CN113914140A - Biodegradable high-barrier coated paper and preparation method and application thereof - Google Patents
Biodegradable high-barrier coated paper and preparation method and application thereof Download PDFInfo
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- CN113914140A CN113914140A CN202111269535.5A CN202111269535A CN113914140A CN 113914140 A CN113914140 A CN 113914140A CN 202111269535 A CN202111269535 A CN 202111269535A CN 113914140 A CN113914140 A CN 113914140A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/82—Paper comprising more than one coating superposed
- D21H19/824—Paper comprising more than one coating superposed two superposed coatings, both being non-pigmented
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- 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
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Abstract
The invention relates to biodegradable high-barrier coated paper and a preparation method and application thereof, wherein the method comprises the following steps: preparation of S1 Barrier layer: coating the polyvinyl alcohol/nano-cellulose composite coating on the surface of base paper, and drying the coated paper at 40-70 ℃ for 30-120min after the coating is finished to obtain the coated paper with the barrier layer; preparation of S2 Heat-seal layer: and (4) coating the cellulose acetate solution on the barrier layer obtained in the step (S1), and after the coating is finished, placing the coated paper indoors for natural air drying for 30-120min to obtain the high-barrier coated paper. The coated paper prepared by the invention has good oxygen barrier and water vapor barrier properties, and can realize heat sealing, so that the requirements of simultaneously finishing feeding and packaging on an automatic packaging machine can be well met, and the coated paper is an environment-friendly packaging material with excellent performance and can be used for packaging food such as fruits and vegetables, biscuits and the like and products such as medicines, electronic devices and the like.
Description
Technical Field
The invention relates to the field of coated paper, in particular to biodegradable high-barrier coated paper and a preparation method and application thereof.
Background
Packaging materials with high barrier properties are indispensable to industries such as food, medicine, electronics and the like, and most of the traditional barrier packaging materials are based on non-degradable petroleum-based plastic materials. In recent years, the problem of serious environmental pollution is brought about by the mass use of disposable plastic products, and with the improvement of environmental awareness and the strictness of the policy of 'plastic forbidding', the urgent need of the current society is to find an environment-friendly and economic biodegradable high-barrier material.
The paper is used as a renewable, sustainable and biodegradable green material and is widely applied to the field of packaging. However, most of the existing high-barrier paper-based packaging materials are formed by compounding paper with non-degradable plastics such as Polyethylene (PE), polypropylene (PP), ethylene-vinyl alcohol copolymer (EVOH) and the like, cannot meet the requirement of biodegradability, and still have the problem of environmental pollution. Therefore, the development of the biodegradable high-barrier paper-based packaging material has important practical significance for the sustainable development of society and the ecological civilization construction of China.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a biodegradable high-barrier coated paper, and a preparation method and applications thereof, and to solve the technical problem of complete biodegradation while having good processability and excellent functional properties.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The invention provides a preparation method of biodegradable high-barrier coated paper, which comprises the following steps:
preparation of S1 Barrier layer: coating the polyvinyl alcohol/nano-cellulose composite coating on the surface of base paper, and drying the coated paper at 40-70 ℃ for 30-120min after coating to obtain the coated paper with the barrier layer;
preparation of S2 Heat-seal layer: and (4) coating the cellulose acetate solution on the barrier layer obtained in the step (S1), and after the coating is finished, placing the coated paper indoors for natural air drying for 30-120min to obtain the high-barrier coated paper.
Preferably, in the preparation method of the biodegradable high-barrier coated paper, in step S1, the coating base paper is 20-50g/m2The thickness of the single-sided glossy paper is 10-80 μm.
Preferably, in the preparation method of the biodegradable high-barrier coated paper, in step S1, the coating speed is 30-150m/min, and the thickness of the coating layer is 10-30 μm.
Preferably, in the preparation method of the biodegradable high-barrier coated paper, in step S1, the polyvinyl alcohol/nanocellulose composite coating is prepared by the following steps:
s11 adding deionized water into the nano-cellulose according to the mass ratio of 1-5:900, fully stirring until no obvious agglomeration exists, and carrying out ultrasonic treatment for 0.5-1h under the conditions of 80-100Hz and 0 ℃ ice water bath to obtain a nano-cellulose solution; adding 95-99% of polyvinyl alcohol by mass into the nano-cellulose solution, heating at 80-100 ℃, and stirring at the rotating speed of 300-450r/min for 3-5h until a uniform and transparent polyvinyl alcohol/nano-cellulose mixed solution is obtained;
s12, standing and defoaming the polyvinyl alcohol/nano-cellulose mixed solution for 1-2h, and cooling the solution to room temperature to obtain the polyvinyl alcohol/nano-cellulose composite coating.
Preferably, in the preparation method of the biodegradable high-barrier coated paper, in step S11, the polymerization degree of the polyvinyl alcohol is 1700-1900, and the alcoholysis degree is 88% or more.
Preferably, in the preparation method of the biodegradable high-barrier coated paper, in step S11, the nanocellulose is 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide oxidized cellulose nanofibril, mechanical cellulose nanofibril, sulfuric acid cellulose nanocrystal or quaternary ammonium salt modified cellulose nanofibril.
Preferably, in the preparation method of the biodegradable high-barrier coated paper, in step S2, the cellulose acetate solution is prepared by the following steps:
mixing the cellulose acetate particles with a solvent according to the mass ratio of 1:5.5-10, and stirring for 5-8h at the temperature of 25-50 ℃ to obtain a cellulose acetate solution.
Preferably, the method for preparing the biodegradable high barrier coated paper is as described above, wherein the degree of substitution of the cellulose acetate is in the range of 2.2 to 2.5.
Preferably, the method for preparing the biodegradable high barrier coated paper comprises a step of dissolving the solvent in a solvent selected from at least one of N, N-dimethylacetamide, acetone, dimethylsulfoxide, N-methylmorpholine-N-oxide hydrate and methyl 3-methoxypropionate.
Preferably, the method for preparing the biodegradable high-barrier coated paper comprises the step of dissolving the solvent in N-methylmorpholine-N-oxide hydrate or methyl 3-methoxypropionate.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures. The invention provides biodegradable high-barrier coated paper which comprises a base material layer, a high-barrier layer and a heat sealing layer which are sequentially connected.
Preferably, the biodegradable high-barrier coated paper is a polyvinyl alcohol/nano-cellulose composite coating; the heat sealing layer is a cellulose acetate coating.
Preferably, the biodegradable high barrier coated paper described above, which has an oxygen transmission rate of 13-28cm3/m224 h.0.1 MPa, water vapor transmission rate of 210-g/m2Under 24h, the tensile strength is 106-.
Preferably, the biodegradable high barrier coated paper has an oxygen transmission rate of 13cm3/m224h 0.1MPa, water vapor transmission rate of 210g/m224h, the tensile strength is 130Mpa, the elongation at break is 5.3 percent, the 90-day degradation rate reaches 91.4 percent, and the oil resistance reaches the highest grade-12 grade of a grease resistance test TAPPI-T559.
Preferably, the biodegradable high barrier coated paper is prepared by the method.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures. The invention provides application of biodegradable high-barrier coated paper in food packaging materials, medicine and health, aerospace or electronic devices.
By the technical scheme, the biodegradable high-barrier coated paper and the preparation method and application thereof provided by the invention at least have the following advantages:
the coated paper prepared by the invention has good oxygen barrier and water vapor barrier properties, and can realize heat sealing, so that the requirements of simultaneously finishing feeding and packaging on an automatic packaging machine can be well met, and the coated paper is an environment-friendly packaging material with excellent performance and can be used for packaging food such as fruits and vegetables, biscuits and the like and products such as medicines, electronic devices and the like.
The coated paper prepared by the invention has biodegradability, and degradation products are carbon dioxide and water, so that plastic waste and other pollution can not be caused.
The raw materials of the coated paper prepared by the invention are green and environment-friendly, and the coated paper can be well applied to the packaging fields of food, medicine and the like, so that the coated paper can replace the traditional plastic products and effectively relieve the problem of environmental pollution.
The polyvinyl alcohol/nano cellulose composite coating of the coated paper prepared by the invention has good oxygen barrier and water vapor barrier properties; the main reason is that hydrogen bond combination exists between the polyvinyl alcohol and the nano-cellulose, and the nano-cellulose has a crystalline structure, so that the polyvinyl alcohol/nano-cellulose composite coating shows excellent barrier property, and can be further compounded with other functional coatings as a barrier coating to prepare a moisture-proof and oxidation-resistant green packaging material.
The cellulose acetate coating of the coated paper prepared by the invention has good heat sealing, water resistance and oil resistance, and high-strength heat sealing (>20N/15mm) can be realized at the temperature of 150-.
The lowest oxygen transmission rate of the coated paper prepared by the invention can reach 13cm3/m224h 0.1Mpa, the lowest water vapor transmission rate can reach 210g/m2·24h。
The oil resistance of the coated paper prepared by the invention can reach the highest grade 12 of an oil resistance test TAPPI-T559, and the coated paper can be well applied to food packaging with high oil content.
The coated paper prepared by the invention has good mechanical strength and toughness, the tensile strength and the elongation at break can respectively reach more than 106Mpa and 4.6 percent, and the coated paper is a paper-based high-barrier flexible packaging material with good processing adaptability and excellent functional characteristics.
The coated paper prepared by the invention has the degradation rate of over 86.5 percent in 90 days, and is a green paper-based functional material with development prospect.
Compared with a film coating process, the preparation method provided by the invention has the advantages that the coating process is simpler to operate and lower in cost, the original production mode is not required to be changed for a plurality of enterprises only provided with a coating assembly line, and the expenditure for replacing instruments and equipment is saved.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Drawings
FIG. 1 is a schematic structural view of a biodegradable high barrier coated paper of the present invention; a substrate layer-1, a high barrier layer-2 and a heat sealing layer-3.
FIG. 2 is a scanning electron micrograph of front (left) and back (right) sides of single-sided glossy base paper used in examples 1 to 6 and comparative examples 1 to 6 of the present invention.
FIG. 3 is a scanning electron micrograph of the plane of the coated paper prepared in example 1 of the present invention.
FIG. 4 is a scanning electron micrograph of the plane of the coated paper prepared in comparative example 1.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made on the biodegradable high barrier coated paper and the preparation method thereof and the specific implementation, structure, characteristics and effects thereof according to the present invention with reference to the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those described herein. Therefore, the invention is not limited to the specific embodiments disclosed. The following materials or reagents, unless otherwise specified, are all commercially available.
The invention provides a preparation method of biodegradable high-barrier coated paper, which comprises the following steps:
preparation of S1 Barrier layer: coating the polyvinyl alcohol/nano-cellulose composite coating on the surface of base paper, and drying the coated paper at 40-70 ℃ for 30-120min after coating, wherein the preferable drying mode and conditions are as follows: oven drying at 70 deg.C for 60min, wherein the drying mode can be selected from natural drying, hot plate drying, far infrared drying, vacuum drying, microwave drying, etc. according to requirement and condition;
preparation of S2 Heat-seal layer: and (4) coating the cellulose acetate solution on the barrier layer obtained in the step S1, and after the coating is finished, placing the coated paper indoors for natural air drying for 30-120min to obtain the biodegradable high-barrier coated paper.
In some embodiments of the invention, in step S1, the coated base paper is single-sided glossy paper (20-50 g/m)2) But in practice may be any cellulosic paper based material such as: kraft paper, glassine paper.
In some embodiments of the present invention, in step S1, the thickness of the coating base paper is 10 to 80 μm, which may be selected to prepare paper-based packaging materials with different thicknesses according to different application scenarios, for example, if the high-barrier coating paper is used for coffee and milk powder type packaging, the thickness of the coating base paper may be selected to be 10 to 15 μm; if the high-barrier coating paper is used for packaging biscuits, cakes and the like, the thickness of the coating base paper can be selected to be 20-30 mu m; if the high-barrier coating paper is used for packaging fruits and vegetables, the thickness of the coating base paper can be selected to be 20-40 μm, and if the high-barrier coating paper is used for packaging beans and coarse cereals, the thickness of the coating base paper can be selected to be 50-80 μm.
In some embodiments of the present invention, in step S1, the coating speed is 30-150m/min, and in order to enhance the adaptability of the coating material to the coating process and obtain a smoother and more uniform coating structure, the coating speed is preferably 50m/min, and the coating thickness is 10-30 μm.
In some embodiments of the present invention, in step S1, the polyvinyl alcohol/nanocellulose composite coating is prepared by:
s11 adding deionized water into the nano-cellulose according to the mass ratio of 1-5:900, fully stirring the mixture by using a glass rod until no obvious agglomeration exists, and carrying out ultrasonic treatment for 0.5-1h under the conditions of 80-100Hz and 0 ℃ ice-water bath to obtain a nano-cellulose solution; adding 95-99% of polyvinyl alcohol by mass into the nano-cellulose solution, heating at 80-100 ℃, and stirring at the rotating speed of 300-450r/min for 3-5h until a uniform and transparent polyvinyl alcohol/nano-cellulose mixed solution is obtained;
s12, standing and defoaming the polyvinyl alcohol/nano-cellulose mixed solution for 1-2h, and cooling the solution to room temperature to obtain the polyvinyl alcohol/nano-cellulose composite coating.
In some preferred embodiments of the present invention, in step S1, the polyvinyl alcohol/nanocellulose composite coating is prepared by:
s11, adding deionized water into the nano-cellulose according to the mass ratio of 5:900, fully stirring the mixture by using a glass rod until no obvious agglomeration exists, and carrying out ultrasonic treatment for 0.5h under the conditions of 100Hz and 0 ℃ ice-water bath to obtain a nano-cellulose solution; adding 99% of polyvinyl alcohol by mass into the nano-cellulose solution, heating at 90 ℃, and stirring at the rotating speed of 350r/min for 4 hours until a uniform and transparent polyvinyl alcohol/nano-cellulose mixed solution is obtained;
s12, standing and defoaming the polyvinyl alcohol/nano-cellulose mixed solution for 2 hours, and cooling the solution to room temperature to obtain the polyvinyl alcohol/nano-cellulose composite coating.
In some embodiments of the present invention, in step S11, the polymerization degree of the polyvinyl alcohol is 1700-1900, the alcoholysis degree is 88% or more, the polymerization degree and the alcoholysis degree can also be changed according to the product requirements, and the higher the polymerization degree, the higher the viscosity of the prepared coating, and the higher the alcoholysis degree, the better the hydrophobicity of the prepared coating.
In some embodiments of the present invention, in step S11, the nanocellulose may be wood pulp-derived 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO) oxidized cellulose nanofibrils (length 5-10 μm, diameter 10-20nm), and in practical applications, other sources and types of nanocellulose may be purchased, such as mechanical cellulose nanofibrils (length 5-20 μm, diameter 10-20nm), sulfuric acid cellulose nanocrystals (length 100-.
In some embodiments of the invention, in step S2, the cellulose acetate solution is prepared by:
adding the cellulose acetate particles and a solvent into a reaction vessel according to the mass ratio of 1:5.5-10, mixing, and stirring at 25-50 ℃ for 5-8h to obtain a cellulose acetate solution so as to ensure that the cellulose acetate can be fully dissolved by the solvent.
In some embodiments of the invention, the degree of substitution of the cellulose acetate ranges from 2.2 to 2.5.
In some embodiments of the invention, the solvent includes, but is not limited to, N-dimethylacetamide (DMAc), acetone, dimethyl sulfoxide (DMSO), N-methylmorpholine-N-oxide hydrate (NMMO · H)2At least one of O) and methyl 3-methoxypropionate; in order to improve the environmental friendliness of the product, N-methylmorpholine-N-oxide hydrate or methyl 3-methoxypropionate is further preferable.
As shown in fig. 1, the invention also provides biodegradable high-barrier coated paper prepared by the method, which comprises a substrate layer 1, a high-barrier layer 2 and a heat-sealing layer 3 which are connected in sequence.
In other embodiments of the present invention, the substrate layer 1 may be single-sided glossy paper, and the thickness of the substrate paper is 10 to 80 μm; the high barrier layer 2 is a polyvinyl alcohol/nano-cellulose composite coating and can provide excellent barrier property and mechanical property at the same time; the heat sealing layer 3 is a cellulose acetate coating and can provide good water resistance, oil resistance and heat sealing performance.
The oxygen transmission rate of the high-barrier coated paper is 13-28cm through experimental tests3/m224 h.0.1 MPa, water vapor transmission rate of 210-2Under 24h, the tensile strength is 106-.
Further, the oxygen transmission rate of the biodegradable high-barrier coated paper can reach 13cm at the lowest3/m224h 0.1Mpa, the lowest water vapor transmission rate can reach 210g/m224h, the maximum tensile strength can reach 130Mpa, the maximum elongation at break can reach 5.3%, the maximum degradation rate in 90 days can reach 91.4%, and the oil resistance can reach the highest level-12 of the grease resistance test TAPPI-T559.
The biodegradable high-barrier coated paper can be applied to the fields of food packaging materials, medicine and health, aerospace or electronic devices.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
In the following examples of the present invention, the components referred to are all commercially available products well known to those skilled in the art unless otherwise specified. The following examples 1 to 6 are coated papers obtained by coating a polyvinyl alcohol/nanocellulose composite coating material with a cellulose acetate solution in this order.
Example 1
A preparation method of biodegradable high-barrier coated paper comprises the following steps:
(1) preparing a polyvinyl alcohol/nano cellulose composite coating: adding 8.62g of TEMPO oxidized nano-cellulose (with the length of 5-10 mu m and the diameter of 10-20nm) with the solid content of 1.16 percent into 81.48ml of deionized water, fully stirring the mixture by using a glass rod until no obvious agglomeration exists, and carrying out ultrasonic treatment for 1h under the conditions of 80Hz and 0 ℃ ice-water bath to obtain a nano-cellulose solution. Adding 9.9g of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 90 percent (mole fraction) into the nano-cellulose solution, heating at 90 ℃, and stirring at the rotating speed of 350r/min for 4 hours until a uniform and transparent solution, namely a polyvinyl alcohol/nano-cellulose mixed solution, is obtained; standing and defoaming the polyvinyl alcohol/nano-cellulose mixed solution for 2 hours, and cooling the solution to room temperature for later use to obtain the polyvinyl alcohol/nano-cellulose composite coating.
(2) Preparation of cellulose acetate solution: 10g of cellulose acetate particles (80 meshes) with the degree of substitution of 2.2 and 90g N-methylmorpholine-N-oxide aqueous solution (50 wt%) are added into a reaction vessel together, stirred at the constant temperature of 25 ℃ for 5 hours, and a cellulose acetate solution with the mass fraction of 10% is obtained after the cellulose acetate particles are completely dissolved.
(3) Coating: selecting a quantitative 28g/m2The single-sided glossy paper of (1) is used as a substrate layer 1, and the polyvinyl alcohol/nano-cellulose composite coating prepared in the step (1) is coated on the front side of the substrate layer 1 through a coating machine (the front side of the single-sided glossy paper is calendered from the front side and the back side of the single-sided glossy paper in the figure 2The fiber arrangement of the coating is more compact as seen by a scanning electron microscope on two sides, a more compact coating structure can be formed on the surface of the coating after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated, the coating speed is 70m/min, and the thickness of the coating layer is 10 microns. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min, and coating the cellulose acetate solution prepared in the step (2) on the surface of the coating layer 2 by a coating machine, wherein the coating speed and the coating thickness are the same as the above operation. And after the coating is finished, the coated paper is placed indoors for natural air drying for 60min, and the high-barrier coated paper can be obtained.
And (3) testing: and performing functional detection on the obtained high-barrier coated paper, wherein the functional detection comprises physical property detection, oil resistance detection, barrier property detection and biodegradable property detection.
And (3) detecting the tensile property: according to the test of GB/T1040.3-2006, the test sample is in a long strip shape, the length is 150mm, the width is 15mm, the gauge length is (100 +/-1) mm, and the stretching speed of the test sample is (250 +/-25) mm/min.
And (3) detecting the oil resistance: the relevant tests were performed according to TAPPI-T559.
And (3) detection of barrier property: the oxygen transmission capacity is tested according to GB/T1038-; the water vapor transmission capacity is tested according to GB/T16928-1997, and the tester is a blue-light electromechanical PERME W3/031 water vapor transmission rate tester.
And (3) detecting the biodegradable performance: the biodegradability test adopts a soil landfill method, a square sample with the size of 4 multiplied by 4mm is taken, dried to constant weight, buried in soil simulating natural conditions after being weighed, taken out every 10 days, treated and weighed, and the weight loss rate is calculated.
Example 2
A preparation method of biodegradable high-barrier coated paper comprises the following steps:
(1) preparing a polyvinyl alcohol/nano cellulose composite coating: adding 8.62g of quaternary ammonium salt modified cationic nanocellulose (with the length of 1-10 mu m and the diameter of less than 20nm) with the solid content of 1.27% into 81.48ml of deionized water, fully stirring by using a glass rod until no obvious agglomeration exists, adding 9.8g of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 97% (mole fraction) into the nanocellulose solution under the conditions of 90Hz and 0 ℃ ice-water bath by ultrasonic treatment for 1h, heating at 90 ℃, and stirring at the rotating speed of 400r/min for 4h until a uniform transparent solution, namely a polyvinyl alcohol/nanocellulose mixed solution, is obtained; standing and defoaming the polyvinyl alcohol/nano-cellulose mixed solution for 2 hours, and cooling the solution to room temperature for later use.
(2) Preparation of cellulose acetate solution: 10g of cellulose acetate particles (80 meshes) with the degree of substitution of 2.2 and 90g N-methylmorpholine-N-oxide aqueous solution (50 wt%) are added into a reaction vessel together, stirred at the constant temperature of 25 ℃ for 5 hours, and a cellulose acetate solution with the mass fraction of 10% is obtained after the cellulose acetate particles are completely dissolved.
(3) Coating: selecting a quantitative 28g/m2The single-sided glossy paper is used as a substrate layer 1, the polyvinyl alcohol/nano cellulose composite coating prepared in the step (1) is coated on the front side of the substrate layer 1 through a coating machine (the front side of the single-sided glossy paper is calendered, the fiber arrangement of the single-sided glossy paper can be seen to be more compact through a front scanning electron microscope image and a back scanning electron microscope image in the figure 2, a more compact coating structure can be formed on the surface of the single-sided glossy paper after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated), the coating speed is 60m/min, and the thickness of the coating layer is 15 microns. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min, and coating the cellulose acetate solution prepared in the step (2) on the surface of the coating layer 2 by a coating machine, wherein the coating speed and the coating thickness are the same as the above operation. And after the coating is finished, the coated paper is placed indoors for natural air drying for 60min, and the high-barrier coated paper can be obtained.
And (3) testing: the functionality tests of the high-barrier coated paper obtained in the above way are performed in the same way as in example 1, wherein the tests include physical property test, oil resistance test, barrier property test and biodegradable property test.
Example 3
A preparation method of biodegradable high-barrier coated paper comprises the following steps:
(1) preparing a polyvinyl alcohol/nano cellulose composite coating: adding 8.62g of nano crystalline cellulose (with the particle size of 200nm) with the solid content of 2.77 percent into 81.48ml of deionized water, fully stirring by using a glass rod until no obvious agglomeration exists, and carrying out ultrasonic treatment for 0.5h under the conditions of 100Hz and 0 ℃ ice-water bath; adding 9.9g of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 99 percent (mole fraction) into the nano-cellulose solution, heating at 90 ℃, and stirring at the rotating speed of 350r/min for 4 hours until a uniform and transparent solution, namely a polyvinyl alcohol/nano-cellulose mixed solution, is obtained; standing and defoaming the polyvinyl alcohol/nano-cellulose mixed solution for 2 hours, and cooling the solution to room temperature for later use.
(2) Preparation of cellulose acetate solution: 10g of cellulose acetate particles (80 meshes) with the degree of substitution of 2.2 and 90g N-methylmorpholine-N-oxide aqueous solution (50 wt%) are added into a reaction vessel together, stirred at the constant temperature of 25 ℃ for 5 hours, and a cellulose acetate solution with the mass fraction of 10% is obtained after the cellulose acetate particles are completely dissolved.
(3) Coating: selecting a quantitative 28g/m2The single-sided glossy paper is used as a substrate layer 1, the polyvinyl alcohol/nano cellulose composite coating prepared in the step (1) is coated on the front side of the substrate layer 1 through a coating machine (the front side of the single-sided glossy paper is calendered, the fiber arrangement of the single-sided glossy paper can be seen to be more compact through a front scanning electron microscope image and a back scanning electron microscope image in the figure 2, a more compact coating structure can be formed on the surface of the single-sided glossy paper after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated), the coating speed is 50m/min, and the thickness of the coating layer is 30 microns. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min, and coating the cellulose acetate solution prepared in the step (2) on the surface of the coating layer 2 by a coating machine, wherein the coating speed and the coating thickness are the same as the above operation. And after the coating is finished, the coated paper is placed indoors for natural air drying for 60min, and the high-barrier coated paper can be obtained.
And (3) testing: the functionality tests of the high-barrier coated paper obtained in the above way are performed in the same way as in example 1, wherein the tests include physical property test, oil resistance test, barrier property test and biodegradable property test.
Example 4
A preparation method of biodegradable high-barrier coated paper comprises the following steps:
(1) preparing a polyvinyl alcohol/nano cellulose composite coating: adding 8.62g of TEMPO oxidized nano-cellulose (the length is 5-10 mu m, the diameter is 10-20nm) with the solid content of 1.16% into 81.48ml of deionized water, fully stirring the mixture by using a glass rod until no obvious agglomeration exists, adding 9.9g of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 90% (mole fraction) into the nano-cellulose solution after ultrasonic treatment for 0.5h under the conditions of 100Hz and 0 ℃ ice-water bath, heating the mixture at 90 ℃, and stirring the mixture for 4h at the rotating speed of 350r/min until a uniform transparent solution, namely a polyvinyl alcohol/nano-cellulose mixed solution, is obtained; standing and defoaming the polyvinyl alcohol/nano-cellulose mixed solution for 2 hours, and cooling the solution to room temperature for later use.
(2) Preparation of cellulose acetate solution: adding 14g of cellulose acetate particles (80 meshes) with the degree of substitution of 2.5 and 86g of acetone and DMAc mixed solution into a reaction container, stirring for 5 hours at 40 ℃, and obtaining a cellulose acetate solution with the mass fraction of 14% after the cellulose acetate particles are completely dissolved.
(3) Coating: selecting a quantitative 28g/m2The single-sided glossy paper is used as a substrate layer 1, the polyvinyl alcohol/nano cellulose composite coating prepared in the step (1) is coated on the front side of the substrate layer 1 through a coating machine (the front side of the single-sided glossy paper is calendered, the fiber arrangement of the single-sided glossy paper can be seen to be more compact through a front scanning electron microscope image and a back scanning electron microscope image in the figure 2, a more compact coating structure can be formed on the surface of the single-sided glossy paper after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated), the coating speed is 70m/min, and the thickness of the coating layer is 10 microns. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min, and coating the cellulose acetate solution prepared in the step (2) on the surface of the coating layer 2 by a coating machine, wherein the coating speed and the coating thickness are the same as the above operation. And after the coating is finished, the coated paper is placed indoors for natural air drying for 60min, and the high-barrier coated paper can be obtained.
And (3) testing: the functionality tests of the high-barrier coated paper obtained in the above way are performed in the same way as in example 1, wherein the tests include physical property test, oil resistance test, barrier property test and biodegradable property test.
Example 5
A preparation method of biodegradable high-barrier coated paper comprises the following steps:
(1) preparing a polyvinyl alcohol/nano cellulose composite coating: adding 8.62g of quaternary ammonium salt modified cationic nanocellulose (with the length of 1-10 mu m and the diameter of less than 20nm) with the solid content of 1.27% into 81.48ml of deionized water, fully stirring by using a glass rod until no obvious agglomeration exists, adding 9.8g of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 97% (mole fraction) into the nanocellulose solution under the conditions of 100Hz and 0 ℃ ice-water bath by ultrasonic waves for 0.5h, heating at 90 ℃, and stirring at the rotating speed of 400r/min for 4h until a uniform transparent solution, namely a polyvinyl alcohol/nanocellulose mixed solution, is obtained; standing and defoaming the polyvinyl alcohol/nano-cellulose mixed solution for 2 hours, and cooling the solution to room temperature for later use.
(2) Preparation of cellulose acetate solution: 12g of cellulose acetate particles (80 meshes) with the degree of substitution of 2.2 and 88g of acetone aqueous solution (the volume ratio of acetone to water is 5:1) are added into a reaction vessel together, stirred for 5 hours at the temperature of 35 ℃, and a cellulose acetate solution with the mass fraction of 12 percent is obtained after the cellulose acetate particles are completely dissolved.
(3) Coating: selecting a quantitative 28g/m2The single-sided glossy paper is used as a substrate layer 1, the polyvinyl alcohol/nano cellulose composite coating prepared in the step (1) is coated on the front side of the substrate layer 1 through a coating machine (the front side of the single-sided glossy paper is calendered, the fiber arrangement of the single-sided glossy paper can be seen to be more compact through a front scanning electron microscope image and a back scanning electron microscope image in the figure 2, a more compact coating structure can be formed on the surface of the single-sided glossy paper after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated), the coating speed is 60m/min, and the thickness of the coating layer is 15 microns. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min, and coating the cellulose acetate solution prepared in the step (2) on the surface of the coating layer 2 by a coating machine, wherein the coating speed and the coating thickness are the same as the above operation. And after the coating is finished, the coated paper is placed indoors for natural air drying for 60min, and the high-barrier coated paper can be obtained.
And (3) testing: the functionality tests of the high-barrier coated paper obtained in the above way are performed in the same way as in example 1, wherein the tests include physical property test, oil resistance test, barrier property test and biodegradable property test.
Example 6
A preparation method of biodegradable high-barrier coated paper comprises the following steps:
(1) preparing a polyvinyl alcohol/nano cellulose composite coating: adding 8.62g of nano crystalline cellulose (with the particle size of 200nm) with the solid content of 2.77% into 81.48ml of deionized water, fully stirring by using a glass rod until no obvious agglomeration exists, adding 9.9g of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 99% (mole fraction) into the nano cellulose solution under the conditions of 100Hz and 0 ℃ ice-water bath by ultrasonic treatment for 0.5h, heating at 90 ℃, and stirring at the rotating speed of 350r/min for 4h until a uniform transparent solution, namely a polyvinyl alcohol/nano cellulose mixed solution is obtained; standing and defoaming the polyvinyl alcohol/nano-cellulose mixed solution for 2 hours, and cooling the solution to room temperature for later use.
(2) Preparation of cellulose acetate solution: adding 14g of cellulose acetate particles (80 meshes) with the degree of substitution of 2.2 and 86g N, N-dimethylformamide into a reaction vessel, stirring for 5 hours at 40 ℃, and obtaining a cellulose acetate solution with the mass fraction of 14% after the cellulose acetate particles are completely dissolved.
(3) Coating: selecting a quantitative 28g/m2The single-sided glossy paper is used as a substrate layer 1, the polyvinyl alcohol/nano cellulose composite coating prepared in the step (1) is coated on the front side of the substrate layer 1 through a coating machine (the front side of the single-sided glossy paper is calendered, the fiber arrangement of the single-sided glossy paper can be seen to be more compact through a front scanning electron microscope image and a back scanning electron microscope image in the figure 2, a more compact coating structure can be formed on the surface of the single-sided glossy paper after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated), the coating speed is 50m/min, and the thickness of the coating layer is 30 microns. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min, and coating the cellulose acetate solution prepared in the step (2) on the surface of the coating layer 2 by a coating machine, wherein the coating speed and the coating thickness are the same as the above operation. After coating, the coated paper is placed indoors for natural air drying for 60min, and the coating paper can be obtainedAnd obtaining the high-barrier coated paper.
And (3) testing: the functionality tests of the high-barrier coated paper obtained in the above way are performed in the same way as in example 1, wherein the tests include physical property test, oil resistance test, barrier property test and biodegradable property test.
Application examples
The following coated paper was a biodegradable high barrier coated paper obtained in example 6, applied to a biscuit package, comprising the following steps:
(1) after the coated paper is dried, folding a 40 cm-by-20 cm coated paper pattern along the long edge, and then carrying out heat sealing treatment on two side edges of the coated paper pattern at 150 ℃ by using a heat sealing machine;
(2) putting 8 biscuit samples of which the sizes are 5cm multiplied by 3cm into the semi-sealed paper bag prepared in the step (1), and sealing the semi-sealed paper bag at the same temperature (150 ℃) by using a heat sealing machine to obtain a fully-sealed paper-based biscuit packaging bag filled with the biscuit samples;
(3) taking 8 biscuit samples with the size of 5cm multiplied by 3cm, placing the biscuit samples in a naked room temperature environment (25 ℃) to be compared with the samples in the step (2);
and (3) testing: and (3) carrying out compression test on the biscuit samples in the steps (2) and (3) every 24h by using a universal testing machine.
The test data show that the compression strength of the biscuit sample in the step (3) after 24h is 2/3 in the step (2), the compression strength reduction range is further increased after 48h, and the compression strength of the biscuit sample packaged by the coated paper is relatively stable from the early stage of the test to slowly reduced, which shows that the coated paper prepared by the invention can play a good role in protecting hygroscopic foods such as biscuits and the like, and can be used for short-term packaging of products with certain requirements on oxygen resistance and water vapor resistance.
The following comparative examples 1 to 6 are coated papers obtained by coating a polyvinyl alcohol solution and a cellulose acetate solution in this order or single-layer coated papers containing only a barrier layer/heat-seal layer.
Comparative example 1
A method of making coated paper comprising the steps of:
(1) preparing a polyvinyl alcohol solution: adding 5g of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 90 percent (mole fraction) into 95ml of deionized water, heating at 90 ℃, and stirring for 2 hours at the rotating speed of 300r/min until a uniform and transparent solution, namely a polyvinyl alcohol solution, is obtained; standing the polyvinyl alcohol solution for defoaming for 2 hours, and cooling the solution to room temperature for later use.
(2) Preparation of cellulose acetate solution: 10g of cellulose acetate particles (80 meshes) with the degree of substitution of 2.2 and 90g N-methylmorpholine-N-oxide aqueous solution (50 wt%) are added into a reaction vessel together, stirred at the constant temperature of 25 ℃ for 5 hours, and a cellulose acetate solution with the mass fraction of 10% is obtained after the cellulose acetate particles are completely dissolved.
(3) Coating: selecting a quantitative 28g/m2The single-sided glossy paper is used as a substrate layer 1, the polyvinyl alcohol/nano cellulose composite coating prepared in the step (1) is coated on the front side of the substrate layer 1 through a coating machine (the front side of the single-sided glossy paper is calendered, the fiber arrangement of the single-sided glossy paper can be seen to be more compact through a front scanning electron microscope image and a back scanning electron microscope image in the figure 2, a more compact coating structure can be formed on the surface of the single-sided glossy paper after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated), the coating speed is 70m/min, and the thickness of the coating layer is 10 microns. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min, and coating the cellulose acetate solution prepared in the step (2) on the surface of the coating layer 2 by a coating machine, wherein the coating speed and the coating thickness are the same as the above operation. And after the coating is finished, the coated paper is placed indoors for natural air drying for 60min, and the barrier coated paper can be obtained.
And (3) testing: the functional tests of the coated paper obtained in the above were carried out in the same manner as in example 1, including physical property test, oil resistance test, barrier property test, and biodegradability test.
Comparative example 2
A method of making coated paper comprising the steps of:
(1) preparing a polyvinyl alcohol solution: adding 10g of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 97 percent (mole fraction) into 90ml of deionized water, heating at 90 ℃, and stirring for 3 hours at the rotating speed of 350r/min until a uniform and transparent solution, namely a polyvinyl alcohol solution, is obtained; standing the polyvinyl alcohol solution for defoaming for 2 hours, and cooling the solution to room temperature for later use.
(2) Preparation of cellulose acetate solution: 12g of cellulose acetate particles (80 meshes) with the degree of substitution of 2.2 and 88g of acetone aqueous solution (the volume ratio of acetone to water is 5:1) are added into a reaction vessel together, stirred for 5 hours at the temperature of 35 ℃, and a cellulose acetate solution with the mass fraction of 12 percent is obtained after the cellulose acetate particles are completely dissolved.
(3) Coating: selecting a quantitative 28g/m2The single-sided glossy paper is used as a substrate layer 1, the polyvinyl alcohol/nano cellulose composite coating prepared in the step (1) is coated on the front side of the substrate layer 1 through a coating machine (the front side of the single-sided glossy paper is calendered, the fiber arrangement of the single-sided glossy paper can be seen to be more compact through a front scanning electron microscope image and a back scanning electron microscope image in the figure 2, a more compact coating structure can be formed on the surface of the single-sided glossy paper after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated), the coating speed is 60m/min, and the thickness of the coating layer is 15 microns. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min, and coating the cellulose acetate solution prepared in the step (2) on the surface of the coating layer 2 by a coating machine, wherein the coating speed and the coating thickness are the same as the above operation. And after the coating is finished, the coated paper is placed indoors for natural air drying for 60min, and the barrier coated paper can be obtained.
And (3) testing: the functional tests of the coated paper obtained in the above were carried out in the same manner as in example 1, including physical property test, oil resistance test, barrier property test, and biodegradability test.
Comparative example 3
A method of making coated paper comprising the steps of:
(1) preparing a polyvinyl alcohol solution: adding 12g of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 99% (mole fraction) into 88ml of deionized water, heating at 90 ℃, and stirring for 3 hours at the rotating speed of 350r/min until a uniform and transparent solution, namely a polyvinyl alcohol solution, is obtained; standing the polyvinyl alcohol solution for defoaming, and cooling the solution to room temperature for later use.
(2) Preparation of cellulose acetate solution: adding 14g of cellulose acetate particles (80 meshes) with the degree of substitution of 2.2 and 86g N, N-dimethylformamide into a reaction vessel, stirring for 5 hours at 40 ℃, and obtaining a cellulose acetate solution with the mass fraction of 14% after the cellulose acetate particles are completely dissolved.
(3) Coating: selecting a quantitative 28g/m2The single-sided glossy paper is used as a substrate layer 1, the polyvinyl alcohol/nano cellulose composite coating prepared in the step (1) is coated on the front side of the substrate layer 1 through a coating machine (the front side of the single-sided glossy paper is calendered, the fiber arrangement of the single-sided glossy paper can be seen to be more compact through a front scanning electron microscope image and a back scanning electron microscope image in the figure 2, a more compact coating structure can be formed on the surface of the single-sided glossy paper after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated), the coating speed is 50m/min, and the thickness of the coating layer is 30 microns. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min, and coating the cellulose acetate solution prepared in the step (2) on the surface of the coating layer 2 by a coating machine, wherein the coating speed and the coating thickness are the same as the above operation. And after the coating is finished, the coated paper is placed indoors for natural air drying for 60min, and the barrier coated paper can be obtained.
And (3) testing: the functional tests of the coated paper obtained in the above were carried out in the same manner as in example 1, including physical property test, oil resistance test, barrier property test, and biodegradability test.
Comparative example 4
A method of making coated paper comprising the steps of:
(1) preparing a polyvinyl alcohol solution: adding 12g of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 99% (mole fraction) into 88ml of deionized water, heating at 90 ℃, and stirring for 3 hours at the rotating speed of 350r/min until a uniform and transparent solution, namely a polyvinyl alcohol solution, is obtained; standing the polyvinyl alcohol solution for defoaming, and cooling the solution to room temperature for later use.
(2) Coating: selecting a quantitative 28g/m2The single-sided glossy paper of (1) is used as a base material layer 1, and the polyvinyl alcohol solution prepared in step (1) is applied to the front surface of the base material layer 1 by a coater (the front surface of the single-sided glossy paper is calendered and can be seen from the front and back scanning electron micrographs of fig. 2)The fiber arrangement of the coating is more compact, a more compact coating structure can be formed on the surface of the coating after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated), the coating speed is 50m/min, and the thickness of the coating layer is 30 mu m. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min to obtain the polyvinyl alcohol single-layer barrier coated paper.
And (3) testing: the functional tests of the coated paper obtained in the above were carried out in the same manner as in example 1, including physical property test, oil resistance test, barrier property test, and biodegradability test.
Comparative example 5
A method of making coated paper comprising the steps of:
(1) preparing a polyvinyl alcohol/nano cellulose composite coating: 43.10g of TEMPO oxidized nano-cellulose (5-10 μm in length and 10-20nm in diameter) with a solid content of 1.16% is added into 47.40ml of deionized water, fully stirred by a glass rod until no obvious agglomeration occurs, and subjected to ultrasonic treatment for 1h under the conditions of 80Hz and 0 ℃ ice-water bath. Adding 9.5g of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 90 percent (mole fraction) into the nano-cellulose solution, heating at 90 ℃, and stirring at the rotating speed of 400r/min for 5 hours until a uniform and transparent solution, namely a polyvinyl alcohol/nano-cellulose mixed solution, is obtained; standing and defoaming the polyvinyl alcohol/nano-cellulose mixed solution for 1-2h, and cooling the solution to room temperature for later use.
(2) Coating: selecting a quantitative 28g/m2The single-sided glossy paper is used as a substrate layer 1, the polyvinyl alcohol/nano cellulose composite coating prepared in the step (1) is coated on the front side of the substrate layer 1 through a coating machine (the front side of the single-sided glossy paper is calendered, the fiber arrangement of the single-sided glossy paper can be seen to be more compact through a front scanning electron microscope image and a back scanning electron microscope image in the figure 2, a more compact coating structure can be formed on the surface of the single-sided glossy paper after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated), the coating speed is 50m/min, and the thickness of the coating layer is 30 microns. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min to obtain the single-layer barrier coated paper.
And (3) testing: the functional tests of the coated paper obtained in the above were carried out in the same manner as in example 1, including physical property test, oil resistance test, barrier property test, and biodegradability test.
Comparative example 6
A method of making coated paper comprising the steps of:
(1) preparation of cellulose acetate solution: adding 14g of cellulose acetate particles (80 meshes) with the degree of substitution of 2.5 and 86g of acetone and DMAc mixed solution into a reaction container, stirring for 5 hours at 40 ℃, and obtaining a cellulose acetate solution with the mass fraction of 14% after the cellulose acetate particles are completely dissolved.
(2) Selecting a quantitative 28g/m2The single-sided glossy paper is used as a substrate layer 1, the cellulose acetate solution prepared in the step (1) is coated on the front surface of the substrate layer 1 through a coating machine (the front surface of the single-sided glossy paper is calendered, the fiber arrangement of the single-sided glossy paper is more compact as can be seen from a front scanning electron microscope image and a back scanning electron microscope image in a figure 2, a more compact coating structure can be formed on the surface of the single-sided glossy paper after the subsequent coating is coated, the improvement of the comprehensive performance of the coated paper is facilitated), the coating speed is 50m/min, and the thickness of the coating layer is 30 mu m. And (3) after coating, drying the coated paper in an oven at 70 ℃ for 60min to obtain the single-layer barrier coated paper.
And (3) testing: the functional tests of the coated paper obtained in the above were carried out in the same manner as in example 1, including physical property test, oil resistance test, barrier property test, and biodegradability test.
The data of the functional test of the coated papers obtained in examples 1 to 6 are summarized in Table 1 below.
TABLE 1
The data of the functional tests of the coated papers obtained in the above comparative examples 1 to 6 are summarized in Table 2 below.
TABLE 2
As can be seen from the data in tables 1 and 2, the coated papers prepared in examples 1 to 6 of the present invention all had good physical properties, oil resistance, barrier properties and biodegradability, while the coated papers in comparative examples 1 to 6 all had various property reductions. Analysis of the data of the examples and comparative examples 1 to 3 shows that the addition of nanocellulose improves the overall performance of the composite coated paper, because a complex cellulose interwoven network structure is formed in the coating, the gas diffusion path is prolonged, the oxygen and water vapor transmission capacity is reduced, and the nanocellulose has a fine structure and can form hydrogen bond with polyvinyl alcohol, so that the mechanical properties of the coated paper can be further improved while the barrier property of the coating is enhanced, and a prerequisite condition is provided for applying the coated paper to the packaging field. The analysis is also verified in the electron microscope images of example 1 and comparative example 1, and it can be seen from the electron microscope images that the surface of the coated paper prepared by adding the nanocellulose is smoother and denser, and can better play a role in blocking (see fig. 3 and fig. 4). In addition, the nano-cellulose is derived from plants, has the characteristics of abundant reserves, natural degradability and the like, and accords with the green, environment-friendly and renewable concept advocated by the current society.
Analysis of the data from examples 1-6 and comparative examples 4-6 shows that the water vapor barrier and oil resistance of single layer polyvinyl alcohol coated papers are much lower than the multi-layer coated papers of the examples, which highlights the importance of the cellulose acetate coating for water vapor and grease barrier. The oxygen barrier property of the single-layer cellulose acetate coated paper is poor, which shows that the polyvinyl alcohol coating is the main part of the oxygen barrier of the coated paper, and the nano-cellulose is also the key component for improving the oxygen barrier of the coating. From relevant mechanical test data, the multi-layer coating is beneficial to enhancing the tensile strength of the coated paper, so that the coated paper has better processing adaptability. Since polyvinyl alcohol, nanocellulose and cellulose acetate can be biodegraded, the biodegradability of the coated paper in the examples and the comparative examples is not greatly changed, and the degradability of the coated paper is not influenced by multi-layer coating, which creates favorable conditions for improving other comprehensive properties by a multi-layer coating process.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
The recitation of numerical ranges herein includes all numbers subsumed within that range and includes any two numbers subsumed within that range. Different values of the same index appearing in all embodiments of the invention can be combined arbitrarily to form a range value.
The features of the invention claimed and/or described in the specification may be combined, and are not limited to the combinations set forth in the claims by the recitations therein. The technical solutions obtained by combining the technical features in the claims and/or the specification also belong to the scope of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of biodegradable high-barrier coated paper is characterized by comprising the following steps:
preparation of S1 Barrier layer: coating the polyvinyl alcohol/nano-cellulose composite coating on the surface of base paper, and drying the coated paper at 40-70 ℃ for 30-120min after the coating is finished to obtain the coated paper with the barrier layer;
preparation of S2 Heat-seal layer: and (4) coating the cellulose acetate solution on the barrier layer obtained in the step (S1), and after the coating is finished, placing the coated paper indoors for natural air drying for 30-120min to obtain the high-barrier coated paper.
2. The method of making a biodegradable high barrier coated paper according to claim 1 whereinIn step S1, the base paper is 20-50g/m2The thickness of the single-sided glossy paper is 10-80 μm; the coating speed is 30-150m/min, and the thickness of each layer of the coating is 10-30 μm.
3. The method of preparing biodegradable high barrier coated paper according to claim 1, wherein in step S1, the polyvinyl alcohol solution and polyvinyl alcohol/nanocellulose composite coating material are prepared by the following steps:
s11 adding deionized water into the nano-cellulose according to the mass ratio of 1-5:900, fully stirring until no obvious agglomeration exists, and carrying out ultrasonic treatment for 0.5-1h under the conditions of 80-100Hz and 0 ℃ ice water bath to obtain a nano-cellulose solution; adding 95-99% of polyvinyl alcohol by mass into the nano-cellulose solution, heating at 80-100 ℃, and stirring at the rotating speed of 300-450r/min for 3-5h until a uniform and transparent polyvinyl alcohol/nano-cellulose mixed solution is obtained;
s12, standing and defoaming the polyvinyl alcohol/nano-cellulose mixed solution for 1-2h, and cooling the solution to room temperature to obtain the polyvinyl alcohol/nano-cellulose composite coating.
4. The method as claimed in claim 3, wherein in step S11, the degree of polymerization of the polyvinyl alcohol is 1700-1900, and the degree of alcoholysis is 88% or more; the nano-cellulose is 2,2,6, 6-tetramethyl piperidine-nitrogen-oxide oxidized cellulose nano-fibril, a mechanical method cellulose nano-fibril, a sulfuric acid method cellulose nano-crystal or a quaternary ammonium salt modified cellulose nano-fibril.
5. The method of preparing biodegradable high barrier coated paper according to claim 1, wherein in step S2, the cellulose acetate solution is prepared by the steps of:
mixing the cellulose acetate particles with a solvent according to the mass ratio of 1:5.5-10, and stirring for 5-8h at the temperature of 25-50 ℃ to obtain a cellulose acetate solution.
6. The method of making biodegradable high barrier coated paper according to claim 5 wherein the degree of substitution of said cellulose acetate is in the range of 2.2 to 2.5; the solvent is at least one selected from the group consisting of N, N-dimethylacetamide, acetone, dimethyl sulfoxide, N-methylmorpholine-N-oxide hydrate and methyl 3-methoxypropionate.
7. A biodegradable high-barrier coated paper, which is characterized by comprising a substrate layer, a high-barrier layer and a heat-sealing layer which are connected in sequence, wherein the high-barrier coated paper is prepared by the method of any one of claims 1 to 6.
8. The biodegradable high barrier coated paper according to claim 7 wherein the high barrier layer is a polyvinyl alcohol/nanocellulose composite coating; the heat sealing layer is a cellulose acetate coating.
9. The biodegradable high barrier coated paper according to claim 8 wherein the high barrier coated paper has an oxygen transmission rate of 13-28cm3/m224 h.0.1 MPa, water vapor transmission rate of 210-2Under 24h, the tensile strength is 106-.
10. Use of the biodegradable high barrier coated paper according to any one of claims 7-9 in food packaging materials, medical and health, aerospace or electronic devices.
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| CN114808543A (en) * | 2022-03-31 | 2022-07-29 | 浙江工业大学 | Preparation method of high-performance food oil-proof paper base material containing nano-fibril cellulose composite coating |
| CN115573190A (en) * | 2022-09-22 | 2023-01-06 | 天津科技大学 | Preparation method of reaction type self-crosslinking PVA high-barrier paper base material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114808543A (en) * | 2022-03-31 | 2022-07-29 | 浙江工业大学 | Preparation method of high-performance food oil-proof paper base material containing nano-fibril cellulose composite coating |
| CN114808543B (en) * | 2022-03-31 | 2022-12-09 | 浙江工业大学 | Preparation method of high-performance food oil-proof paper-based material containing nano-fibril cellulose composite coating |
| WO2023236784A1 (en) * | 2022-06-08 | 2023-12-14 | 山东恒联新材料股份有限公司 | Barrier and heat-sealable cellulose film, preparation method therefor, and application thereof |
| GB2623887A (en) * | 2022-06-08 | 2024-05-01 | Shandong Henglian New Mat Co Ltd | Barrier and heat-sealable cellulose film, preparation method therefor, and application thereof |
| CN115573190A (en) * | 2022-09-22 | 2023-01-06 | 天津科技大学 | Preparation method of reaction type self-crosslinking PVA high-barrier paper base material |
| CN115573190B (en) * | 2022-09-22 | 2024-01-26 | 天津科技大学 | Preparation method of reactive self-crosslinking PVA high-barrier paper-based material |
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Application publication date: 20220111 |