WO2021179306A1 - Biodegradable oil-proof paper without fluorocarbon compound, and preparation method therefor - Google Patents

Biodegradable oil-proof paper without fluorocarbon compound, and preparation method therefor Download PDF

Info

Publication number
WO2021179306A1
WO2021179306A1 PCT/CN2020/079304 CN2020079304W WO2021179306A1 WO 2021179306 A1 WO2021179306 A1 WO 2021179306A1 CN 2020079304 W CN2020079304 W CN 2020079304W WO 2021179306 A1 WO2021179306 A1 WO 2021179306A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
paper
polyvinyl alcohol
oil
preparation
Prior art date
Application number
PCT/CN2020/079304
Other languages
French (fr)
Chinese (zh)
Inventor
童树华
华飞果
张宇
童力
孟育
倪永浩
何志斌
Original Assignee
浙江金加浩绿色纳米材料股份有限公司
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 浙江金加浩绿色纳米材料股份有限公司 filed Critical 浙江金加浩绿色纳米材料股份有限公司
Priority to PCT/CN2020/079304 priority Critical patent/WO2021179306A1/en
Publication of WO2021179306A1 publication Critical patent/WO2021179306A1/en

Links

Classifications

    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material

Definitions

  • the invention relates to a biodegradable greaseproof paper that does not contain fluorocarbon compounds and a preparation method thereof, and particularly relates to a surface treatment process and uses of cellulose-based paper as an object.
  • cellulose-based paper is a paper mainly composed of cellulose and a small amount of other compounds. It is a material with pores on the surface and no oil resistance.
  • coated oil-repellent paper is a product that uses oil-repellent coatings to modify the surface of base paper. Under normal circumstances, the oil-repellent properties of the oil-repellent layer of coated paper are mainly composed of fluorine-containing compounds or latex or Paraffin wax is provided, but they are either toxic and harmful to the human body and the environment, or the oil-resistant paper produced has poor recycling performance and biodegradability.
  • countries all over the world have paid more attention to the environmental protection of disposable plastic products, and have put the ban on plastics on the agenda. This invention can replace plastic products to a certain extent.
  • Patent Document 1 U.S. Patent No. 5,674,961
  • Patent Document 2 U.S. Patent No. 5,330,622 propose the following surface modification methods.
  • the fluorocarbon is attached to the surface of the base paper by infiltration or coating.
  • the base paper obtains grease resistance.
  • fluorocarbon paper modification methods are very mature and effective, fluorocarbons are harmful to the human body and the environment, and will be transferred and accumulated along the food chain.
  • Patent Document 3 (US Patent US4418119A) proposes the following coating process.
  • the effective ingredients of the coating are mainly composed of polyvinyl alcohol and silicone grease.
  • the coating technology is used to improve the grease resistance provided by the two components. Anti-grease effect.
  • this method requires the use of easily vaporized organic solvents, such as heptane or toluene, when processing the mixed silicone grease components, which requires very high air purification in the production environment and has production safety issues.
  • Patent Document 4 Choinese Patent CN103669105A proposes the following coating process.
  • the base paper is first coated with a coating composed of starch, plasticizer, film-forming aids, and fluorine-containing compounds, and then dried to obtain the finished product.
  • Paper The fluorine-containing compound is perfluoropolyether phosphate and fluorine-containing acrylate, and the solid content of the coating is 5% to 15%.
  • the coating process does not use fluorocarbon compounds, it still uses fluorine-containing compounds, which will be potentially harmful.
  • plasticizers and some other additives there will also be some other potential hazards.
  • Patent Document 5 Choinese Patent CN110258184A proposes the following coating process.
  • the base paper is coated with modified starch and chitosan and then dried to obtain food-grade greaseproof paper.
  • the applicable scenarios are limited, and the extreme anti-grease performance of this method is limited.
  • the polyvinyl alcohol solution can be dried to form a smooth and dense film.
  • it When it is covered on the top layer of the base paper, it has a good anti-grease effect.
  • the paper has good hydrophilicity.
  • the polyvinyl alcohol solution can penetrate into the paper through the holes on the surface of the base paper, and the polyvinyl alcohol on the surface of the base paper cannot form a dense and thick anti-oil film, so the traditional method of PVA coating The process cannot provide excellent grease resistance.
  • the existing coated greaseproof paper has some problems.
  • people hope to use green, biodegradable, and highly oil-resistant greaseproof paper, not only in food packaging, but also in industrial applications, such as sandpaper base paper. Therefore, the original coating process that uses fluorine-containing compounds and volatile organic solvents needs to be replaced by a new, environmentally friendly, high-performance coating greaseproof paper process.
  • the purpose of the present invention is to provide a simple surface modification process to avoid the use of fluorocarbons, silicone greases and fluorocarbons in the coating process in view of the current technical problems of non-green environmental protection, poor recycling performance and difficult biodegradability of greaseproof paper.
  • it can improve the grease resistance of food packaging base paper or superfine sandpaper base paper, without losing the ability to bind with other polymer compounds (such as polyurethane), and without losing the base paper.
  • a biodegradable greaseproof paper that does not contain fluorocarbon compounds and has the recovery pulping ability and a preparation method thereof.
  • the present invention adopts the following technical solution: a biodegradable greaseproof paper that does not contain fluorocarbons and a preparation method thereof, characterized in that: pre-coating on cellulose-based paper A layer of modified starch-based reinforced pre-coating paint is used to obtain a reinforced pre-coating layer, and then an oil-repellent coating of nano cellulose/polyvinyl alcohol is coated to obtain an oil-repellent layer.
  • the biodegradable greaseproof paper containing no fluorocarbon and the preparation method thereof is characterized in that the preparation method of the reinforced pre-coating paint is: adding cationic starch or other cationic polymer compounds to a mass ratio of 1 ⁇ 10:90 ⁇ 99 Add deionized water, put in magnets, and place on 70 ⁇ 90 degrees Celsius magnetic heating stirrer to dissolve until a homogeneous solution, glue or dispersion is obtained.
  • the biodegradable oil-repellent paper containing no fluorocarbon and its preparation method is characterized in that the specific steps of preparing the oil-repellent coating are as follows: (1) Take polyvinyl alcohol in a mass ratio of 5-20 : Add deionized water from 80 to 95 degrees Celsius and stir at 80 to 100 degrees Celsius until a uniform solution is obtained; (2) Wait for the polyvinyl alcohol solution to cool to room temperature; (3) After cooling, follow the solid content of polyvinyl alcohol and nanocellulose After adding nano cellulose in a ratio of 20-100:1, ultrasonication is performed until uniform under ice-water cooling.
  • the polyvinyl alcohol can be any kind of polyvinyl alcohol or a mixture of two or more polyvinyl alcohols.
  • the degree of hydrolysis and molecular weight of polyvinyl alcohol can be changed according to the requirements of product production;
  • the nano cellulose can be It is any kind of nanocellulose, including but not limited to cellulose nanocrystals (CNC), cellulose nanofibrils (CNF) and TEMPO oxidized cellulose nanofibrils.
  • the biodegradable greaseproof paper containing no fluorocarbon and its preparation method is characterized in that the cellulose-based paper can be any cellulose-based paper material, including but not limited to copy paper, filter paper, kraft paper , Paperboard and coated paper, the fiber source can be virgin or recycled.
  • the biodegradable greaseproof paper containing no fluorocarbon and its preparation method is characterized in that the specific steps of its preparation are as follows: (1) Coating of enhanced pre-coating: using a multifunctional coating machine, Coat the configured enhanced pre-coating paint (ie cationic starch solution) on the cellulose-based paper and then dry (including but not limited to heating plate drying, drying cylinder drying, hot air drying and natural drying); (2) coating of oil-proof layer : Use a multifunctional coating machine to apply the configured nano-cellulose/polyvinyl alcohol oil-repellent paint, and dry (including but not limited to hot plate drying, dryer drying, hot air drying and natural drying) at 103-107 degrees Celsius Heat treatment on the heating plate or in the drying cylinder, or directly heat treatment, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper; among them, the enhanced pre-coating
  • the basis weight of the coating is 0.1 g/m 2 to 10 g/m 2 ,
  • the present invention has the following beneficial technical effects:
  • the greaseproof paper obtained in the present invention can pass the highest grade 12 in the TAPPI T559 greaseproof test, and has excellent grease resistance. However, the same amount of polyvinyl alcohol coated paper can only pass grade 4 depending on the base paper. TAPPI T559 anti-grease test to 7.
  • the invention adds the charge effect of nano cellulose and cationic starch. Through electrostatic action, the positively charged starch will interact with the negatively charged nano-cellulose, which greatly prevents or delays the penetration effect of the nano-cellulose/polyvinyl alcohol solution, so that the polyvinyl alcohol forms a denser and thicker on the top of the base paper. Anti-oil layer to achieve a stronger anti-grease effect.
  • the present invention adds nano-cellulose and polyvinyl alcohol to the mixture, through hydrogen bonding, the viscosity of the polyvinyl alcohol/nano-cellulose mixed solution is increased, so that the coating is less likely to penetrate into the inside of the paper, and then as it dries, the poly(vinyl alcohol) Vinyl alcohol will form a better anti-grease layer on the surface of the base paper.
  • the mixing of nanocellulose and polyvinyl alcohol is added, and through hydrogen bonding, the shear thinning effect of the polyvinyl alcohol/nanocellulose mixed solution becomes stronger.
  • the shearing force of the coating knife (rod) increases, the viscosity of the solution decreases, making it easier to coat.
  • All raw materials used in the present invention can be gradually and completely degraded into carbon dioxide and water in nature, without the production of microplastics.
  • All the raw materials used in the present invention are non-toxic, and the obtained greaseproof paper can be used not only in industrial applications, such as sandpaper base paper, but also in the field of food packaging.
  • the coating process of the present invention is simple and easy to operate. For coated specialty paper companies, it can be produced without the need to purchase other equipment or use volatile organic solvents to ensure green production.
  • Preparation of oil-repellent coating (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 10:90, and stir at 95 degrees Celsius until Obtain a uniform 10% polyvinyl alcohol solution; (2) Wait for the polyvinyl alcohol solution to cool to room temperature.
  • Spare base paper copy paper with a grammage of 90g/m 2 , a density of 0.763g/cm 3 , and a Gurley air permeability of 18.6s/100ml.
  • Coating process Use K303 multi-functional coater to coat the configured polyvinyl alcohol oil-resistant paint with a JS10 bar at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate for 5 minutes Finally, it is transferred to a standard test environment and allowed to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the coating amount is 2g/m 2 .
  • the greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 7.
  • Preparation of oil-repellent coating (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 10:90, and stir at 95 degrees Celsius. Until a uniform 10% polyvinyl alcohol solution is obtained; (2) Wait for the polyvinyl alcohol solution to cool to room temperature.
  • Spare base paper unbleached packaging kraft paper with a weight of 50g/m 2 , a density of 0.722g/cm 3 , and a Gurley air permeability of 36.5s/100ml.
  • Coating process Use K303 multi-functional coater to coat the configured polyvinyl alcohol oil-resistant paint with a JS10 bar at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate for 5 minutes Finally, it is transferred to a standard test environment and allowed to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the coating amount is 2g/m 2 .
  • the greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 7.
  • Preparation of oil-repellent coating (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 10:90, and stir at 95 degrees Celsius until Obtain a uniform 10% polyvinyl alcohol solution; (2) Wait for the polyvinyl alcohol solution to cool to room temperature.
  • Spare base paper waste paper pulp cardboard with a grammage of 170g/m2, a density of 0.656g/cm3, and a Gurley air permeability of 20.5s/100ml.
  • Coating process Use K303 multi-functional coater to coat the configured polyvinyl alcohol oil-resistant paint with a JS10 bar at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate for 5 minutes Finally, it is transferred to a standard test environment and allowed to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the coating amount is 2g/m 2 .
  • the greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 4.
  • Preparation of oil-repellent coating (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nanofibers ( The cellulose nanofibrils oxidized by TEMPO method, TEMPO ⁇ CNF, provided by the University of Maine, USA, were sonicated to uniformity with a Q1375 (Qsonica) ultrasonic disruptor under ice water cooling. The solid content of the coating is the same as the coating in the first embodiment.
  • Spare base paper copy paper with a grammage of 90g/m 2 , a density of 0.763g/cm 3 , and a Gurley air permeability of 18.6s/100ml.
  • Coating process (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, then air dry naturally, and then heat it at 105°C. Heat treatment on the heating plate for 5 minutes, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the above-mentioned total coating amount is 2.4 g/m 2
  • the reinforced pre-coating layer is 0.4 g/m 2
  • the oil-repellent layer is 2 g/m 2 .
  • Test The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 12.
  • Preparation of oil-repellent coating (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nanocellulose in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nanocellulose (Cellulose nanofibrils oxidized by TEMPO method, TEMPO ⁇ CNF, provided by the University of Maine, USA) After cooling with ice water, use Q1375 (Qsonica) ultrasonic disintegrator to sonicate to uniformity.
  • the solid content of the coating is the same as that of the coating in the first embodiment.
  • Spare base paper unbleached packaging kraft paper with a grammage of 50g/m2, a density of 0.722g/cm3, and a Gurley air permeability of 36.5s/100ml.
  • Coating process (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, air dry, and then heat at 105 degrees The board is heat-treated for 5 minutes, and finally transferred to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
  • Test The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 12.
  • Preparation of oil-repellent coating (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Refer to a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nanofibers in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nanocellulose After the cellulose (cellulose nanofibrils oxidized by TEMPO method, TEMPO ⁇ CNF, provided by the University of Maine), under ice water cooling, the Q1375 (Qsonica) ultrasonic disintegrator was used to sonicate to uniformity.
  • the solid content of the coating is the same as that of the coating in Example 1.
  • Spare base paper waste paper pulp cardboard with a grammage of 170g/m 2 , a density of 0.656g/cm 3 , and a Gurley air permeability of 20.5s/100ml.
  • Coating process (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, then air dry naturally, and then heat it at 105°C. Heat treatment on the heating plate for 5 minutes, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
  • Spare base paper copy paper with a grammage of 90g/m 2 , a density of 0.763g/cm 3 , and a Gurley air permeability of 18.6s/100ml.
  • Coating process (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate 5 minutes, and finally transferred to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
  • Test The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559. The highest grade is 8, which is slightly higher than Example 1, but far lower than Example 4.
  • Spare base paper unbleached packaging kraft paper with a grammage of 50g/m2, a density of 0.722g/cm3, and a Gurley air permeability of 36.5s/100ml.
  • Coating process (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate 5 minutes, and finally transferred to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
  • the greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 7, which is the same as the second embodiment, but far lower than the fifth embodiment.
  • Spare base paper waste paper pulp cardboard with a grammage of 170g/m 2 , a density of 0.656g/cm 3 , and a Gurley air permeability of 20.5s/100ml.
  • Coating process (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured polyvinyl alcohol oil-repellent paint with a JS10 scraper at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate 5 minutes, and finally transferred to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
  • Test The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559. The highest grade is 7, which is higher than the third embodiment, but far lower than the sixth embodiment.
  • the present invention is implemented without the addition of nanocellulose.
  • the anti-grease based on the TAPPI T559 standard The grade has dropped significantly, which illustrates the importance of nanocellulose in the coating process of the present invention.
  • Preparation of oil-repellent coating (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nanocellulose in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nanocellulose (Cellulose nanofibrils oxidized by TEMPO method, TEMPO ⁇ CNF, provided by the University of Maine, USA) After cooling with ice water, use Q1375 (Qsonica) ultrasonic disintegrator to sonicate to uniformity.
  • the solid content of the above coating is the same as that of the coating in Example 1.
  • Spare base paper copy paper with a grammage of 90g/m 2 , a density of 0.763g/cm 3 , and a Gurley air permeability of 18.6s/100ml.
  • Coating process Use K303 multi-function coating machine to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent coating with JS10 at a speed of 3m/min, air dry, and then place it on a 105 degree heating plate Carry out heat treatment for 5 minutes, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the above-mentioned coating amount is 2 g/m 2 .
  • Test The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559. The highest grade is 8, which is higher than Example 1, but lower than Example 4.
  • Preparation of oil-repellent coating (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nano cellulose in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nano cellulose (Cellulose nanofibrils oxidized by TEMPO method, TEMPO ⁇ CNF, provided by the University of Maine, USA) After cooling with ice water, use Q1375 (Qsonica) ultrasonic disintegrator to sonicate to uniformity.
  • the solid content of the coating is the same as that of the coating in the first embodiment.
  • Spare base paper unbleached packaging kraft paper with a grammage of 50g/m2, a density of 0.722g/cm3, and a Gurley air permeability of 36.5s/100ml.
  • Coating process Use K303 multi-function coating machine to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent coating with JS10 at a speed of 3m/min, air dry, and then place it on a 105 degree heating plate Carry out heat treatment for 5 minutes, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the above-mentioned coating amount is 2 g/m 2 .
  • the greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559.
  • the highest grade is 8, which is slightly higher than the second embodiment, but significantly lower than the fifth embodiment.
  • Preparation of oil-repellent coating (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nano cellulose in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nano cellulose (Cellulose nanofibrils oxidized by TEMPO method, TEMPO ⁇ CNF, provided by the University of Maine, USA) After cooling with ice water, use Q1375 (Qsonica) ultrasonic disintegrator to sonicate to uniformity.
  • the solid content of the above coating is the same as that of the coating in Example 1.
  • Spare base paper waste paper pulp cardboard with a grammage of 170g/m2, a density of 0.656g/cm3, and a Gurley air permeability of 20.5s/100ml.
  • Coating process Use K303 multi-function coating machine to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent coating with JS10 at a speed of 3m/min, air dry, and then place it on a 105 degree heating plate Carry out heat treatment for 5 minutes, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the above-mentioned coating amount is 2 g/m 2 .
  • Examples 10 to 12 illustrate that without pre-coating treatment, in the case of a similar total coating amount, in the case of the same coating amount of the oil-resistant layer, the anti-grease grade based on the TAPPI T559 standard has The obvious decrease indicates that the increase in anti-grease ability is mainly due to the interaction of charges, and indicates the importance of cationic starch in the coating process system of the present invention.
  • the following example 13 used different types of polyvinyl alcohol for coating to prove that the type of polyvinyl alcohol has no effect on the anti-grease performance.
  • the following example 13 illustrates that under the nanocellulose/polyvinyl alcohol coating and process of the present invention, the grease resistance grade of the base paper of copy paper is not affected by changing the type of polyvinyl alcohol.
  • Preparation of oil-repellent paint (1) Take polyvinyl alcohol with a degree of hydrolysis of 98% to 99% and a molecular weight of 80,000 to 124,000, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nanocellulose in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nanocellulose (Cellulose nanofibrils oxidized by TEMPO method, TEMPO ⁇ CNF, provided by the University of Maine, USA) After cooling with ice water, use Q1375 (Qsonica) ultrasonic disintegrator to sonicate to uniformity.
  • the solid content of the above coating is the same as that of the coating in Example 1.
  • Spare base paper copy paper with a grammage of 90g/m 2 , a density of 0.763g/cm 3 , and a Gurley air permeability of 18.6s/100ml.
  • Coating process (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, air dry, and then heat at 105 degrees The board is heat-treated for 5 minutes, and finally transferred to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper.
  • the above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
  • Test The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 12.
  • Example 13 using polyvinyl alcohols with different molecular weights and different degrees of hydrolysis for coating experiments, the theory, effect, and grease resistance of the obtained paper of the present invention are not affected. Therefore, in actual production, it can be According to the actual demand of the product, change the type of polyvinyl alcohol. If the product needs better water resistance, you can use polyvinyl alcohol with a higher degree of hydrolysis; if you need a lower viscosity to meet the needs of the equipment in production, you can use polyvinyl alcohol with a lower molecular weight.

Abstract

The present invention relates to a biodegradable oil-proof paper without a fluorocarbon compound, and a preparation method therefor. The method comprises: first pre-coating cellulose base paper with a modified starch reinforced pre-coating layer, drying same, and then applying a prepared nanocellulose/polyvinyl alcohol (PVA) oil-proof layer. By means of the present invention, the problem of PVA permeation in the process of applying an oil-resistant layer using PVA as a main component is alleviated by means of the interaction between the nanocellulose and the cationic compound in the reinforced pre-coating layer, and the effect of enhancing the oil resistance of PVA in the coating is achieved, so that the oil permeation resistance of the oil-resistant layer is greatly improved; the present invention does not contain any fluorocarbon additive and is environment-friendly, has no toxic effect on the human body, and can be used as oil-proof paper for various purposes.

Description

一种不含氟碳化合物且可生物降解的防油纸及其制备方法Biodegradable oil-proof paper containing no fluorocarbon and preparation method thereof 技术领域Technical field
本发明涉及一种不含氟碳化合物且可生物降解的防油纸及其制备方法，特别是涉及以纤维素基纸为对象的表面处理工艺及其用途。The invention relates to a biodegradable greaseproof paper that does not contain fluorocarbon compounds and a preparation method thereof, and particularly relates to a surface treatment process and uses of cellulose-based paper as an object.
背景技术Background technique
一般而言，纤维素基纸是一种主要由纤维素和其他少量化合物组成的纸，它是一种表面有孔而毫无抗油性能的材料。工业上，涂布抗油纸是使用防油涂料经涂布的方法对基纸进行表面改性后的产品，通常情况下，涂布纸的抗油层的抗油性能主要由含氟化合物或者胶乳或者石蜡提供，但它们要么对人体、环境有毒有害，要么生产出的抗油纸回收性能、生物降解性能很差。近年来，世界各国都提高了对一次性塑料制品环保问题的重视，并且已经把禁塑令提上了议程，该发明可以一定程度的替代塑料制品。Generally speaking, cellulose-based paper is a paper mainly composed of cellulose and a small amount of other compounds. It is a material with pores on the surface and no oil resistance. Industrially, coated oil-repellent paper is a product that uses oil-repellent coatings to modify the surface of base paper. Under normal circumstances, the oil-repellent properties of the oil-repellent layer of coated paper are mainly composed of fluorine-containing compounds or latex or Paraffin wax is provided, but they are either toxic and harmful to the human body and the environment, or the oil-resistant paper produced has poor recycling performance and biodegradability. In recent years, countries all over the world have paid more attention to the environmental protection of disposable plastic products, and have put the ban on plastics on the agenda. This invention can replace plastic products to a certain extent.
为了让无抗油脂性能的基纸获得抗油性能，在基纸表面施加以抗油脂组分是必要的。具体而言，迄今为止已报道有如下的处理方法。In order for the base paper without anti-grease properties to obtain oil resistance, it is necessary to apply an anti-grease component on the surface of the base paper. Specifically, the following treatment methods have been reported so far.
专利文献1(美国专利US5,674,961)和专利文献2(美国专利US5,330,622)中提出了如下表面改性方法，通过浸润或者涂布的方法，把氟碳化合物附着在基纸的表面，使基纸获得抗油脂性能。尽管氟碳化合物纸张改性方法已经非常成熟且有效，但是氟碳化合物对人体和环境有害，而且会随着食物链转移、堆积。部分发达国家，例如加拿大***，美国环境保护署，德国联邦风险评估研究所，已经把氟碳化合物认定为对有潜在危害的化合物。因此，发展一种非氟碳基的抗油脂纸张涂布改性工艺是非常必要的。Patent Document 1 (U.S. Patent No. 5,674,961) and Patent Document 2 (U.S. Patent No. 5,330,622) propose the following surface modification methods. The fluorocarbon is attached to the surface of the base paper by infiltration or coating. The base paper obtains grease resistance. Although fluorocarbon paper modification methods are very mature and effective, fluorocarbons are harmful to the human body and the environment, and will be transferred and accumulated along the food chain. Some developed countries, such as Health Canada, the U.S. Environmental Protection Agency, and the German Federal Institute for Risk Assessment, have identified fluorocarbons as potentially harmful compounds. Therefore, it is very necessary to develop a non-fluorocarbon-based grease-resistant paper coating modification process.
专利文献3(美国专利US4418119A)中提出了如下的涂布工艺，其涂料有效成分主要由聚乙烯醇和硅脂组成，使用涂布技术，利用该二组分提供的抗油脂性能去提高基纸的抗油脂效果。但是，该方法在处理混合硅脂组分的时候需要利用到易气化的有机溶剂，例如庚烷或者甲苯，这对于生产环境的空气净化要求非常高，并且有生产安全问题。Patent Document 3 (US Patent US4418119A) proposes the following coating process. The effective ingredients of the coating are mainly composed of polyvinyl alcohol and silicone grease. The coating technology is used to improve the grease resistance provided by the two components. Anti-grease effect. However, this method requires the use of easily vaporized organic solvents, such as heptane or toluene, when processing the mixed silicone grease components, which requires very high air purification in the production environment and has production safety issues.
专利文献4(中国专利CN103669105A)中提出了如下的涂布工艺，先在基纸上涂以淀粉、塑化剂、成膜助剂、含氟化合物组成的涂料，然后再经烘干，得到成纸。含氟化合物为全氟聚醚磷酸酯、含氟丙烯酸酯，涂料固含量在5％到15％。但是，该涂布工艺虽然未使用氟碳化合物，但还是使用了含氟化合物，会有潜在危害，同时由于使用了塑化剂和一些其他助剂，也会有一些其它的潜在危害。Patent Document 4 (Chinese Patent CN103669105A) proposes the following coating process. The base paper is first coated with a coating composed of starch, plasticizer, film-forming aids, and fluorine-containing compounds, and then dried to obtain the finished product. Paper. The fluorine-containing compound is perfluoropolyether phosphate and fluorine-containing acrylate, and the solid content of the coating is 5% to 15%. However, although the coating process does not use fluorocarbon compounds, it still uses fluorine-containing compounds, which will be potentially harmful. At the same time, due to the use of plasticizers and some other additives, there will also be some other potential hazards.
专利文献5(中国专利CN110258184A)提出了如下的涂布工艺，在基纸上涂以改性 淀粉和壳聚糖等成分后干燥得到食品级防油纸。但是由于壳聚糖成本过高，适用场景有局限性，并且该方法的极限抗油脂性能有限。Patent Document 5 (Chinese Patent CN110258184A) proposes the following coating process. The base paper is coated with modified starch and chitosan and then dried to obtain food-grade greaseproof paper. However, due to the high cost of chitosan, the applicable scenarios are limited, and the extreme anti-grease performance of this method is limited.
另外，在传统的聚乙烯醇溶液涂布工艺中，聚乙烯醇水溶液可以经干燥而形成一层光滑致密的薄膜，当其覆盖在基纸顶层上时，有良好的抗油脂的作用，但由于纸拥有良好的亲水性，聚乙烯醇溶液可以经基纸表面的孔洞渗透入纸内部，进而基纸表层的聚乙烯醇无法形成一个致密而厚实的抗油脂膜，所以传统方式的PVA涂布工艺无法提供优异的抗油脂性能。In addition, in the traditional polyvinyl alcohol solution coating process, the polyvinyl alcohol solution can be dried to form a smooth and dense film. When it is covered on the top layer of the base paper, it has a good anti-grease effect. The paper has good hydrophilicity. The polyvinyl alcohol solution can penetrate into the paper through the holes on the surface of the base paper, and the polyvinyl alcohol on the surface of the base paper cannot form a dense and thick anti-oil film, so the traditional method of PVA coating The process cannot provide excellent grease resistance.
如上所述，现有的涂布防油纸均存在一些问题。随着人民生活水平的日益提高，人们希望使用绿色环保、可生物降解且高抗油脂性能的防油纸，不仅在食品包装上，而且在工业应用上，比如砂纸原纸。因此，使用含氟化合物和挥发性有机溶剂的原涂布工艺需要被绿色环保的高性能新型涂布防油纸工艺所替代。As mentioned above, the existing coated greaseproof paper has some problems. With the improvement of people's living standards, people hope to use green, biodegradable, and highly oil-resistant greaseproof paper, not only in food packaging, but also in industrial applications, such as sandpaper base paper. Therefore, the original coating process that uses fluorine-containing compounds and volatile organic solvents needs to be replaced by a new, environmentally friendly, high-performance coating greaseproof paper process.
发明内容Summary of the invention
本发明的目的是针对目前防油纸存在的不绿色环保、回收性能差以及难生物降解的技术问题，提供一种简单的表面改性工艺，在涂布工艺中避免使用氟碳化合物、硅脂及挥发性有机化合物的同时，以提升食品包装基纸或者超细砂纸原纸基纸的抗油脂能力，在不损失与其他高分子化合物(如聚氨酯)的结合能力的情况下，且不损失基纸重新回收制浆能力的一种不含氟碳化合物且可生物降解的防油纸及其制备方法。The purpose of the present invention is to provide a simple surface modification process to avoid the use of fluorocarbons, silicone greases and fluorocarbons in the coating process in view of the current technical problems of non-green environmental protection, poor recycling performance and difficult biodegradability of greaseproof paper. In addition to volatile organic compounds, it can improve the grease resistance of food packaging base paper or superfine sandpaper base paper, without losing the ability to bind with other polymer compounds (such as polyurethane), and without losing the base paper. A biodegradable greaseproof paper that does not contain fluorocarbon compounds and has the recovery pulping ability and a preparation method thereof.
为解决上述技术问题，本发明采用如下所述的技术方案是：一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于:在纤维素基纸上先预涂布一层变性淀粉类增强预涂涂料得到增强预涂层，再进行纳米纤维素/聚乙烯醇配合的防油涂料涂布得到防油层。In order to solve the above technical problems, the present invention adopts the following technical solution: a biodegradable greaseproof paper that does not contain fluorocarbons and a preparation method thereof, characterized in that: pre-coating on cellulose-based paper A layer of modified starch-based reinforced pre-coating paint is used to obtain a reinforced pre-coating layer, and then an oil-repellent coating of nano cellulose/polyvinyl alcohol is coated to obtain an oil-repellent layer.
所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于所述的增强预涂涂料的制备方法为：将阳离子淀粉或其它阳离子高分子化合物按质量比1～10:90～99加入去离子水，放入磁子，放置于70～90摄氏度磁力加热搅拌器上溶解，直至得到均一溶液、胶液或分散液。The biodegradable greaseproof paper containing no fluorocarbon and the preparation method thereof is characterized in that the preparation method of the reinforced pre-coating paint is: adding cationic starch or other cationic polymer compounds to a mass ratio of 1 ~10:90~99 Add deionized water, put in magnets, and place on 70~90 degrees Celsius magnetic heating stirrer to dissolve until a homogeneous solution, glue or dispersion is obtained.
所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于所述的防油涂料的制备具体步骤如下：(1)取聚乙烯醇按质量比5～20:80～95加入去离子水，在80～100摄氏度搅拌，直至得到均一的溶液；(2)等待聚乙烯醇溶液冷却至室温；(3)冷却后，按照聚乙烯醇与纳米纤维素固含量比为20～100:1的比例加入纳米纤维素后，在冰水冷却条件 下，超声至均一。所述的聚乙烯醇可以是任何一种聚乙烯醇或者两种、多种聚乙烯醇的混合物，聚乙烯醇的水解度和分子量可以根据产品生产的要求进行变更；所述的纳米纤维素可以是任何一种纳米纤维素，包括但不限于纤维素纳米晶(CNC)、纤维素纳米纤丝(CNF)和TEMPO氧化的纤维素纳米纤丝。The biodegradable oil-repellent paper containing no fluorocarbon and its preparation method is characterized in that the specific steps of preparing the oil-repellent coating are as follows: (1) Take polyvinyl alcohol in a mass ratio of 5-20 : Add deionized water from 80 to 95 degrees Celsius and stir at 80 to 100 degrees Celsius until a uniform solution is obtained; (2) Wait for the polyvinyl alcohol solution to cool to room temperature; (3) After cooling, follow the solid content of polyvinyl alcohol and nanocellulose After adding nano cellulose in a ratio of 20-100:1, ultrasonication is performed until uniform under ice-water cooling. The polyvinyl alcohol can be any kind of polyvinyl alcohol or a mixture of two or more polyvinyl alcohols. The degree of hydrolysis and molecular weight of polyvinyl alcohol can be changed according to the requirements of product production; the nano cellulose can be It is any kind of nanocellulose, including but not limited to cellulose nanocrystals (CNC), cellulose nanofibrils (CNF) and TEMPO oxidized cellulose nanofibrils.
所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于纤维素基纸可以是任意一种纤维素基纸材料，包括并不限于复印纸、滤纸、牛皮纸、纸板和铜版纸，纤维来源可以是原生也可以是再生。The biodegradable greaseproof paper containing no fluorocarbon and its preparation method is characterized in that the cellulose-based paper can be any cellulose-based paper material, including but not limited to copy paper, filter paper, kraft paper , Paperboard and coated paper, the fiber source can be virgin or recycled.
所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于其制备的具体步骤如下：(1)增强预涂层的涂布：使用多功能涂布机，涂配置好的增强预涂涂料(即阳离子淀粉溶液)于纤维素基纸上后干燥(包括但不限于加热板干燥，烘缸干燥，热风干燥和自然干燥)；(2)防油层的涂布：使用多功能涂布机，涂配置好的纳米纤维素/聚乙烯醇防油涂料，干燥(包括但不限于加热板干燥，烘缸干燥，热风干燥和自然干燥)后在103～107度的加热板上或者烘缸中进行热处理，也可直接进行热处理，最后转移至标准测试环境中静置12～24小时使涂布纸各组分间氢键重建并平整纸张；其中的增强预涂层的涂布的定量为0.1g/m 2到10g/m 2，防油层的涂布的定量为0.2g/m 2到20g/m 2。 The biodegradable greaseproof paper containing no fluorocarbon and its preparation method is characterized in that the specific steps of its preparation are as follows: (1) Coating of enhanced pre-coating: using a multifunctional coating machine, Coat the configured enhanced pre-coating paint (ie cationic starch solution) on the cellulose-based paper and then dry (including but not limited to heating plate drying, drying cylinder drying, hot air drying and natural drying); (2) coating of oil-proof layer : Use a multifunctional coating machine to apply the configured nano-cellulose/polyvinyl alcohol oil-repellent paint, and dry (including but not limited to hot plate drying, dryer drying, hot air drying and natural drying) at 103-107 degrees Celsius Heat treatment on the heating plate or in the drying cylinder, or directly heat treatment, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper; among them, the enhanced pre-coating The basis weight of the coating is 0.1 g/m 2 to 10 g/m 2 , and the basis weight of the oil-repellent layer is 0.2 g/m 2 to 20 g/m 2 .
本发明与其它方法相比，有益技术效果是：Compared with other methods, the present invention has the following beneficial technical effects:
(1)本发明所得防油纸可以通过TAPPI T559防油脂测试中最高的等级12，具有优异的抗油脂性能，而相同量的聚乙烯醇涂布纸，根据基纸的不同，只能通过等级4到7的TAPPI T559防油脂测试。(1) The greaseproof paper obtained in the present invention can pass the highest grade 12 in the TAPPI T559 greaseproof test, and has excellent grease resistance. However, the same amount of polyvinyl alcohol coated paper can only pass grade 4 depending on the base paper. TAPPI T559 anti-grease test to 7.
(2)本发明加入纳米纤维素与阳离子淀粉的电荷作用效应。通过静电作用，带正点的淀粉会和带负电的纳米纤维素作用，大幅度阻止或者延缓了纳米纤维素/聚乙烯醇溶液的渗透效应，使聚乙烯醇在基纸顶部形成更加致密且厚实的抗油层，以达到更强的抗油脂效果。(2) The invention adds the charge effect of nano cellulose and cationic starch. Through electrostatic action, the positively charged starch will interact with the negatively charged nano-cellulose, which greatly prevents or delays the penetration effect of the nano-cellulose/polyvinyl alcohol solution, so that the polyvinyl alcohol forms a denser and thicker on the top of the base paper. Anti-oil layer to achieve a stronger anti-grease effect.
(3)本发明加入纳米纤维素和聚乙烯醇的混合，通过氢键结合，聚乙烯醇/纳米纤维素混合溶液的粘度增强，使涂料更不容易渗透进纸内部，进而随着干燥，聚乙烯醇会在基纸表面生成更好的抗油脂层。(3) The present invention adds nano-cellulose and polyvinyl alcohol to the mixture, through hydrogen bonding, the viscosity of the polyvinyl alcohol/nano-cellulose mixed solution is increased, so that the coating is less likely to penetrate into the inside of the paper, and then as it dries, the poly(vinyl alcohol) Vinyl alcohol will form a better anti-grease layer on the surface of the base paper.
(4)本发明加入纳米纤维素和聚乙烯醇的混合，通过氢键结合，聚乙烯醇/纳米纤维素混合溶液的剪切变稀效应变强。在涂布时，溶液粘度随着涂布刀(棒)的剪切力的变大，溶液粘度变小，更易于涂布。(4) In the present invention, the mixing of nanocellulose and polyvinyl alcohol is added, and through hydrogen bonding, the shear thinning effect of the polyvinyl alcohol/nanocellulose mixed solution becomes stronger. During coating, as the shearing force of the coating knife (rod) increases, the viscosity of the solution decreases, making it easier to coat.
(5)本发明所用所有原料，均可在自然中天然逐渐完全降解为二氧化碳和水，无 微塑料产生。(5) All raw materials used in the present invention can be gradually and completely degraded into carbon dioxide and water in nature, without the production of microplastics.
(6)本发明所用所有原料，均无毒害作用，所得防油纸不仅可以用于工业应用，如砂纸原纸，也可应用于食品包装领域。(6) All the raw materials used in the present invention are non-toxic, and the obtained greaseproof paper can be used not only in industrial applications, such as sandpaper base paper, but also in the field of food packaging.
(7)本发明涂布过程简单，易于操作，对于涂布特种纸企业，无需多余采购其他设备即可生产，也无需使用易挥发的有机溶剂，以保证绿色生产。(7) The coating process of the present invention is simple and easy to operate. For coated specialty paper companies, it can be produced without the need to purchase other equipment or use volatile organic solvents to ensure green production.
具体实施方式Detailed ways
下面结合具体的实施例对传统工艺与本发明作进一步详细说明和对比，包括但不仅限于实施例。The following is a detailed description and comparison between the traditional process and the present invention in combination with specific embodiments, including but not limited to the embodiments.
一、以下实施例一至三是说明传统聚乙烯醇涂布工艺下的防油纸抗油脂等级。1. The following examples 1 to 3 illustrate the grease resistance grade of greaseproof paper under the traditional polyvinyl alcohol coating process.
(一)实施例一。(1) Example one.
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯醇按质量比10:90加入去离子水，在95摄氏度搅拌，直至得到均一的10％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温。1. Preparation of oil-repellent coating: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 10:90, and stir at 95 degrees Celsius until Obtain a uniform 10% polyvinyl alcohol solution; (2) Wait for the polyvinyl alcohol solution to cool to room temperature.
2、基纸备用：克重为90g/m 2，密度为0.763g/cm 3，Gurley透气度为18.6s/100ml的复印纸。 2. Spare base paper: copy paper with a grammage of 90g/m 2 , a density of 0.763g/cm 3 , and a Gurley air permeability of 18.6s/100ml.
3、涂布工艺：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的聚乙烯醇防油涂料，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张，其中的涂布量为2g/m 2。 3. Coating process: Use K303 multi-functional coater to coat the configured polyvinyl alcohol oil-resistant paint with a JS10 bar at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate for 5 minutes Finally, it is transferred to a standard test environment and allowed to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The coating amount is 2g/m 2 .
4、测试：本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为7。4. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 7.
(二)实施例二。(2) The second embodiment.
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯醇按质量比10:90加入去离子水，于95摄氏度下搅拌，直至得到均一的10％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温。1. Preparation of oil-repellent coating: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 10:90, and stir at 95 degrees Celsius. Until a uniform 10% polyvinyl alcohol solution is obtained; (2) Wait for the polyvinyl alcohol solution to cool to room temperature.
2、基纸备用：克重为50g/m 2，密度为0.722g/cm 3，Gurley透气度为36.5s/100ml的未漂包装牛皮纸。 2. Spare base paper: unbleached packaging kraft paper with a weight of 50g/m 2 , a density of 0.722g/cm 3 , and a Gurley air permeability of 36.5s/100ml.
3、涂布工艺：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的聚乙烯醇防油涂料，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张，其中的涂布量为 2g/m 2。 3. Coating process: Use K303 multi-functional coater to coat the configured polyvinyl alcohol oil-resistant paint with a JS10 bar at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate for 5 minutes Finally, it is transferred to a standard test environment and allowed to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The coating amount is 2g/m 2 .
4、测试：本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为7。4. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 7.
(三)实施例三。(3) The third embodiment.
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯醇按质量比10:90加入去离子水，在95摄氏度搅拌，直至得到均一的10％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温。1. Preparation of oil-repellent coating: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 10:90, and stir at 95 degrees Celsius until Obtain a uniform 10% polyvinyl alcohol solution; (2) Wait for the polyvinyl alcohol solution to cool to room temperature.
2、基纸备用：克重为170g/m2，密度为0.656g/cm3，Gurley透气度为20.5s/100ml的废纸浆纸板。2. Spare base paper: waste paper pulp cardboard with a grammage of 170g/m2, a density of 0.656g/cm3, and a Gurley air permeability of 20.5s/100ml.
3、涂布工艺：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的聚乙烯醇防油涂料，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张，其中的涂布量为2g/m 2。 3. Coating process: Use K303 multi-functional coater to coat the configured polyvinyl alcohol oil-resistant paint with a JS10 bar at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate for 5 minutes Finally, it is transferred to a standard test environment and allowed to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The coating amount is 2g/m 2 .
4、测试：本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为4。4. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 4.
(四)结论一。(4) Conclusion one.
基于实施例一至三，我们可以得出，传统的基于聚乙烯醇的纸表面涂布工艺不能给予纸产品足够高的抗油脂性能。Based on Examples 1 to 3, we can conclude that the traditional polyvinyl alcohol-based paper surface coating process cannot give paper products high enough grease resistance.
二、以下实施例四至六是说明在本发明的纳米纤维素/聚乙烯醇涂料与工艺下的防油纸抗油脂等级。2. The following Examples 4 to 6 illustrate the anti-grease grade of greaseproof paper under the nanocellulose/polyvinyl alcohol coating and process of the present invention.
(一)实施例四。(1) The fourth embodiment.
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯醇按质量比19:81加入去离子水，在95摄氏度搅拌，直至得到均一的19％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温；(3)冷却后，按照聚乙烯醇与纳米纤维素固含量比为19～1的比例加入纳米纤维(TEMPO法氧化的纤维素纳米纤丝，TEMPO～CNF，美国缅因大学提供)后，在冰水冷却条件下，使用Q1375(Qsonica)超声破碎仪超声至均一。其中所述涂料固含量与上述实施例一中的涂料相同。1. Preparation of oil-repellent coating: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nanofibers ( The cellulose nanofibrils oxidized by TEMPO method, TEMPO～CNF, provided by the University of Maine, USA, were sonicated to uniformity with a Q1375 (Qsonica) ultrasonic disruptor under ice water cooling. The solid content of the coating is the same as the coating in the first embodiment.
2、增强预涂涂料的制备：(1)取阳离子淀粉(HI CAT 5283A)按质量比2:98加入去离子水，放入磁子，放置于80摄氏度磁力加热搅拌器上溶解30分钟，直至均一；(2)等待阳离子淀粉溶液冷却至室温。2. Preparation of enhanced pre-coating paint: (1) Take cationic starch (HI CAT 5283A) and add deionized water at a mass ratio of 2:98, put in a magnet, and place it on a magnetic heating stirrer at 80 degrees Celsius to dissolve for 30 minutes until Uniformity; (2) Wait for the cationic starch solution to cool to room temperature.
3、基纸备用：克重为90g/m 2，密度为0.763g/cm 3，Gurley透气度为18.6s/100ml的复印纸。 3. Spare base paper: copy paper with a grammage of 90g/m 2 , a density of 0.763g/cm 3 , and a Gurley air permeability of 18.6s/100ml.
4、涂布工艺：(1)增强预涂层的涂布：用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的阳离子淀粉增强预涂涂料，自然风干；(2)防油层的涂布：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的纳米纤维素/聚乙烯醇防油涂料后，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张。上述的总涂布量为2.4g/m 2，增强预涂层0.4g/m 2，防油层2g/m 2。 4. Coating process: (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, then air dry naturally, and then heat it at 105°C. Heat treatment on the heating plate for 5 minutes, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The above-mentioned total coating amount is 2.4 g/m 2 , the reinforced pre-coating layer is 0.4 g/m 2 , and the oil-repellent layer is 2 g/m 2 .
5、测试：本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为12，5. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 12.
为该测试标准最高的抗油脂等级。同时，仅经预涂处理的基纸抗油脂等级为0。It is the highest anti-grease grade of the test standard. At the same time, only the pre-coated base paper has an anti-grease rating of 0.
(二)实施例五。(2) The fifth embodiment.
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯醇按质量比19:81加入去离子水，在95摄氏度搅拌，直至得到均一的19％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温；(3)冷却后，按照聚乙烯醇与纳米纤维素固含量比为19～1的比例加入纳米纤维素(TEMPO法氧化的纤维素纳米纤丝，TEMPO～CNF，美国缅因大学提供)后，在冰水冷却条件下，使用Q1375(Qsonica)超声破碎仪超声至均一。其中所述涂料固含量与上述实施例一中涂料的相同。1. Preparation of oil-repellent coating: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nanocellulose in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nanocellulose (Cellulose nanofibrils oxidized by TEMPO method, TEMPO～CNF, provided by the University of Maine, USA) After cooling with ice water, use Q1375 (Qsonica) ultrasonic disintegrator to sonicate to uniformity. The solid content of the coating is the same as that of the coating in the first embodiment.
2、增强预涂涂料的制备：(1)取阳离子淀粉(HI CAT 5283A)按质量比2:98加入去离子水，放入磁子，放置于80摄氏度磁力加热搅拌器上溶解30分钟，直至均一；(2)等待阳离子淀粉溶液冷却至室温。2. Preparation of enhanced pre-coating paint: (1) Take cationic starch (HI CAT 5283A) and add deionized water at a mass ratio of 2:98, put in a magnet, and place it on a magnetic heating stirrer at 80 degrees Celsius to dissolve for 30 minutes until Uniformity; (2) Wait for the cationic starch solution to cool to room temperature.
3、基纸备用：克重为50g/m2，密度为0.722g/cm3，Gurley透气度为36.5s/100ml的未漂包装牛皮纸。3. Spare base paper: unbleached packaging kraft paper with a grammage of 50g/m2, a density of 0.722g/cm3, and a Gurley air permeability of 36.5s/100ml.
4、涂布工艺：(1)增强预涂层的涂布：用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的阳离子淀粉增强预涂涂料，自然风干；(2)防油层的涂布：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的纳米纤维素/聚乙烯醇防油涂料，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张。上述总涂布量为2.4g/m 2，其中增强预涂层0.4g/m 2，防油层2g/m 2。 4. Coating process: (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, air dry, and then heat at 105 degrees The board is heat-treated for 5 minutes, and finally transferred to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
5、测试：本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为12，5. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 12.
为该测试标准最高的抗油脂等级。同时，仅经预涂处理的基纸抗油脂等级为0。It is the highest anti-grease grade of the test standard. At the same time, only the pre-coated base paper has an anti-grease rating of 0.
(三)实施例六。(3) The sixth embodiment.
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯 醇按质量比19:81加入去离子水，在95摄氏度搅拌，直至提到均一的19％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温；(3)冷却后，按照聚乙烯醇与纳米纤维素固含量比为19～1的比例加入纳米纤维素(TEMPO法氧化的纤维素纳米纤丝，TEMPO～CNF，美国缅因大学提供)后，在冰水冷却条件下，使用Q1375(Qsonica)超声破碎仪超声至均一。其中所述涂料固含量与实施例一中涂料的相同。1. Preparation of oil-repellent coating: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Refer to a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nanofibers in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nanocellulose After the cellulose (cellulose nanofibrils oxidized by TEMPO method, TEMPO～CNF, provided by the University of Maine), under ice water cooling, the Q1375 (Qsonica) ultrasonic disintegrator was used to sonicate to uniformity. The solid content of the coating is the same as that of the coating in Example 1.
2、增强预涂涂料的制备：(1)取阳离子淀粉(HI CAT 5283A)按质量比2:98加入去离子水，放入磁子，放置于80摄氏度磁力加热搅拌器上溶解30分钟，直至均一；(2)等待阳离子淀粉溶液冷却至室温。2. Preparation of enhanced pre-coating paint: (1) Take cationic starch (HI CAT 5283A) and add deionized water at a mass ratio of 2:98, put in a magnet, and place it on a magnetic heating stirrer at 80 degrees Celsius to dissolve for 30 minutes until Uniformity; (2) Wait for the cationic starch solution to cool to room temperature.
3、基纸备用：克重为170g/m 2，密度为0.656g/cm 3，Gurley透气度为20.5s/100ml的废纸浆纸板。 3. Spare base paper: waste paper pulp cardboard with a grammage of 170g/m 2 , a density of 0.656g/cm 3 , and a Gurley air permeability of 20.5s/100ml.
4、涂布工艺：(1)增强预涂层的涂布：用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的阳离子淀粉增强预涂涂料，自然风干；(2)防油层的涂布：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的纳米纤维素/聚乙烯醇防油涂料后，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张。上述总涂布量为2.4g/m 2，其中增强预涂层0.4g/m 2，防油层2g/m 2。 4. Coating process: (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, then air dry naturally, and then heat it at 105°C. Heat treatment on the heating plate for 5 minutes, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
5、测试：本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为10。同时，仅经预涂处理的基纸抗油脂等级为0。5. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 10. At the same time, only the pre-coated base paper has an anti-grease rating of 0.
(四)结论二。(4) Conclusion two.
通过比较实施例一、二、三与实施例四、五、六，在相似的总涂布量的情况下，在相同的抗油层涂布量的情况下，基于TAPPI T559标准的抗油脂等级大幅度提升，甚至牛皮纸与复印纸为基纸的防油纸的抗油脂的抗油脂等级已经达到了该标准的最高标准。实施例四至六说明了本发明中纳米纤维素和阳离子淀粉电荷作用的重要性，抗油脂能力提升主要来源于此。By comparing Examples 1, 2, and 3 with Examples 4, 5, and 6, in the case of a similar total coating amount and the same oil-resistant layer coating amount, the grease resistance level based on the TAPPI T559 standard is higher. The rate has increased, and even the grease-proof grade of greaseproof paper based on kraft paper and copy paper has reached the highest standard of this standard. Examples 4 to 6 illustrate the importance of the charge function of nanocellulose and cationic starch in the present invention, and the improvement of anti-oil ability mainly comes from this.
三、以下实施例七至九是说明在本发明改进后的纳米纤维素/聚乙烯醇涂料与工艺下，在没有添加纳米纤维素的情况下的防油纸抗油脂等级。3. The following Examples 7 to 9 illustrate the anti-grease grade of greaseproof paper without adding nano cellulose under the improved nano cellulose/polyvinyl alcohol coating and process of the present invention.
(一)实施例七。(1) The seventh embodiment.
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯醇按质量比10:90加入去离子水，放置于95摄氏度的烘箱内，每半小时彻底搅拌一次，直至搅拌均一，得到10％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温。其中所述涂料固 含量与上述实施例一中涂料的相同。1. Preparation of oil-repellent paint: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 10:90, and place it in an oven at 95 degrees Celsius. Inside, thoroughly stir once every half an hour until the stirring is uniform to obtain a 10% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature. The solid content of the coating is the same as that of the coating in Example 1 above.
2、增强预涂涂料的制备：(1)取阳离子淀粉(HI CAT 5283A)按质量比2:98加入去离子水，放入磁子，放置于80摄氏度磁力加热搅拌器上溶解30分钟，直至均一；(2)等待阳离子淀粉溶液冷却至室温。2. Preparation of enhanced pre-coating paint: (1) Take cationic starch (HI CAT 5283A) and add deionized water at a mass ratio of 2:98, put in a magnet, and place it on a magnetic heating stirrer at 80 degrees Celsius to dissolve for 30 minutes until Uniformity; (2) Wait for the cationic starch solution to cool to room temperature.
3、基纸备用：克重为90g/m 2，密度为0.763g/cm 3，Gurley透气度为18.6s/100ml的复印纸。 3. Spare base paper: copy paper with a grammage of 90g/m 2 , a density of 0.763g/cm 3 , and a Gurley air permeability of 18.6s/100ml.
4、涂布工艺：(1)增强预涂层的涂布：用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的阳离子淀粉增强预涂涂料，自然风干；(2)防油层的涂布：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的聚乙烯醇防油涂料，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张。上述总涂布量为2.4g/m 2，其中增强预涂层0.4g/m 2，防油层2g/m 2。 4. Coating process: (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate 5 minutes, and finally transferred to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
5、测试：本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为8，略高于实施例一，但远低于实施例四。5. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559. The highest grade is 8, which is slightly higher than Example 1, but far lower than Example 4.
(二)实施例八(2) Example 8
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯醇按质量比10:90加入去离子水，在95摄氏度搅拌，直至得到均一的10％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温。上述涂料固含量与实施例一中涂料的相同。1. Preparation of oil-repellent coating: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 10:90, and stir at 95 degrees Celsius until Obtain a uniform 10% polyvinyl alcohol solution; (2) Wait for the polyvinyl alcohol solution to cool to room temperature. The solid content of the above coating is the same as that of the coating in Example 1.
2、增强预涂涂料的制备：(1)取阳离子淀粉(HI CAT 5283A)按质量比2:98加入去离子水，放入磁子，放置于80摄氏度磁力加热搅拌器上溶解30分钟，直至均一；(2)等待阳离子淀粉溶液冷却至室温。2. Preparation of enhanced pre-coating paint: (1) Take cationic starch (HI CAT 5283A) and add deionized water at a mass ratio of 2:98, put in a magnet, and place it on a magnetic heating stirrer at 80 degrees Celsius to dissolve for 30 minutes until Uniformity; (2) Wait for the cationic starch solution to cool to room temperature.
3、基纸备用：克重为50g/m2，密度为0.722g/cm3，Gurley透气度为36.5s/100ml的未漂包装牛皮纸。3. Spare base paper: unbleached packaging kraft paper with a grammage of 50g/m2, a density of 0.722g/cm3, and a Gurley air permeability of 36.5s/100ml.
4、涂布工艺：(1)增强预涂层的涂布：用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的阳离子淀粉增强预涂涂料，自然风干；(2)防油层的涂布：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的聚乙烯醇防油涂料，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张。上述总涂布量为2.4g/m 2，其中增强预涂层0.4g/m 2，防油层2g/m 2。 4. Coating process: (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate 5 minutes, and finally transferred to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为7，与实施例二相同， 但远低于实施例五。The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 7, which is the same as the second embodiment, but far lower than the fifth embodiment.
(三)实施例九(3) Example 9
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯醇按质量比10:90加入去离子水，在95摄氏度搅拌，直至得到均一的10％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温。上述涂料固含量与实施例一中涂料的相同。1. Preparation of oil-repellent coating: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 10:90, and stir at 95 degrees Celsius until Obtain a uniform 10% polyvinyl alcohol solution; (2) Wait for the polyvinyl alcohol solution to cool to room temperature. The solid content of the above coating is the same as that of the coating in Example 1.
2、增强预涂涂料的制备：(1)取阳离子淀粉(HI CAT 5283A)按质量比2:98加入去离子水，放入磁子，放置于80摄氏度磁力加热搅拌器上溶解30分钟，直至均一；(2)等待阳离子淀粉溶液冷却至室温。2. Preparation of enhanced pre-coating paint: (1) Take cationic starch (HI CAT 5283A) and add deionized water at a mass ratio of 2:98, put in a magnet, and place it on a magnetic heating stirrer at 80 degrees Celsius to dissolve for 30 minutes until Uniformity; (2) Wait for the cationic starch solution to cool to room temperature.
3、基纸备用：克重为170g/m 2，密度为0.656g/cm 3，Gurley透气度为20.5s/100ml的废纸浆纸板。 3. Spare base paper: waste paper pulp cardboard with a grammage of 170g/m 2 , a density of 0.656g/cm 3 , and a Gurley air permeability of 20.5s/100ml.
4、涂布工艺：(1)增强预涂层的涂布：用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的阳离子淀粉增强预涂涂料，自然风干；(2)防油层的涂布：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的聚乙烯醇防油涂料，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张。上述总涂布量为2.4g/m 2，其中增强预涂层0.4g/m 2，防油层2g/m 2。 4. Coating process: (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured polyvinyl alcohol oil-repellent paint with a JS10 scraper at a speed of 3m/min, air dry, and heat treatment on a 105 degree heating plate 5 minutes, and finally transferred to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
5、测试：本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为7，比实施例三高，但远低于实施例六。5. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559. The highest grade is 7, which is higher than the third embodiment, but far lower than the sixth embodiment.
四、结论三。Fourth, conclusion three.
通过实施例七至九，在不添加纳米纤维素的情况下实施本发明，在相似的总涂布量的情况下，在相同的防油层涂布量的情况下，基于TAPPI T559标准的抗油脂等级有了明显下降，说明了纳米纤维素在本发明的涂布工艺中的重要性。Through Examples 7-9, the present invention is implemented without the addition of nanocellulose. In the case of a similar total coating amount and the same oil-repellent layer coating amount, the anti-grease based on the TAPPI T559 standard The grade has dropped significantly, which illustrates the importance of nanocellulose in the coating process of the present invention.
五、以下实施例十至十二是说明在本发明的纳米纤维素/聚乙烯醇涂料与工艺下，在没有阳离子淀粉预涂的情况下的防油纸抗油脂等级。5. The following examples ten to twelve illustrate the anti-grease grade of greaseproof paper without cationic starch pre-coating under the nanocellulose/polyvinyl alcohol coating and process of the present invention.
(一)实施例十。(1) The tenth embodiment.
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯醇按质量比19:81加入去离子水，在95摄氏度搅拌，直至得到均一的19％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温；(3)冷却后，按照聚乙烯醇与纳米纤维素固含量比为19～1的比例加入纳米纤维素(TEMPO法氧化的纤维素纳米纤丝，TEMPO～CNF，美国缅因大学提供)后，在冰水冷却条件下，使用Q1375(Qsonica)超声破碎仪超声至均一。上述 涂料固含量与实施例一中涂料的相同。1. Preparation of oil-repellent coating: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nanocellulose in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nanocellulose (Cellulose nanofibrils oxidized by TEMPO method, TEMPO～CNF, provided by the University of Maine, USA) After cooling with ice water, use Q1375 (Qsonica) ultrasonic disintegrator to sonicate to uniformity. The solid content of the above coating is the same as that of the coating in Example 1.
2、基纸备用：克重为90g/m 2，密度为0.763g/cm 3，Gurley透气度为18.6s/100ml的复印纸。 2. Spare base paper: copy paper with a grammage of 90g/m 2 , a density of 0.763g/cm 3 , and a Gurley air permeability of 18.6s/100ml.
3、涂布工艺：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的纳米纤维素/聚乙烯醇防油涂料，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张。上述涂布量为2g/m 2。 3. Coating process: Use K303 multi-function coating machine to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent coating with JS10 at a speed of 3m/min, air dry, and then place it on a 105 degree heating plate Carry out heat treatment for 5 minutes, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The above-mentioned coating amount is 2 g/m 2 .
4、测试：本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为8，高于实施例一，但低于实施例四。4. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559. The highest grade is 8, which is higher than Example 1, but lower than Example 4.
(二)实施例十一。(2) The eleventh embodiment.
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯醇按质量比19:81加入去离子水，在95摄氏度搅拌，直至得到均一的19％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温；(3)冷却后，按照聚乙烯醇与纳米纤维素固含量比为19～1的比例加入纳米纤维素(TEMPO法氧化的纤维素纳米纤丝，TEMPO～CNF，美国缅因大学提供)后，在冰水冷却条件下，使用Q1375(Qsonica)超声破碎仪超声至均一。上述涂料固含量与上述实施例一中涂料的相同。1. Preparation of oil-repellent coating: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nano cellulose in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nano cellulose (Cellulose nanofibrils oxidized by TEMPO method, TEMPO～CNF, provided by the University of Maine, USA) After cooling with ice water, use Q1375 (Qsonica) ultrasonic disintegrator to sonicate to uniformity. The solid content of the coating is the same as that of the coating in the first embodiment.
2、基纸备用：克重为50g/m2，密度为0.722g/cm3，Gurley透气度为36.5s/100ml的未漂包装牛皮纸。2. Spare base paper: unbleached packaging kraft paper with a grammage of 50g/m2, a density of 0.722g/cm3, and a Gurley air permeability of 36.5s/100ml.
3、涂布工艺：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的纳米纤维素/聚乙烯醇防油涂料，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张。上述涂布量为2g/m 2。 3. Coating process: Use K303 multi-function coating machine to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent coating with JS10 at a speed of 3m/min, air dry, and then place it on a 105 degree heating plate Carry out heat treatment for 5 minutes, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The above-mentioned coating amount is 2 g/m 2 .
4、测试：本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为8，略高于实施例二，但大幅度低于实施例五。4. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559. The highest grade is 8, which is slightly higher than the second embodiment, but significantly lower than the fifth embodiment.
(三)实施例十二。(3) The twelfth embodiment.
1、防油涂料的制备：(1)取87％～89％水解度、分子量在8万5到12万4的聚乙烯醇按质量比19:81加入去离子水，在95摄氏度搅拌，直至得到均一的19％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温；(3)冷却后，按照聚乙烯醇与纳米纤维素固含量比为19～1的比例加入纳米纤维素(TEMPO法氧化的纤维素纳米纤丝，TEMPO～CNF，美国缅因大学提供)后，在冰水冷却条件下，使用Q1375(Qsonica)超声破碎仪超声至均一。上述 涂料固含量与实施例一中涂料的相同。1. Preparation of oil-repellent coating: (1) Take polyvinyl alcohol with a degree of hydrolysis of 87% to 89% and a molecular weight of 80,000 to 120,400, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nano cellulose in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nano cellulose (Cellulose nanofibrils oxidized by TEMPO method, TEMPO～CNF, provided by the University of Maine, USA) After cooling with ice water, use Q1375 (Qsonica) ultrasonic disintegrator to sonicate to uniformity. The solid content of the above coating is the same as that of the coating in Example 1.
2、基纸备用：克重为170g/m2，密度为0.656g/cm3，Gurley透气度为20.5s/100ml的废纸浆纸板。2. Spare base paper: waste paper pulp cardboard with a grammage of 170g/m2, a density of 0.656g/cm3, and a Gurley air permeability of 20.5s/100ml.
3、涂布工艺：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的纳米纤维素/聚乙烯醇防油涂料，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张。上述涂布量为2g/m 2。 3. Coating process: Use K303 multi-function coating machine to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent coating with JS10 at a speed of 3m/min, air dry, and then place it on a 105 degree heating plate Carry out heat treatment for 5 minutes, and finally transfer to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The above-mentioned coating amount is 2 g/m 2 .
4、测试：本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为8，高于实施例三，但大幅度低于实施例六。4. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559. The highest grade is 8, which is higher than Example 3, but significantly lower than Example 6.
六、结论四。Sixth, conclusion four.
通过实施例十至十二说明不进行预涂处理的情况下，在相似的总涂布量的情况下，在相同的抗油层涂布量的情况下，基于TAPPI T559标准的抗油脂等级有了明显下降，说明了抗油脂能力提升主要来源于电荷相互作用，说明阳离子淀粉在本发明的涂布工艺体系中的重要性。Examples 10 to 12 illustrate that without pre-coating treatment, in the case of a similar total coating amount, in the case of the same coating amount of the oil-resistant layer, the anti-grease grade based on the TAPPI T559 standard has The obvious decrease indicates that the increase in anti-grease ability is mainly due to the interaction of charges, and indicates the importance of cationic starch in the coating process system of the present invention.
下述实例13使用了不同种类的聚乙烯醇进行涂布，以证明聚乙烯醇的种类对抗油脂性能无影响。The following example 13 used different types of polyvinyl alcohol for coating to prove that the type of polyvinyl alcohol has no effect on the anti-grease performance.
七、以下实施例十三是说明在本发明的纳米纤维素/聚乙烯醇涂料与工艺下，基纸为复印纸的防油纸抗油脂等级不受改变聚乙烯醇种类的影响。7. The following example 13 illustrates that under the nanocellulose/polyvinyl alcohol coating and process of the present invention, the grease resistance grade of the base paper of copy paper is not affected by changing the type of polyvinyl alcohol.
(一)实施例十三。(1) Embodiment thirteen.
1、防油涂料的制备：(1)取98％～99％水解度、分子量在8万5到12万4的聚乙烯醇按质量比19:81加入去离子水，在95摄氏度搅拌，直至得到均一的19％的聚乙烯醇溶液；(2)等待聚乙烯醇溶液冷却至室温；(3)冷却后，按照聚乙烯醇与纳米纤维素固含量比为19～1的比例加入纳米纤维素(TEMPO法氧化的纤维素纳米纤丝，TEMPO～CNF，美国缅因大学提供)后，在冰水冷却条件下，使用Q1375(Qsonica)超声破碎仪超声至均一。上述涂料固含量与实施例一中涂料的相同。1. Preparation of oil-repellent paint: (1) Take polyvinyl alcohol with a degree of hydrolysis of 98% to 99% and a molecular weight of 80,000 to 124,000, add deionized water at a mass ratio of 19:81, and stir at 95 degrees Celsius until Obtain a uniform 19% polyvinyl alcohol solution; (2) wait for the polyvinyl alcohol solution to cool to room temperature; (3) after cooling, add nanocellulose in a ratio of 19 to 1 in the solid content ratio of polyvinyl alcohol to nanocellulose (Cellulose nanofibrils oxidized by TEMPO method, TEMPO～CNF, provided by the University of Maine, USA) After cooling with ice water, use Q1375 (Qsonica) ultrasonic disintegrator to sonicate to uniformity. The solid content of the above coating is the same as that of the coating in Example 1.
2、增强预涂涂料的制备：(1)取阳离子淀粉(HI CAT 5283A)按质量比2:98加入去离子水，放入磁子，放置于80摄氏度磁力加热搅拌器上溶解30分钟，直至均一；(2)等待阳离子淀粉溶液冷却至室温。2. Preparation of enhanced pre-coating paint: (1) Take cationic starch (HI CAT 5283A) and add deionized water at a mass ratio of 2:98, put in a magnet, and place it on a magnetic heating stirrer at 80 degrees Celsius to dissolve for 30 minutes until Uniformity; (2) Wait for the cationic starch solution to cool to room temperature.
3、基纸备用：克重为90g/m 2，密度为0.763g/cm 3，Gurley透气度为18.6s/100ml的复印纸。 3. Spare base paper: copy paper with a grammage of 90g/m 2 , a density of 0.763g/cm 3 , and a Gurley air permeability of 18.6s/100ml.
4、涂布工艺：(1)增强预涂层的涂布：用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的阳离子淀粉增强预涂涂料，自然风干；(2)防油层的涂布：使用K303多功能涂布机，以3m/min的速度用JS10刮棒涂配置好的纳米纤维素/聚乙烯醇防油涂料，自然风干，然后在105度的加热板上进行热处理5分钟，最后转移至标准测试环境中静置12～24小时，使涂布纸各组分间氢键重建并平整纸张。上述总涂布量为2.4g/m 2，其中增强预涂层0.4g/m 2，防油层2g/m 2。 4. Coating process: (1) Coating of reinforced pre-coating: Use K303 multi-function coating machine to coat the configured cationic starch reinforced pre-coating with JS10 bar at a speed of 3m/min, and then air dry; 2) Coating of oil-repellent layer: Use K303 multifunctional coater to coat the configured nano-cellulose/polyvinyl alcohol oil-repellent paint with a JS10 bar at a speed of 3m/min, air dry, and then heat at 105 degrees The board is heat-treated for 5 minutes, and finally transferred to a standard test environment to stand for 12-24 hours to rebuild the hydrogen bonds between the components of the coated paper and level the paper. The above-mentioned total coating amount is 2.4 g/m 2 , of which the reinforced pre-coating layer is 0.4 g/m 2 and the oil-repellent layer is 2 g/m 2 .
5、测试:本例所得防油纸能通过抗油脂测试TAPPI T559的最高等级为12，5. Test: The greaseproof paper obtained in this example can pass the grease resistance test TAPPI T559, the highest grade is 12.
为该测试标准最高的抗油脂等级,而仅经预涂处理的基纸的抗油脂等级为0。It is the highest anti-grease grade of the test standard, and the anti-grease grade of only the pre-coated base paper is 0.
八、结论五。Eight, conclusion five.
通过对比实施例四至六与实施例七至十二，证明了带负电的纳米纤维素与带正电的阳离子淀粉的电荷作用在本发明涂布工艺体系中的重要性。纳米纤维素/聚乙烯醇涂料在阳离子淀粉增强层上方因为纳米纤维素和阳离子淀粉的电荷作用，其渗透性大幅度减小，随之干燥后的防油层相较传统聚乙烯醇涂布工艺，在相同的涂布量下，形成的聚乙烯醇防油层更厚，以达到更高抗油脂等级，也充分说明了本发明的超级防油纸性能的优越性及其工艺的先进性。By comparing Examples 4 to 6 with Examples 7 to 12, it is proved that the charge effect of the negatively charged nanocellulose and the positively charged cationic starch is important in the coating process system of the present invention. The permeability of nano cellulose/polyvinyl alcohol coating on the top of the cationic starch reinforcement layer is greatly reduced due to the charge effect of nano cellulose and cationic starch, and the oil-repellent layer after drying is compared with the traditional polyvinyl alcohol coating process. Under the same coating amount, the formed polyvinyl alcohol oil-repellent layer is thicker to achieve a higher anti-grease grade, which also fully demonstrates the superiority of the super oil-repellent paper of the present invention and its technological advancement.
与此同时，通过实施例十三，使用不同分子量和不同水解度的聚乙烯醇进行涂布实验，本发明的理论、效果、所得纸的抗油脂性能不受影响，因此在实际生产中，可以根据产品的实际需求，改变聚乙烯醇的种类。如果产品需要更好的防水性能，可以使用更高水解度的聚乙烯醇；如果生产中需要更低的粘度满足设备需要，可以使用分子量更低的聚乙烯醇。At the same time, through Example 13, using polyvinyl alcohols with different molecular weights and different degrees of hydrolysis for coating experiments, the theory, effect, and grease resistance of the obtained paper of the present invention are not affected. Therefore, in actual production, it can be According to the actual demand of the product, change the type of polyvinyl alcohol. If the product needs better water resistance, you can use polyvinyl alcohol with a higher degree of hydrolysis; if you need a lower viscosity to meet the needs of the equipment in production, you can use polyvinyl alcohol with a lower molecular weight.

Claims (11)

  1. 一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于:在纤维素基纸上先预涂布一层变性淀粉类的增强预涂涂料得到增强预涂层，再进行纳米纤维素/聚乙烯醇配合的防油涂料涂布得到防油层。A fluorocarbon-free and biodegradable greaseproof paper and a preparation method thereof are characterized in that: a layer of modified starch-based reinforced pre-coating paint is pre-coated on the cellulose-based paper to obtain a reinforced pre-coating, and then An oil-repellent coating of nano cellulose/polyvinyl alcohol is coated to obtain an oil-repellent layer.
  2. 根据权利要求1所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于：增强预涂涂料的制备方法是：将阳离子淀粉或其它阳离子高分子聚合物按质量比1～10:90～99加入去离子水，在70～100摄氏度下搅拌，直至得到均一溶液、胶液或分散液。The biodegradable greaseproof paper containing no fluorocarbon and its preparation method according to claim 1, characterized in that: the preparation method of the reinforced pre-coating coating is: press cationic starch or other cationic polymer Add deionized water with a mass ratio of 1-10:90-99, and stir at 70-100 degrees Celsius until a uniform solution, glue or dispersion is obtained.
  3. 根据权利要求2所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于在加入去离子水后，混合的方法包括但不限于机械混合、超声混合和高压均质机混合。The biodegradable greaseproof paper containing no fluorocarbon and its preparation method according to claim 2, characterized in that after adding deionized water, the mixing method includes but not limited to mechanical mixing, ultrasonic mixing and high pressure The homogenizer mixes.
  4. 根据权利要求1所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于所述的防油涂料的制备具体步骤如下：(1)取聚乙烯醇按质量比5～20:80～95加入水，在80～100摄氏度下搅拌，直至得到均一的溶液；(2)等待聚乙烯醇溶液冷却至室温；(3)冷却后，按照聚乙烯醇与纳米纤维素固含量比为20～100:1的比例加入纳米纤维素后，在冰水冷却条件下，混合至均一。The biodegradable greaseproof paper containing no fluorocarbon and its preparation method according to claim 1, characterized in that the specific steps of preparing said greaseproof coating are as follows: (1) Take polyvinyl alcohol according to the quality Add water at a ratio of 5-20:80-95 and stir at 80-100 degrees Celsius until a homogeneous solution is obtained; (2) Wait for the polyvinyl alcohol solution to cool to room temperature; (3) After cooling, follow the steps of polyvinyl alcohol and nanofiber After adding nano cellulose with a ratio of element to solid content of 20-100:1, mix until uniform under ice-water cooling.
  5. 根据权利要求4所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于在步骤(3)中，混合的方法包括但不限于机械混合、超声混合和高压均质机混合。A biodegradable greaseproof paper containing no fluorocarbon and its preparation method according to claim 4, characterized in that in step (3), the mixing method includes but not limited to mechanical mixing, ultrasonic mixing and high pressure The homogenizer mixes.
  6. 根据权利要求1所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于所述的聚乙烯醇可以是任何一种聚乙烯醇或者两种、多种聚乙烯醇的混合物，聚乙烯醇的水解度和分子量可以根据产品生产的要求进行变更。The biodegradable greaseproof paper containing no fluorocarbon and its preparation method according to claim 1, characterized in that the polyvinyl alcohol can be any polyvinyl alcohol or two or more polyvinyl alcohols. The mixture of vinyl alcohol, the degree of hydrolysis and molecular weight of polyvinyl alcohol can be changed according to the requirements of product production.
  7. 根据权利要求1所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于所述的纳米纤维素可以是任何一种纳米纤维素，包括但不限于纤维素纳米晶(CNC)、纤维素纳米纤丝(CNF)和TEMPO氧化的纤维素纳米纤丝。The biodegradable greaseproof paper containing no fluorocarbon and its preparation method according to claim 1, characterized in that the nano cellulose can be any kind of nano cellulose, including but not limited to cellulose Nanocrystals (CNC), cellulose nanofibrils (CNF) and TEMPO oxidized cellulose nanofibrils.
  8. 根据权利要求1所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于所述的纤维素基纸可以是任意一种纤维素基纸材料，包括但不限于复印纸、滤纸、牛皮纸、纸板和铜版纸，纤维来源可以是原生也可以是再生。The biodegradable greaseproof paper containing no fluorocarbon and its preparation method according to claim 1, characterized in that the cellulose-based paper can be any cellulose-based paper material, including but not Limited to copy paper, filter paper, kraft paper, cardboard and coated paper, the fiber source can be virgin or recycled.
  9. 根据权利要求1所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于其具体步骤如下：(1)增强预涂层的涂布：使用多功能涂布机，涂配置好的增强预涂涂料于纤维素基纸上后干燥；(2)防油层的涂布：使用多功能涂布机，涂配置好的纳米纤维素/聚乙烯醇配合的防油涂料后干燥。The biodegradable greaseproof paper containing no fluorocarbon and its preparation method according to claim 1, characterized in that the specific steps are as follows: (1) Coating of enhanced pre-coating: using multifunctional coating Coat the prepared reinforced pre-coating paint on the cellulose-based paper and then dry; (2) Coating of the oil-repellent layer: Use a multi-functional coating machine to coat the well-configured nano-cellulose/polyvinyl alcohol-coated oil-repellent Dry after coating.
  10. 根据权利要求9所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于其所述的干燥方法可以是任意一种干燥方法，包括并不限于加热板干燥，烘缸干燥， 热风干燥和自然干燥。The biodegradable greaseproof paper containing no fluorocarbon and its preparation method according to claim 9, characterized in that the drying method can be any drying method, including but not limited to heating plate drying , Dryer drying, hot air drying and natural drying.
  11. 根据权利要求9所述的一种不含氟碳化合物且可生物降解的防油纸及其制备方法，其特征在于所述的增强预涂层的涂布的定量为0.1g/m 2到10g/m 2；所述的防油层的涂布的定量为0.2g/m 2到20g/m 2。 The biodegradable greaseproof paper containing no fluorocarbon and its preparation method according to claim 9, characterized in that the coating weight of the reinforced pre-coating layer is 0.1g/m 2 to 10g/m2. m 2 ; The coating weight of the oil-repellent layer is 0.2 g/m 2 to 20 g/m 2 .
PCT/CN2020/079304 2020-03-13 2020-03-13 Biodegradable oil-proof paper without fluorocarbon compound, and preparation method therefor WO2021179306A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2020/079304 WO2021179306A1 (en) 2020-03-13 2020-03-13 Biodegradable oil-proof paper without fluorocarbon compound, and preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2020/079304 WO2021179306A1 (en) 2020-03-13 2020-03-13 Biodegradable oil-proof paper without fluorocarbon compound, and preparation method therefor

Publications (1)

Publication Number Publication Date
WO2021179306A1 true WO2021179306A1 (en) 2021-09-16

Family

ID=77671108

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/079304 WO2021179306A1 (en) 2020-03-13 2020-03-13 Biodegradable oil-proof paper without fluorocarbon compound, and preparation method therefor

Country Status (1)

Country Link
WO (1) WO2021179306A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116876261A (en) * 2023-08-04 2023-10-13 湖南妙工环保科技有限公司 Pure plant fiber coating for preparing plastic-free oil-proof paper and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006085572A1 (en) * 2005-02-10 2006-08-17 Tokushu Paper Mfg. Co., Ltd. Oil-resistant sheet material
WO2011114311A1 (en) * 2010-03-18 2011-09-22 Stora Enso Oyj Method for providing a substrate with a barrier and a substrate comprising a barrier
US9034146B2 (en) * 2008-09-22 2015-05-19 Solenis Technologies, L.P. Copolymer blend compositions for use to increase paper filler content
CN106833139A (en) * 2016-12-24 2017-06-13 胡云 A kind of preparation of cellulose nano-fibrous base oil fat barrier coat and its application process
CN108625219A (en) * 2018-05-21 2018-10-09 浙江杭化新材料科技有限公司 A kind of preparation method of hydrophobic greaseproof
CN108688285A (en) * 2017-04-06 2018-10-23 郄冰玉 A kind of the biomass overlay film greaseproof and preparation process of nano-cellulose enhancing
CN110593011A (en) * 2019-10-16 2019-12-20 深圳市裕同包装科技股份有限公司 Cellulose-based fluorine-free heat-proof oil packaging paper and preparation method thereof
CN111519466A (en) * 2020-03-13 2020-08-11 浙江金加浩绿色纳米材料股份有限公司 Fluorocarbon-free biodegradable oil-proof paper and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006085572A1 (en) * 2005-02-10 2006-08-17 Tokushu Paper Mfg. Co., Ltd. Oil-resistant sheet material
US9034146B2 (en) * 2008-09-22 2015-05-19 Solenis Technologies, L.P. Copolymer blend compositions for use to increase paper filler content
WO2011114311A1 (en) * 2010-03-18 2011-09-22 Stora Enso Oyj Method for providing a substrate with a barrier and a substrate comprising a barrier
CN106833139A (en) * 2016-12-24 2017-06-13 胡云 A kind of preparation of cellulose nano-fibrous base oil fat barrier coat and its application process
CN108688285A (en) * 2017-04-06 2018-10-23 郄冰玉 A kind of the biomass overlay film greaseproof and preparation process of nano-cellulose enhancing
CN108625219A (en) * 2018-05-21 2018-10-09 浙江杭化新材料科技有限公司 A kind of preparation method of hydrophobic greaseproof
CN110593011A (en) * 2019-10-16 2019-12-20 深圳市裕同包装科技股份有限公司 Cellulose-based fluorine-free heat-proof oil packaging paper and preparation method thereof
CN111519466A (en) * 2020-03-13 2020-08-11 浙江金加浩绿色纳米材料股份有限公司 Fluorocarbon-free biodegradable oil-proof paper and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WU WEI ; LIU ZEHUA: "The effect of starch on the water and oil resistance of greaseproof paper", TIANJIN PAPER MAKING, 15 March 2017 (2017-03-15), pages 17 - 30, XP055846594 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116876261A (en) * 2023-08-04 2023-10-13 湖南妙工环保科技有限公司 Pure plant fiber coating for preparing plastic-free oil-proof paper and preparation method thereof

Similar Documents

Publication Publication Date Title
JP7097356B2 (en) How to Form a Coating Layer Containing Microfibrillated Cellulose
CN111519466A (en) Fluorocarbon-free biodegradable oil-proof paper and preparation method thereof
JP6849669B2 (en) Dense film surface sizing
RU2365696C2 (en) Production of paper using latex with agglomerated hollow particles
JP2020537060A (en) Oxygen barrier film
SE539786C2 (en) Microfibrillated cellulose film
EA028696B1 (en) Process for producing a coated packaging material and packaging material having at least one barrier layer for hydrophobic compounds
JP4846733B2 (en) Chemical compositions and methods
JP2008525570A (en) Chemical compositions and methods
CN115516168B (en) Coated paper substrate suitable for metallization
KR20140143292A (en) Water-dispersed composition of hydrophobic powder and method for preparing pulp paper and glass fiber using the same
WO2021179306A1 (en) Biodegradable oil-proof paper without fluorocarbon compound, and preparation method therefor
JP2023500241A (en) MFC substrate with increased water vapor barrier properties
CA3179407A1 (en) Process for production of nano-coated substrate
EP3423629B1 (en) Method of manufacturing 3d shaped articles
WO2021074879A1 (en) Mfc composition with phosphorylated cellulose fibers
RU2665514C2 (en) Paper with increased strength and improved fat resistance
EP4146864A1 (en) Process for production of nano-coated substrate
CN113563762A (en) Water-based hydrophobic slurry and preparation method and application thereof
CA3142586A1 (en) A method to produce a fibrous product comprising microfibrillated cellulose
KR20220022812A (en) Eco-friendly Composition for paper coating comprising CNF
CZ27280U1 (en) Paper of enhanced strength and increased resistance to fats

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20924087

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20924087

Country of ref document: EP

Kind code of ref document: A1