ratio of the polyurethane emulsion in the step A3 to the 2-amino-1, 3-propylene glycol is as follows: 5, the adding amount of KH560 is 3 percent of the mass of the substrate, and the viscosity of the enhanced emulsion is 48.5 mPas.
Wherein, the blocking filler is prepared by the following steps:
step B1: mixing graphite powder, concentrated sulfuric acid and phosphorus pentoxide, stirring for 30min at the rotation speed of 150r/min and the temperature of 0 ℃, adding potassium permanganate, continuing stirring for 1.5h, heating to the temperature of 30 ℃, stirring for 1.5h, heating to the temperature of 80 ℃, adding deionized water, adding hydrogen peroxide until the color of the reaction solution is yellow and bright, cooling to room temperature, centrifuging to remove supernatant, dispersing a substrate in the deionized water, ultrasonically stripping, and centrifuging again to obtain graphene oxide;
and step B2: dispersing graphene oxide in deionized water, adding 2-perfluoroalkyl ethyl alcohol and p-toluenesulfonic acid, performing reflux reaction for 8 hours at the rotation speed of 200r/min and the temperature of 110 ℃, filtering to remove filtrate, drying a filter cake to prepare modified graphene, adding montmorillonite into the deionized water, stirring for 2 hours at the rotation speed of 600r/min and the temperature of 20 ℃ to prepare montmorillonite dispersion, dissolving chitosan in an acetic acid solution, and adjusting the pH value to 4.5 to prepare a chitosan solution;
and step B3: adding the modified graphene into montmorillonite dispersion liquid, carrying out ultrasonic treatment for 10min under the condition of frequency of 20kHz, adding chitosan solution, stirring for 5h under the conditions of rotation speed of 800r/min and temperature of 60 ℃, centrifuging to remove supernatant, washing a substrate with deionized water until a washing liquid is neutral, drying and grinding to 200 meshes to obtain the blocking filler.
The use ratio of the graphite powder, concentrated sulfuric acid, phosphorus pentoxide, potassium permanganate and deionized water in the step B1 is 2g 46mL;
the dosage of the 2-perfluoroalkyl ethyl alcohol in the step B2 is 10% of the mass of the graphene oxide, the dosage ratio of the montmorillonite to the ionized water is 1g;
the dosage ratio of the modified graphene, the montmorillonite and the chitosan solution in the step B3 is 1g.
Example 2
An aluminum-free high-barrier degradable composite paper for food is composed of a barrier agent coating layer, base paper, an adhesive layer, a barrier agent coating layer and base paper from top to bottom in sequence; the barrier agent coating comprises the following raw materials in parts by weight: 55 parts of reinforced emulsion, 8 parts of barrier filler, 2 parts of sodium dodecyl benzene sulfonate and 4 parts of polyacrylic acid.
Wherein, the barrier agent coating is prepared by the following steps: adding the blocking filler into the reinforced emulsion, stirring and adjusting the pH value of the reaction solution to 4.5 under the conditions of the rotating speed of 180r/min and the temperature of 65 ℃, adjusting the pH value to 7 after stirring for 13 hours, adding sodium dodecyl benzene sulfonate and polypropylene, and stirring for 25 minutes under the condition of the rotating speed of 800r/min to prepare the blocking agent coating.
The solid content of the barrier agent coating is 48 percent, and the wet coating content of the barrier agent coating is 11.5g/m 2 The dry coating amount of the barrier agent coating is 5.2g/m 2 。
And the adhesive layer is a starch-based adhesive.
Wherein, the reinforced emulsion is prepared by the following steps:
step A1: dissolving polylactic acid in toluene, adding 2, 2-dimethylolpropionic acid and p-toluenesulfonic acid under the conditions of the rotating speed of 180r/min and the temperature of 95 ℃, heating to 125 ℃ after the addition is finished, reacting for 5 hours, distilling to remove toluene to obtain an intermediate 1, uniformly mixing the intermediate 1, 4' -diphenylmethane diisocyanate and PPG-1000, and reacting for 2 hours under the conditions of the rotating speed of 300r/min and the temperature of 83 ℃ to obtain a prepolymer;
step A2: uniformly mixing the prepolymer, dibutyltin dilaurate and acetone, stirring for 1-2h at the rotation speed of 180r/min and the temperature of 80 ℃, cooling to the temperature of 45 ℃, adding triethylamine, stirring for 20min, continuously cooling to the temperature of 3 ℃, adding deionized water, continuously stirring for 18min, and distilling to remove acetone to obtain a polyurethane emulsion;
step A3: uniformly mixing polyurethane emulsion, 2-amino-1, 3-propylene glycol and zinc chloride, carrying out reflux reaction for 9 hours at the rotation speed of 180r/min and the temperature of 135 ℃, filtering to remove filtrate, dispersing a substrate in deionized water, dropwise adding KH560, adjusting the pH value of a reaction solution to 8, and carrying out reaction for 5 hours at the rotation speed of 200r/min and the temperature of 28 ℃ to obtain the enhanced emulsion.
The molar ratio of the polylactic acid and the 2, 2-dihydroxypropionic acid in the step A1 is 3;
the using amount ratio of the prepolymer in the step A2 to the dibutyltin dilaurate to acetone to triethylamine to deionized water is 5 g;
the polyurethane emulsion of the step A3 and the 2-amino-1, 3-propylene glycol have the following dosage mass ratio: 5, the adding amount of KH560 is 4 percent of the mass of the substrate, and the viscosity of the enhanced emulsion is 49.0 mPas.
Wherein, the blocking filler is prepared by the following steps:
step B1: mixing graphite powder, concentrated sulfuric acid and phosphorus pentoxide, stirring for 35min at the rotation speed of 180r/min and the temperature of 1 ℃, adding potassium permanganate, continuing stirring for 2h, heating to 35 ℃, stirring for 2h, heating to 85 ℃, adding deionized water, adding hydrogen peroxide until the color of the reaction solution is yellow and bright, cooling to room temperature, centrifuging to remove supernatant, dispersing a substrate in deionized water, ultrasonically stripping, and centrifuging again to obtain graphene oxide;
and step B2: dispersing graphene oxide in deionized water, adding 2-perfluoroalkyl ethyl alcohol and p-toluenesulfonic acid, performing reflux reaction for 9 hours at the rotation speed of 200r/min and the temperature of 115 ℃, filtering to remove filtrate, drying a filter cake to prepare modified graphene, adding montmorillonite into the deionized water, stirring for 2.5 hours at the rotation speed of 800r/min and the temperature of 23 ℃ to prepare montmorillonite dispersion, dissolving chitosan in an acetic acid solution, and adjusting the pH value to 4.5 to prepare a chitosan solution;
and step B3: adding the modified graphene into the montmorillonite dispersion liquid, carrying out ultrasonic treatment for 15min under the condition of the frequency of 20kHz, adding a chitosan solution, stirring for 6h under the conditions of the rotating speed of 800r/min and the temperature of 65 ℃, centrifuging to remove a supernatant, washing a substrate with deionized water until a washing liquid is neutral, drying and grinding to 200 meshes to obtain the blocking filler.
The use ratio of the graphite powder, concentrated sulfuric acid, phosphorus pentoxide, potassium permanganate and deionized water in the step B1 is 2g, 4646mL;
the dosage of the 2-perfluoroalkyl ethyl alcohol in the step B2 is 10 percent of the mass of the graphene oxide, the dosage ratio of the montmorillonite to the ionized water is 1g;
the dosage ratio of the modified graphene, the montmorillonite and the chitosan solution in the step B3 is 1g.
Example 3
An aluminum-free high-barrier degradable composite paper for food is composed of a barrier agent coating layer, base paper, an adhesive layer, a barrier agent coating layer and base paper from top to bottom in sequence; the barrier agent coating comprises the following raw materials in parts by weight: 60 parts of reinforced emulsion, 10 parts of barrier filler, 3 parts of sodium dodecyl benzene sulfonate and 5 parts of polyacrylic acid.
Wherein, the barrier agent coating is prepared by the following steps: adding the blocking filler into the reinforced emulsion, stirring and adjusting the pH value of the reaction solution to 5 under the conditions of the rotation speed of 200r/min and the temperature of 70 ℃, after stirring for 15 hours, adjusting the pH value to 7, adding sodium dodecyl benzene sulfonate and polypropylene, and stirring for 30 minutes under the condition of the rotation speed of 1000r/min to prepare the blocking agent coating.
The solid content of the barrier agent coating is 50 percent, and the wet coating content of the barrier agent coating is 8g/m 2 The dry coating amount of the barrier agent coating is 4g/m 2 。
And the adhesive layer is a starch-based adhesive.
Wherein, the reinforced emulsion is prepared by the following steps:
step A1: dissolving polylactic acid in toluene, adding 2, 2-dimethylolpropionic acid and p-toluenesulfonic acid under the conditions of the rotating speed of 200r/min and the temperature of 100 ℃, heating to 130 ℃ after the addition, reacting for 6 hours, distilling to remove toluene to obtain an intermediate 1, uniformly mixing the intermediate 1, 4' -diphenylmethane diisocyanate and PPG-1000, and reacting for 2.5 hours under the conditions of the rotating speed of 300r/min and the temperature of 85 ℃ to obtain a prepolymer;
step A2: uniformly mixing the prepolymer, dibutyltin dilaurate and acetone, stirring for 2 hours at the rotation speed of 200r/min and the temperature of 80 ℃, cooling to the temperature of 50 ℃, adding triethylamine, stirring for 30 minutes, continuously cooling to the temperature of 5 ℃, adding deionized water, continuously stirring for 20 minutes, and distilling to remove acetone to obtain a polyurethane emulsion;
step A3: uniformly mixing polyurethane emulsion, 2-amino-1, 3-propylene glycol and zinc chloride, carrying out reflux reaction for 10h at the rotation speed of 200r/min and the temperature of 140 ℃, filtering to remove filtrate, dispersing a substrate in deionized water, dropwise adding KH560, adjusting the pH value of a reaction solution to 8, and carrying out reaction for 6h at the rotation speed of 300r/min and the temperature of 30 ℃ to obtain the enhanced emulsion.
The molar ratio of the polylactic acid and the 2, 2-dihydroxypropionic acid in the step A1 is 3;
the using amount ratio of the prepolymer in the step A2 to the dibutyltin dilaurate to acetone to triethylamine to deionized water is 5 g;
the dosage mass ratio of the polyurethane emulsion in the step A3 to the 2-amino-1, 3-propylene glycol is as follows: 5, the adding amount of KH560 is 5 percent of the mass of the substrate, and the viscosity of the enhanced emulsion is 50.0mPa & s.
Wherein, the blocking filler is prepared by the following steps:
step B1: mixing graphite powder, concentrated sulfuric acid and phosphorus pentoxide, stirring for 40min at the rotation speed of 200r/min and the temperature of 3 ℃, adding potassium permanganate, continuing stirring for 2.5h, heating to 40 ℃, stirring for 2.5h, heating to 90 ℃, adding deionized water, adding hydrogen peroxide until the color of the reaction solution is yellow and bright, cooling to room temperature, centrifuging to remove supernatant, dispersing a substrate in the deionized water, ultrasonically stripping, and centrifuging again to obtain graphene oxide;
and step B2: dispersing graphene oxide in deionized water, adding 2-perfluoroalkyl ethyl alcohol and p-toluenesulfonic acid, performing reflux reaction for 10 hours at the rotation speed of 300r/min and the temperature of 120 ℃, filtering to remove filtrate, drying a filter cake to prepare modified graphene, adding montmorillonite into the deionized water, stirring for 3 hours at the rotation speed of 800r/min and the temperature of 25 ℃ to prepare montmorillonite dispersion, dissolving chitosan in an acetic acid solution, and adjusting the pH value to 4.5 to prepare a chitosan solution;
and step B3: adding the modified graphene into montmorillonite dispersion liquid, carrying out ultrasonic treatment for 15min under the condition of 30kHz frequency, adding chitosan solution, stirring for 7h under the conditions of 1000r/min of rotation speed and 70 ℃, centrifuging to remove supernatant, washing a substrate with deionized water until a washing liquid is neutral, drying and grinding to 200 meshes to obtain the blocking filler.
The use ratio of the graphite powder, concentrated sulfuric acid, phosphorus pentoxide, potassium permanganate and deionized water in the step B1 is 2g 46mL;
the dosage of the 2-perfluoroalkyl ethyl alcohol in the step B2 is 10% of the mass of the graphene oxide, the dosage ratio of the montmorillonite to the ionized water is 1g;
the dosage ratio of the modified graphene, the montmorillonite and the chitosan solution in the step B3 is 1g.
Comparative example 1
The comparative example is the lining paper disclosed in Chinese patent CN 11167676729A.
Comparative example 2
The comparative example is the lining paper disclosed in Chinese patent CN 110004762A.
The lining paper prepared in the examples 1-3 and the comparative examples 1-2 is tested, soil is paved into a container, all samples are sequentially placed into the container in parallel at the interval of 30cm, and the container is placed in a room with illumination; carrying out processes of simulating the weather of nature such as water spraying, soil scattering experiments, clear water washing, blower cold air blowing and the like on the sample strips in the container every day, fixing the time interval of each operation to be 2 hours, taking out the sample strips every 30 days, carrying out clear water washing, drying in an oven and recording the quality; the barrier properties were measured according to the GB/T1038-2000 standard and the results are shown in the following table:
Figure 821828DEST_PATH_IMAGE003
as can be seen from the above table, the inner liner paper prepared in examples 1 to 3 has a degradation rate of 10.35 to 10.41% in 30 days, a degradation rate of 20.67 to 21.12% in 60 days, a degradation rate of 42.68 to 43.15% in 90 days, and an air permeability of 2431 to 2498cm 3 /(m 2 d.Pa), water vapor permeability of 586 to 592g/m 2 24h shows that the lining paper prepared by the method has good degradability, the montmorillonite in the blocking agent coating has a multi-sheet structure, the graphene is a two-dimensional sheet carbon material with anti-permeability performance, the blocking performance of the blocking agent coating can be effectively improved, and meanwhile, the long-chain fluorocarbon on the surface of the blocking agent coating has a good hydrophobic effect, so that the composite paper can effectively isolate oxygen, water and steam.
The foregoing is illustrative and explanatory only of the present invention, and it is intended that the present invention cover modifications, additions, or substitutions by those skilled in the art, without departing from the spirit of the invention or exceeding the scope of the claims.

Claims (5)

1. The aluminum-free high-barrier degradable composite paper for food is characterized in that: the coating of the blocking agent, the base paper, the adhesive layer, the coating of the blocking agent and the base paper are sequentially arranged from top to bottom;
the barrier agent coating comprises the following raw materials in parts by weight: 50-60 parts of reinforced emulsion, 5-10 parts of barrier filler, 1-3 parts of sodium dodecyl benzene sulfonate and 3-5 parts of polyacrylic acid;
the barrier agent coating is prepared by the following steps:
adding the barrier filler into the reinforced emulsion, stirring and adjusting the pH value of the reaction solution to 4-5 under the conditions of the rotating speed of 150-200r/min and the temperature of 60-70 ℃, adjusting the pH value to 7 after stirring for 10-15h, adding sodium dodecyl benzene sulfonate and polypropylene, and stirring for 20-30min under the condition of the rotating speed of 800-1000r/min to prepare a barrier agent coating;
the reinforced emulsion is prepared by the following steps:
step A1: dissolving polylactic acid in toluene, stirring, adding 2, 2-dimethylolpropionic acid and p-toluenesulfonic acid, heating to react after the addition is finished, distilling to remove toluene to obtain an intermediate 1, and mixing and reacting the intermediate 1, 4' -diphenylmethane diisocyanate and PPG-1000 to obtain a prepolymer;
step A2: mixing and stirring the prepolymer, dibutyltin dilaurate and acetone, cooling, adding triethylamine, stirring, continuously cooling, adding deionized water, continuously stirring, and distilling to remove acetone to obtain a polyurethane emulsion;
step A3: mixing and refluxing polyurethane emulsion, 2-amino-1, 3-propylene glycol and zinc chloride for reaction, filtering to remove filtrate, dispersing a substrate in deionized water, dropwise adding KH560, adjusting the pH value of a reaction solution, and reacting to obtain enhanced emulsion;
the blocking filler is prepared by the following steps:
step B1: mixing graphite powder, concentrated sulfuric acid and phosphorus pentoxide, stirring for 30-40min at the rotation speed of 150-200r/min and the temperature of 0-3 ℃, adding potassium permanganate, continuously stirring for 1.5-2.5h, heating to 30-40 ℃, stirring for 1.5-2.5h, heating to 80-90 ℃, adding deionized water, adding hydrogen peroxide until the color of the reaction solution is yellow and bright, cooling to room temperature, centrifuging to remove supernatant, dispersing a substrate in the deionized water, ultrasonically stripping, and centrifuging again to obtain graphene oxide;
and step B2: dispersing graphene oxide in deionized water, adding 2-perfluoroalkyl ethyl alcohol and p-toluenesulfonic acid, performing reflux reaction for 8-10h at the rotation speed of 200-300r/min and the temperature of 110-120 ℃, filtering to remove filtrate, drying a filter cake to prepare modified graphene, adding montmorillonite into deionized water, stirring for 2-3h at the rotation speed of 600-800r/min and the temperature of 20-25 ℃ to prepare montmorillonite dispersion, dissolving chitosan in an acetic acid solution, and adjusting the pH value to 4.5 to prepare a chitosan solution;
and step B3: adding modified graphene into montmorillonite dispersion liquid, carrying out ultrasonic treatment for 10-15min under the condition of frequency of 20-30kHz, adding chitosan solution, stirring for 5-7h under the conditions of rotation speed of 800-1000r/min and temperature of 60-70 ℃, centrifuging to remove supernatant, washing a substrate with deionized water until washing liquid is neutral, drying and grinding to 200 meshes to obtain the blocking filler.
2. The aluminum-free high-barrier degradable composite paper for food as claimed in claim 1, wherein the aluminum-free high-barrier degradable composite paper comprises: the molar ratio of the polylactic acid and the 2, 2-dihydroxypropionic acid in the step A1 is 3.
3. The aluminum-free high-barrier degradable composite paper for food as claimed in claim 1, wherein the aluminum-free high-barrier degradable composite paper comprises: the using ratio of the prepolymer in the step A2 to the dibutyltin dilaurate to acetone to triethylamine to deionized water is 5 g.
4. The aluminum-free high-barrier degradable composite paper for food as claimed in claim 1, wherein: the polyurethane emulsion and the 2-amino-1, 3-propylene glycol in the step A3 have the following dosage mass ratio: 5, the addition amount of KH560 is 3-5% of the mass of the substrate, and the viscosity of the enhanced emulsion is 48.5-50.0 mPa.s.
5. The preparation method of the aluminum-free high-barrier degradable composite paper for food as claimed in claim 1, wherein the preparation method comprises the following steps: the method specifically comprises the following steps:
the method comprises the following steps: uniformly coating the barrier agent coating on the base paper to form a composite form of the barrier agent coating and the base paper, wherein the composite form is provided with an upper composite surface and a lower composite surface;
step two: coating the adhesive layer between the upper layer composite surface and the lower layer composite surface in a gravure printing mode from top to bottom according to the composite form of the barrier agent coating, the base paper, the adhesive layer, the barrier agent coating and the base paper;
step three: drying and cutting to obtain the composite paper.
CN202210586166.0A 2022-05-27 2022-05-27 Aluminum-free high-barrier degradable composite paper for food and preparation method thereof Active CN114889298B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210586166.0A CN114889298B (en) 2022-05-27 2022-05-27 Aluminum-free high-barrier degradable composite paper for food and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210586166.0A CN114889298B (en) 2022-05-27 2022-05-27 Aluminum-free high-barrier degradable composite paper for food and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114889298A CN114889298A (en) 2022-08-12
CN114889298B true CN114889298B (en) 2023-02-07

Family

ID=82725889

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210586166.0A Active CN114889298B (en) 2022-05-27 2022-05-27 Aluminum-free high-barrier degradable composite paper for food and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114889298B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008155432A (en) * 2006-12-22 2008-07-10 Dainippon Printing Co Ltd Heat-sealable film having barrier properties
CN101992888A (en) * 2009-08-21 2011-03-30 翁文桂 Laminated material without metal foil for blocking package
CN103038270A (en) * 2010-07-29 2013-04-10 巴斯夫欧洲公司 Biologically disintegratable composite films
CN106351071A (en) * 2016-08-24 2017-01-25 湖北金天门包装材料有限公司 Production process of aluminum-free degradable laser anti-counterfeiting and environment-friendly lining paper
CN107969124A (en) * 2015-07-03 2018-04-27 安姆科软包装克罗伊茨林根公司 Flexible multi-layered packaging film with super high separate behavior energy
CN109249668A (en) * 2017-07-14 2019-01-22 Sig技术股份公司 Flaky composite material, it is especially useful in the food or beverage container for producing dimensionally stable include the polymeric layer P with a L value
CN111386196A (en) * 2017-12-21 2020-07-07 斯道拉恩索公司 Heat-sealable packaging material
US20210246333A1 (en) * 2019-06-03 2021-08-12 Board Of Trustees Of Mighigan State University Biodegradable omniphobic and high-barrier coatings, related articles, and related methods
CN113619242A (en) * 2021-08-09 2021-11-09 江苏利特尔绿色包装股份有限公司 Biodegradable high-barrier paper-plastic packaging composite film and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008155432A (en) * 2006-12-22 2008-07-10 Dainippon Printing Co Ltd Heat-sealable film having barrier properties
CN101992888A (en) * 2009-08-21 2011-03-30 翁文桂 Laminated material without metal foil for blocking package
CN103038270A (en) * 2010-07-29 2013-04-10 巴斯夫欧洲公司 Biologically disintegratable composite films
CN107969124A (en) * 2015-07-03 2018-04-27 安姆科软包装克罗伊茨林根公司 Flexible multi-layered packaging film with super high separate behavior energy
CN106351071A (en) * 2016-08-24 2017-01-25 湖北金天门包装材料有限公司 Production process of aluminum-free degradable laser anti-counterfeiting and environment-friendly lining paper
CN109249668A (en) * 2017-07-14 2019-01-22 Sig技术股份公司 Flaky composite material, it is especially useful in the food or beverage container for producing dimensionally stable include the polymeric layer P with a L value
CN111386196A (en) * 2017-12-21 2020-07-07 斯道拉恩索公司 Heat-sealable packaging material
US20210246333A1 (en) * 2019-06-03 2021-08-12 Board Of Trustees Of Mighigan State University Biodegradable omniphobic and high-barrier coatings, related articles, and related methods
CN113619242A (en) * 2021-08-09 2021-11-09 江苏利特尔绿色包装股份有限公司 Biodegradable high-barrier paper-plastic packaging composite film and preparation method thereof

Also Published As

Publication number Publication date
CN114889298A (en) 2022-08-12

Similar Documents

Publication Publication Date Title
CN110154488A (en) Three layers of composite waterproof corrugated board of one kind and its preparation process
CN112778571A (en) Food-grade silica gel foam and manufacturing method thereof
CN106634770A (en) A transparent type one-component silane-modified polyether sealant and a preparing method thereof
CN105255439A (en) High-elongation two-component silicone structural adhesive and preparation method thereof
CN104059592A (en) Single-component silane modified polyether sealant and preparation method thereof
CN110157329A (en) A kind of nano-composite coating material
CN114889298B (en) Aluminum-free high-barrier degradable composite paper for food and preparation method thereof
CN115056556A (en) Durable photovoltaic waterproof roll and preparation method thereof
CN1687264A (en) Method for fabricating obstruction coating film of modified polyvinyl alcohol and coating film produced thereby
CN115029041A (en) Graphene modified nanoscale waterproof anticorrosive paint
CN109233352A (en) A kind of white carbon black surface treatment method
CN105778621A (en) Water-resistant waterborne polyurethane ink vehicle and preparation method thereof
CN112094494B (en) Super-barrier thermoplastic polyurethane elastomer and preparation method thereof
CN106947426A (en) A kind of preparation method of weather resistant fluid sealant for building
CN113667441A (en) Reactive polyurethane hot melt adhesive for high-moisture-permeability functional fabric and preparation method thereof
CN110551429B (en) Method for improving adhesion of high-humidity-resistant coating adhesive of anhydride-epoxy system
CN114292537A (en) Elastic waterproof nano coating and preparation method thereof
CN112844994A (en) Temperature-resistant silica gel leather and preparation method thereof
CN1978489A (en) Silicane terminated polysulfide rubber, and its preparing method
CN114806170B (en) Hybrid polyimide foam material and preparation method thereof
CN103553360A (en) Heat-insulation antifogging film agent
CN111677218B (en) Preparation process of decorative plate containing polyurethane heat-insulating layer
CN109679377A (en) A kind of preparation method of depickling type silicone adhesive composite calcium carbonate
CN115340773B (en) Preparation method of high-strength flame-retardant wood-plastic composite material
CN108034397A (en) A kind of anti-ultraviolet modified silane polyethers glue

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant