CN109706792B - Transparent release paper and preparation method thereof - Google Patents

Transparent release paper and preparation method thereof Download PDF

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CN109706792B
CN109706792B CN201910008899.4A CN201910008899A CN109706792B CN 109706792 B CN109706792 B CN 109706792B CN 201910008899 A CN201910008899 A CN 201910008899A CN 109706792 B CN109706792 B CN 109706792B
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transparent
cellulose
release paper
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sticking
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CN109706792A (en
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赵磊
黄晔
王晓明
赵春风
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Wuzhou Special Paper Industry Jiangxi Co ltd
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Zhangzhou Wuzhou Special Paper Co ltd
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Abstract

The invention relates to transparent release paper and a preparation method thereof, and relates to the field of industrial paper. The transparent anti-sticking paper consists of a glassine base body and a transparent anti-sticking coating, wherein the transparent anti-sticking coating comprises the following components in percentage by mass: 40-60: 40-60 of modified nano-cellulose, carboxymethyl cellulose (CMC) and styrene-acrylate copolymer, wherein: the modified nano-cellulose is prepared from the following components in percentage by mass of 4-5: 1.5-2.5: 1, uniformly mixing pentafluorobenzoyl chloride, an organic amine solution of potassium thiocyanate and a nano cellulose crystal, heating to 80-90 ℃ in a nitrogen atmosphere, stirring and reacting for 2.5-4 h at 80-90 ℃, centrifuging and concentrating a generated product, removing redundant solvent, washing, and centrifugally separating to obtain the modified nano cellulose. The transparent release paper has high surface smoothness, transparency and strength, low oil absorption, excellent stripping effect and low production cost.

Description

Transparent release paper and preparation method thereof
Technical Field
The invention relates to the technical field of industrial paper, in particular to transparent release paper and a preparation method thereof.
Background
Glassine paper is also called semi-transparent glassine paper, which is special paper with good internal strength and transparency prepared by coating and processing special base paper for glassine. The product has the functions of high temperature resistance, moisture resistance, oil resistance and the like, and is generally used as a release substrate of product labels, laser anti-counterfeiting labels, bar code information labels, double-sided tapes and special tapes in the industries of food, medicine, daily chemicals, logistics, supermarkets and the like. Driven by downstream industries such as logistics labels and electronic tapes, the demand of glassine paper as labels and tape backing paper is increasing dramatically. In order to meet the requirements of high-speed processing and high-speed automatic labeling, the glassine paper has the advantages of smooth surface, uniform thickness, higher tensile strength and transparency, uniform silicon coating, consistent release force, no breakage during labeling and correct identification of position information of the label by a photoelectric sensor. However, the currently produced glassine paper in China is inferior to imported products in the aspects of surface smoothness, oil resistance and the like, so that the release performance of the paper is poor, and high surface silicon coating amount is needed, so that the production cost is increased; the stripping effect after silicon coating is poor, and the required stripping force is large; in addition, the strength and the transparency are low, and the requirement of high-speed automatic labeling can not be met.
Surface sizing is the primary method of improving the oil resistance of glassine. However, the surface sizing agent used at present mainly comprises latex mixtures of starch, polyvinyl alcohol, acrylic resin and the like and a proper amount of oil-proof agent, and generally the oil-proof agent has large dosage and low oil-proof efficiency. And the opacity and the strength of the finished paper are lower, so that the application range of the glassine paper is influenced.
Natural cellulose is the most abundant biomass resource on earth, is the most widely distributed biopolymer in nature, and is present in various organisms such as plants, animals, and some bacteria. The Nano Cellulose Crystal (NCC) is nano cellulose extracted from natural fibers, is rigid rod-shaped cellulose with the diameter of 1-100 nm and the length of dozens to hundreds of nanometers, has the characteristics of nano particles, has certain unique strength and optical performance, and has wide application prospect.
The present application has been made for the above reasons.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides the transparent release paper with high transparency, high surface smoothness, good oil resistance, excellent stripping performance and the like and the preparation method thereof.
In order to realize the first purpose of the invention, the invention adopts the following technical scheme:
a transparent release paper consisting of a glassine base and a transparent release coating consisting of modified nanocellulose, carboxymethylcellulose (CMC) and styrene-acrylate copolymer, wherein: the mass ratio of the modified nano-cellulose to the carboxymethyl cellulose to the styrene-acrylate copolymer is 10: 40-60: 40-60.
Further, according to the technical scheme, the modified nano-cellulose is prepared from the following components in a mass ratio of 4-5: 1.5-2.5: 1, uniformly mixing pentafluorobenzoyl chloride, an organic amine solution of potassium thiocyanate and a nano cellulose crystal, heating to 80-90 ℃ in a nitrogen atmosphere, stirring and reacting for 2.5-4 h at 80-90 ℃, centrifuging and concentrating a generated product, removing redundant solvent, washing, and centrifugally separating to obtain the modified nano cellulose.
Preferably, in the above technical solution, the organic amine is selected from any one of triethylamine and ethylenediamine.
Preferably, in the technical scheme, the mass concentration of the potassium thiocyanate in the potassium thiocyanate solution is 50-60%.
Preferably, in the technical scheme, the diameter of the nano-cellulose crystal is 10-50 nm, and the length of the nano-cellulose crystal is 150-300 nm.
The second object of the present invention is to provide a method for preparing the transparent release paper, which comprises the following steps:
(1) preparation of modified nanocellulose
At room temperature, mixing pentafluorobenzoyl chloride, organic amine solution of potassium thiocyanate and nano cellulose crystals according to a mass ratio of 4-5: 1.5-2.5: 1 are sequentially added into a closed reactor, and are stirred and mixed uniformly; then heating the reactor to 80-90 ℃ in a nitrogen atmosphere, and stirring and reacting for 2.5-4 h at 80-90 ℃; after the reaction is finished, cooling to room temperature, centrifugally concentrating the obtained product, removing redundant solvent, finally washing the product, and centrifugally separating to obtain the modified nano-cellulose;
(2) preparation of transparent anti-sticking coating
Carrying out modification on the modified nanocellulose prepared in the step (1); a carboxymethyl cellulose; the styrene-acrylate copolymer is prepared from the following components in a mass ratio of 10: 40-60: 40-60 ℃, and uniformly mixing and blending at 60-70 ℃ to obtain the transparent anti-sticking coating;
(3) preparation of transparent release paper
Beating softwood pulp to 30-35 DEG SR, beating hardwood pulp to 35-40 DEG SR, beating mechanical wood pulp to 35-40 DEG SR, wherein the mass ratio is 1: 1-2: 1-2, and then making a low-basis-weight glassine paper substrate; and (3) uniformly coating the transparent anti-sticking coating prepared in the step (2) on the surface of the glassine substrate by using a surface sizing metering rod, and drying and calendering to prepare the transparent anti-sticking paper.
Further, according to the technical scheme, the application amount of the transparent anti-sticking coating in the step (3) is 2-5% of the mass of the glassine paper.
Further, according to the technical scheme, the solid content of the transparent anti-sticking coating in the step (2) is 5-10%.
Further, according to the technical scheme, the centrifugal treatment of the product in the step (1) is preferably high-speed centrifugation, the centrifugation speed is 8000-12000 r/min, and the centrifugation time is 20-50 min.
Further, according to the technical scheme, the product obtained in the step (1) is preferably washed by hexane and ethanol for 3-6 times respectively.
The method takes the nano-crystalline cellulose with better strength and transparency as the main raw material, takes pentafluorobenzoyl chloride as a modifier, and carries out oil-proof modification on the nano-crystalline cellulose in triethylamine solution of potassium thiocyanate to prepare modified nano-crystalline cellulose; and then mixing the modified nano-cellulose with carboxymethyl cellulose and styrene-acrylate copolymer to prepare a transparent anti-sticking coating, finally coating the transparent anti-sticking coating on the surface of the glassine substrate, and drying and calendaring to prepare the transparent anti-sticking paper. The transparent release paper prepared by the invention has high surface smoothness, transparency and strength, low oil absorption, excellent stripping effect and low production cost.
The transparency of the transparent release paper prepared by the invention can reach 50 percent, the smoothness reaches 1550s, and the oil absorbency is as low as 1g/m2And excellent properties such as transverse tearing index and tensile index.
Compared with the prior art, the invention has the main advantages that:
(1) improve the oil resistance of the glassine paper, improve the stripping effect of the glassine paper and reduce the production cost
According to the invention, the oil-resistant component is introduced to the nano cellulose crystal molecules through a substitution reaction, so that the nano cellulose crystal molecules have oil resistance, and the nano cellulose crystal molecules are used as an oil-resistant agent to prepare the surface sizing agent for surface sizing of the glassine paper, so that the oil resistance of the glassine paper is improved, the silicon oil coating amount in subsequent processing is reduced, the cost is reduced, and the stripping effect is improved.
(2) Improve the transparency of the glassine paper and meet the requirement of high-speed automatic labeling
The transparency is an important index of the glassine paper, and the high transparency is beneficial for a photoelectric sensor to accurately identify the label of the picture and text to be pasted, so that the continuous automatic labeling is realized by adopting the correct action. The method keeps the characteristics of the nano-crystalline cellulose in the modification process of the nano-crystalline cellulose, and makes full use of the high transparency of the nano-crystalline cellulose, so that the paper after glue application has high transparency, and the paper meets the requirement of high-speed automatic labeling.
(3) Improve the strength and surface performance of the glassine paper and the application range of the paper
To meet the requirement of high-speed processing, the glassine paper needs to have high strength so as to ensure that the glassine paper cannot be easily broken to influence normal continuous use in the using process. According to the invention, the modified nano-cellulose crystal is added into the surface sizing agent, so that the strength performance and the surface performance of paper can be improved, the requirement of high-speed processing is met, and the application range of the paper is enlarged.
Drawings
FIG. 1 is a flow chart of a process for preparing a transparent release paper according to example 1 of the present invention.
Detailed Description
The following is a detailed description of embodiments of the invention. The embodiment is implemented on the premise of the technical scheme of the invention, and a detailed implementation mode and a specific operation process are given, but the protection scope of the invention is not limited to the following embodiment.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Example 1
The preparation method of the transparent release paper of the embodiment comprises the following steps:
(1) preparation of modified nanocellulose
At room temperature, adding 100g of pentafluorobenzoyl chloride into a closed reactor, then sequentially adding 50g of potassium thiocyanate/triethylamine solution (wherein the mass concentration of potassium thiocyanate in triethylamine is 60%) and 20g of nano-cellulose crystal (wherein the diameter of the nano-cellulose crystal is 10-50 nm, and the length of the nano-cellulose crystal is 150-300 nm) into the reactor, and continuously stirring by using a stirrer to uniformly mix; heating the reactor to 90 ℃ in a nitrogen atmosphere, stirring and reacting for 4h at 90 ℃, cooling to room temperature after the reaction is finished, centrifugally treating the obtained product for 50min at a rotating speed of 12000r/min, removing redundant solvent, washing the product for 6 times by using hexane, washing the product for 6 times by using ethanol, and finally centrifugally separating for 50min to obtain the modified nano-cellulose;
(2) preparation of transparent anti-sticking coating
Adding 20g of the modified nanocellulose prepared in the step (1) into another container, then sequentially adding 120g of carboxymethyl cellulose and 120g of styrene-acrylate copolymer into the container, and uniformly mixing and blending at 70 ℃ to obtain the transparent anti-sticking coating, wherein the solid content of the transparent anti-sticking coating is 10%;
(3) preparation of transparent release paper
Beating softwood pulp to 30-degree SR, beating hardwood pulp to 35-degree SR, beating mechanical wood pulp to 35-degree SR, and sequentially mixing the materials according to the mass ratio of 1: 2: 2, the papermaking quantitative is 40g/m2The glassine paper substrate of (1); and (3) uniformly coating the transparent anti-sticking coating prepared in the step (2) on the surface of the glassine substrate by using a surface sizing metering rod, and drying and calendering to prepare the transparent anti-sticking paper, wherein: the application amount of the transparent anti-sticking coating is 5 percent of the mass of the glassine paper.
Example 2
A method of preparing a transparent release coating according to this example, comprising the steps of:
(1) preparation of modified nanocellulose
Adding 100g of pentafluorobenzoyl chloride into a closed reactor at room temperature, then sequentially adding 37.5g of potassium thiocyanate/ethylenediamine solution (wherein the mass concentration of potassium thiocyanate in ethylenediamine is 50%) and 25g of nano-cellulose crystal (wherein the diameter of the nano-cellulose crystal is 10-50 nm, and the length of the nano-cellulose crystal is 150-300 nm) into the reactor, and continuously stirring by using a stirrer to uniformly mix; heating the reactor to 85 ℃ in a nitrogen atmosphere, stirring and reacting for 3.5h at 85 ℃, cooling to room temperature after the reaction is finished, centrifugally treating the obtained product at 10000r/min of rotation speed for 50min, removing redundant solvent, washing the product with hexane for 3 times, washing with ethanol for 3 times, and finally centrifugally separating for 50min to obtain the modified nano-cellulose;
(2) preparation of transparent anti-sticking coating
Adding 20g of the modified nanocellulose prepared in the step (1) into another container, then sequentially adding 80g of carboxymethyl cellulose and 80g of styrene-acrylate copolymer into the container, and uniformly mixing and blending at 65 ℃ to obtain the transparent anti-sticking coating, wherein the solid content of the transparent anti-sticking coating is 8%;
(3) preparation of transparent release paper
Beating softwood pulp to 35-degree SR, beating hardwood pulp to 35-degree SR, beating mechanical wood pulp to 40-degree SR, and sequentially mixing the components in a mass ratio of 1: 1: 1, the papermaking quantitative is 40g/m2The glassine paper substrate of (1); and (3) uniformly coating the transparent anti-sticking coating prepared in the step (2) on the surface of the glassine substrate by using a surface sizing metering rod, and drying and calendering to prepare the transparent anti-sticking paper, wherein: the application amount of the transparent anti-sticking coating is 4 percent of the mass of the glassine paper.
Example 3
A method of preparing a transparent release coating according to this example, comprising the steps of:
(1) preparation of modified nanocellulose
Adding 90g of pentafluorobenzoyl chloride into a closed reactor at room temperature, then sequentially adding 40g of potassium thiocyanate/triethylamine solution (wherein the mass concentration of potassium thiocyanate in triethylamine is 60%) and 20g of nano-cellulose crystal (wherein the diameter of the nano-cellulose crystal is 10-50 nm, and the length of the nano-cellulose crystal is 150-300 nm) into the reactor, and continuously stirring by using a stirrer to uniformly mix; heating the reactor to 80 ℃ in a nitrogen atmosphere, stirring and reacting for 4 hours at 80 ℃, cooling to room temperature after the reaction is finished, centrifugally treating the obtained product for 50 minutes at a rotating speed of 12000r/min, removing redundant solvent, washing the product for 4 times by using hexane, washing the product for 4 times by using ethanol, and finally centrifugally separating for 50 minutes to obtain the modified nano-cellulose;
(2) preparation of transparent anti-sticking coating
Adding 20g of the modified nanocellulose prepared in the step (1) into another container, then sequentially adding 100g of carboxymethyl cellulose and 100g of styrene-acrylate copolymer into the container, and uniformly mixing and blending at 60 ℃ to obtain the transparent anti-sticking coating, wherein the solid content of the transparent anti-sticking coating is 5%;
(3) preparation of transparent release paper
Beating softwood pulp to 30-degree SR, beating hardwood pulp to 40-degree SR, beating mechanical wood pulp to 40-degree SR, and sequentially mixing the materials according to the mass ratio of 1: 1.5: 2, the papermaking quantitative is 40g/m2The glassine paper substrate of (1); and (3) uniformly coating the transparent anti-sticking coating prepared in the step (2) on the surface of the glassine substrate by using a surface sizing metering rod, and drying and calendering to prepare the transparent anti-sticking paper, wherein: the application amount of the transparent anti-sticking coating is 3 percent of the mass of the glassine paper.
Example 4
A method of preparing a transparent release coating according to this example, comprising the steps of:
(1) preparation of modified nanocellulose
Adding 100g of pentafluorobenzoyl chloride into a closed reactor at room temperature, then sequentially adding 50g of potassium thiocyanate/ethylenediamine solution (wherein the mass concentration of potassium thiocyanate in ethylenediamine is 60%) and 25g of nano-cellulose crystal (wherein the diameter of the nano-cellulose crystal is 10-50 nm, and the length of the nano-cellulose crystal is 150-300 nm) into the reactor, and continuously stirring by using a stirrer to uniformly mix; heating the reactor to 90 ℃ in a nitrogen atmosphere, stirring and reacting for 2.5h at 90 ℃, cooling to room temperature after the reaction is finished, centrifuging the obtained product at 8000r/min for 50min, removing redundant solvent, washing the product with hexane for 3 times, washing with ethanol for 3 times, and finally centrifuging for 50min to obtain the modified nano-cellulose;
(2) preparation of transparent anti-sticking coating
Adding 20g of the modified nanocellulose prepared in the step (1) into another container, then sequentially adding 100g of carboxymethyl cellulose and 80g of styrene-acrylate copolymer into the container, and uniformly mixing and blending at 70 ℃ to obtain the transparent anti-sticking coating, wherein the solid content of the transparent anti-sticking coating is 9%;
(3) preparation of transparent release paper
Beating softwood pulp to 32-degree SR, beating hardwood pulp to 38-degree SR, beating mechanical wood pulp to 36-degree SR, wherein the mass ratio is 1: 1.5: 1.5, the papermaking quantitative is 40g/m2The glassine paper substrate of (1); and (3) uniformly coating the transparent anti-sticking coating prepared in the step (2) on the surface of the glassine substrate by using a surface sizing metering rod, and drying and calendering to prepare the transparent anti-sticking paper, wherein: the application amount of the transparent anti-sticking coating is 2.5 percent of the mass of the glassine paper.
Example 5
A method of preparing a transparent release coating according to this example, comprising the steps of:
(1) preparation of modified nanocellulose
At room temperature, adding 100g of pentafluorobenzoyl chloride into a closed reactor, then sequentially adding 40g of potassium thiocyanate/triethylamine solution (wherein the mass concentration of potassium thiocyanate in triethylamine is 50%) and 20g of nano-cellulose crystal (wherein the diameter of the nano-cellulose crystal is 10-50 nm, and the length of the nano-cellulose crystal is 150-300 nm) into the reactor, and continuously stirring by using a stirrer to uniformly mix; heating the reactor to 85 ℃ in a nitrogen atmosphere, stirring and reacting for 3h at 85 ℃, cooling to room temperature after the reaction is finished, centrifugally treating the obtained product for 50min at the rotation speed of 10000r/min, removing redundant solvent, washing the product for 6 times by using hexane, washing the product for 6 times by using ethanol, and finally centrifugally separating for 50min to obtain the modified nano-cellulose;
(2) preparation of transparent anti-sticking coating
Adding 20g of the modified nanocellulose prepared in the step (1) into another container, then sequentially adding 90g of carboxymethyl cellulose and 110g of styrene-acrylate copolymer into the container, and uniformly mixing and blending at 70 ℃ to obtain the transparent anti-sticking coating, wherein the solid content of the transparent anti-sticking coating is 6%;
(3) preparation of transparent release paper
Beating softwood pulp to 33 DEG SR, beating hardwood pulp to 36 DEG SR, beating mechanical wood pulp to 38 DEG SR according to the mass ratio of 1: 2: 2, the papermaking quantitative is 40g/m2The glassine paper substrate of (1); and (3) uniformly coating the transparent anti-sticking coating prepared in the step (2) on the surface of the glassine substrate by using a surface sizing metering rod, and drying and calendering to prepare the transparent anti-sticking paper, wherein: the application amount of the transparent anti-sticking coating is 2 percent of the mass of the glassine paper.
Comparative example 1
The transparent release paper of this comparative example was prepared in substantially the same manner as in example 1, except that: the transparent release coating of this comparative example did not have any modified nanocellulose added.
The transparent release papers obtained in examples 1 to 5 and comparative example 1 were subjected to a performance test, and the results are shown in table 1 below. The properties of the transparent release paper such as oil resistance, physical strength, transparency and the like are detected by adopting the following national standards: GB/T451.2-2002 paper and paperboard quantitative determination; a paper oil absorbency determination method of SCAN 37:77Cobb Unger method; measuring the transparency of GB/T2679.1-2013 paper; GB/T12914-; GB/T455-; GB/T456-2002 paper and board smoothness determination (Buick method).
TABLE 1 Performance test
Figure BDA0001936476650000081

Claims (8)

1. A transparent release paper is characterized in that: the transparent anti-sticking paper consists of a glassine substrate and a transparent anti-sticking coating, wherein the transparent anti-sticking coating consists of modified nano-cellulose, carboxymethyl cellulose and styrene-acrylate copolymer, and the transparent anti-sticking coating consists of: the mass ratio of the modified nano-cellulose to the carboxymethyl cellulose to the styrene-acrylate copolymer is 10: 40-60: 40-60; the transparent release paper is prepared by the following method, comprising the following steps:
(1) preparation of modified nanocellulose
At room temperature, mixing pentafluorobenzoyl chloride, organic amine solution of potassium thiocyanate and nano cellulose crystals according to a mass ratio of 4-5: 1.5-2.5: 1 are sequentially added into a closed reactor, and are stirred and mixed uniformly; then heating the reactor to 80-90 ℃ in a nitrogen atmosphere, and stirring and reacting for 2.5-4 h at 80-90 ℃; after the reaction is finished, cooling to room temperature, centrifugally concentrating the obtained product, removing redundant solvent, finally washing the product, and centrifugally separating to obtain the modified nano-cellulose;
(2) preparation of transparent anti-sticking coating
Carrying out modification on the modified nanocellulose prepared in the step (1); a carboxymethyl cellulose; the styrene-acrylate copolymer is prepared from the following components in a mass ratio of 10: 40-60: 40-60 ℃, and uniformly mixing and blending at 60-70 ℃ to obtain the transparent anti-sticking coating;
(3) preparation of transparent release paper
Beating softwood pulp to 30-35 DEG SR, beating hardwood pulp to 35-40 DEG SR, beating mechanical wood pulp to 35-40 DEG SR, wherein the mass ratio is 1: 1-2: 1-2, and then making a low-basis-weight glassine paper substrate; and (3) uniformly coating the transparent anti-sticking coating prepared in the step (2) on the surface of the glassine substrate by using a surface sizing metering rod, and drying and calendering to prepare the transparent anti-sticking paper.
2. The transparent release paper according to claim 1, wherein: the organic amine is selected from any one of triethylamine and ethylenediamine.
3. The transparent release paper according to claim 1, wherein: the mass concentration of the potassium thiocyanate in the potassium thiocyanate solution is 50-60%.
4. The transparent release paper according to claim 1, wherein: the diameter of the nano-cellulose crystal is 10-50 nm, and the length of the nano-cellulose crystal is 150-300 nm.
5. The transparent release paper according to claim 1, wherein: and (3) applying the transparent anti-sticking coating in the step (3) in an amount of 2-5% of the mass of the glassine paper.
6. The transparent release paper according to claim 1, wherein: and (3) the solid content of the transparent anti-sticking coating in the step (2) is 5-10%.
7. The transparent release paper according to claim 1, wherein: and (2) centrifuging the product obtained in the step (1) at a high speed of 8000-12000 r/min for 20-50 min.
8. The transparent release paper according to claim 1, wherein: and (2) washing the product obtained in the step (1) by using hexane and ethanol respectively for 3-6 times.
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CN110804105B (en) * 2019-11-05 2021-06-04 浙江恒川新材料有限公司 Fluorine-containing hydrophobic oil-resistant modified nano-cellulose for food packaging paper and preparation method thereof
CN112663377B (en) * 2020-12-22 2021-09-14 阿尔诺维根斯(衢州)特种纸有限公司 Preparation method of natural flexible transparent paper

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CN1500563A (en) * 2002-10-15 2004-06-02 Production method of multi-layer coating substrate with improved obstructive performance
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