CN115403850A - High-barrier material and preparation method thereof - Google Patents
High-barrier material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention discloses a high-barrier material, which comprises: 40-60 parts of HDPE, 20-40 parts of PET, 10-30 parts of modified barrier filler, 0.5-1 part of stabilizer and 0.5-1 part of antioxidant; the modified blocking filler is prepared by dispersing nano-cellulose in deionized water, and sequentially adding a silane coupling agent and a hydrophobic agent for ultrasonic treatment; then adding alkali liquor and urea for standing treatment; then adding mica sheets for heating treatment; filtering and drying to obtain the product. The invention takes polyethylene terephthalate (PET) and high-density polyethylene (HDPE) as basic resin, modified barrier filler is added, and a double-screw extruder is utilized to prepare the degradable reinforced composite material with low production cost, high mechanical property and high barrier property, which can be used for the actual production requirement of high-barrier bottles.
Description
Technical Field
The invention relates to the technical field of barrier bottles, in particular to a high-barrier material and a preparation method thereof.
Background
Most of domestic middle and downstream enterprises in blow molding of HDPE and PET carry out layered doping blending on imported high-barrier resin and domestic special resin to produce packaging materials with high barrier property, and the barrier resin needs to be dispersed in matrix resin in a lamellar manner, so that the processing technology has higher requirements. Meanwhile, the cost is expensive under the background that short plates exist in the production of international large-format and domestic high-barrier resin. The sheet inorganic matter is a stable sheet structure in a resin processing environment, and the processing technology requirement is not high, so the sheet inorganic matter modified layered blending barrier technology gradually becomes a research hotspot, wherein the barrier research of the sheet inorganic matter layered blending is the most extensive. Sericite is a silicate mineral substance with lamellar structure, mica powder prepared from sericite has the characteristics of thin lamella and large radius-thickness ratio, has good moisture resistance, oxygen resistance and ultraviolet resistance, is low in price, and is a commonly used functional additive in the paint and cosmetic industries. The mica powder is used for plastic modification and is commonly used for researches on filling reinforcement, heat resistance, electrical property and the like, but the research space for modifying resin by the mica powder is huge in the aspects of development and production of high-performance barrier materials.
With the rapid development and transformation upgrading of the domestic packaging industry, the cosmetic industry, the food industry, the pharmaceutical industry and the like, the use requirements of high polymer materials are continuously improved. The barrier property of common food such as beverage, meat and the like on the packaging material is higher and higher, so that the food is not changed in the display, storage and transportation processes, and meanwhile, the high barrier material is widely applied to packaging of cosmetics, medicines, tea and spices. Especially, the requirements of the blow molding special material on organic solvent, moisture, oxygen barrier property, impact resistance and Environmental Stress Cracking Resistance (ESCR) are continuously improved, but with the increase of plastic materials and the difficult degradability, the special material has serious influence on the natural environment, biodiversity and the like. Therefore, the polymer composite material product which is added with degradable materials and pursues comprehensive properties such as high barrier property, strong impact resistance and the like is in the forefront.
Disclosure of Invention
In view of the above prior art, the present invention aims to provide a high barrier material and a preparation method thereof. According to the invention, the nano-cellulose is modified, so that the nano-cellulose and the mica sheet are bonded together through hydrogen bonds and are used as the filler of the barrier material, thereby not only maintaining the barrier property of the barrier material, but also enabling the barrier material to have degradability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a high-barrier material, which comprises the following raw materials in parts by weight:
40-60 parts of HDPE, 20-40 parts of PET, 10-30 parts of modified blocking filler, 0.5-1 part of stabilizer and 0.5-1 part of antioxidant;
the modified blocking filler is prepared from nano cellulose and mica sheets according to the weight ratio of 1:1, and the mass ratio of the components is obtained.
Preferably, the modified barrier filler is prepared by the following method:
(1) Dispersing nano-cellulose in deionized water, adding a silane coupling agent for ultrasonic treatment, then adding a hydrophobic agent, and continuing ultrasonic treatment; filtering and drying to obtain modified nano-cellulose;
(2) Adding the modified nano-cellulose into alkali liquor, uniformly mixing, adding urea, and standing; finally, adding mica sheets for heating treatment; and filtering and drying to obtain the modified barrier filler.
Preferably, in the step (1), the amount of the hydrophobic agent accounts for 3-7% of the mass of the nanocellulose; the dosage of the silane coupling agent accounts for 0.3 to 0.7 percent of the mass of the nano-cellulose; the ultrasonic treatment time is 10-30 min, the ultrasonic treatment power is 900w, and the ultrasonic treatment frequency is 20KHZ.
Preferably, the hydrophobic agent is selected from dimethyl silicone oil; the silane coupling agent is KH-550.
Preferably, the alkali liquor is selected from NaOH solution or KOH solution, and the concentration of the alkali liquor is 0.1-1.0 moL/L; the mass ratio of the alkali liquor to the urea to the modified nano-cellulose is 1: (0.01-0.1): 1; the standing treatment time is 10-30 min.
Preferably, the mica sheet is a sericite sheet, and the diameter-thickness ratio of the mica sheet is 85-90; the temperature of the heating treatment is 60-80 ℃, and the time is 0.5-1 h.
Preferably, the stabilizer is stearic acid; the antioxidant is 1010.
In a second aspect of the present invention, a method for preparing a high barrier material is provided, the method comprising: weighing the raw materials in parts by weight, uniformly mixing, drying in vacuum, placing in an internal mixer for mixing, cooling, granulating, and extruding in a double-screw extruder to obtain plastic particles, namely the high-barrier material.
Preferably, the temperature of the vacuum drying is 60-70 ℃; the temperature of the internal mixer is 150-180 ℃, and the internal mixing time is 20-30 min.
In a third aspect of the invention, there is provided the use of a high barrier material in the manufacture of a high barrier bottle.
The invention has the beneficial effects that:
(1) The invention takes polyethylene terephthalate (PET) and high-density polyethylene (HDPE) as basic resin, modified barrier filler is added, and a double-screw extruder is utilized to prepare the reinforced composite material with low production cost, high mechanical property, high barrier property and multiple functions, so as to meet the actual production requirements of high-barrier bottles. The project can drive the development of the domestic mica market when producing high-performance HDPE and PET barrier bottles, and meanwhile, the dry modification process adopted by the project is simple and easy to operate, does not need a large amount of solvents, and cannot cause pollution to the environment.
(2) According to the invention, the nano-cellulose is subjected to hydrophobic treatment and is modified by using the silane coupling agent, and then the combination of the nano-cellulose and the mica sheet is promoted by the synergy of the alkali liquor and the urea, so that the modified nano-cellulose and the mica sheet are combined through hydrogen bonds, and the problem that the nano-cellulose has hydrophilicity and is not suitable for barrier materials is solved. The problem that nano cellulose powder is easy to agglomerate is solved by combining the nano cellulose and the mica sheet, a dispersing agent is not required to be added, and the degradability of the barrier material is also improved.
(3) According to the invention, the addition of the nano-cellulose does not reduce the barrier property of the barrier material, and the barrier material has degradability. The invention has the advantages of simple and easily obtained raw materials, no large amount of organic solvent, simple preparation method and low cost, and is suitable for industrialized popularization and preparation of the barrier bottle.
Drawings
FIG. 1: schematic of the distribution of the modified barrier filler in the resin matrix.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described in the background section, the matrix resin of the current barrier material mainly contains flake-like filler materials such as mica, graphene, and montmorillonite. However, as the requirements on the performance of materials such as blow molding and injection molding are continuously mentioned, a large amount of additives are required to improve the performance of the barrier material. Therefore, the environment is polluted, the barrier property of the material cannot be improved, and the degradability of the material is poor.
Based on the above, the invention aims to provide a high-barrier material, which takes HDPE and PET as matrix resins, takes mica sheets as barrier fillers, and improves the degradability of the material by adding nanocellulose with good biocompatibility. The strong hydrogen bonds are formed between the nano-cellulose and the mica sheet through sodium ions or potassium ions, and the nano-cellulose and the mica sheet are combined together. However, the surface of the nano-cellulose is exposed with a large number of hydrophilic groups, so that a hydration layer is easily formed, and strong hydrophilicity is shown. Therefore, in a humid environment, water molecules are easily adsorbed on the surface of the nano-crystalline cellulose, and hydrogen bonding among nano-crystalline celluloses is damaged, so that the isolation performance of the nano-crystalline cellulose is greatly reduced. Therefore, the method firstly uses a small amount of silane coupling agent to treat the nano-cellulose, and then uses the hydrophobic agent to treat the nano-cellulose; and then combined with the mica sheet. However, research shows that in actual processing, the modified blocking filler is influenced by high temperature, the dispersibility of the modified blocking filler is general, the combination of the nano-cellulose and the mica sheet is poor, and the nano-cellulose is easy to fall off. Researches show that when the modified nano-cellulose reacts with mica sheets, a small amount of urea is added, the subsequent processing temperature is increased, and the urea is decomposed, so that the dispersibility is greatly improved, and the nano-cellulose is prevented from falling off the mica sheets in the processing process.
The invention realizes the layered distribution of the modified blocking filler in the matrix resin under the action of the shearing force, researches the influence rule of the modified blocking filler on the microstructure, the mechanical property, the thermal property and the blocking property of the material, and overcomes the defects of high production cost and poor thermal property of the existing HDPE and PET high-performance blocking materials. The most effective method for improving the barrier property is to increase the isolating layer of the gas passing path in the gas passage way, so that the 'tortuous' degree of the path is increased, the permeation time of the gas molecules is prolonged, and the barrier effect is achieved. Under the shearing force during processing, the modified barrier filler is in a flake shape, and peeling occurs to form a distribution in the resin matrix as shown in fig. 1.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention were all conventional in the art and commercially available.
Example 1
Dispersing 1.5kg of nano-cellulose in 10L of deionized water, adding 7.5g of KH-550, and performing ultrasonic treatment for 20min; then 75g of polydimethylsiloxane oil is added for ultrasonic treatment for 20min. The power of ultrasonic treatment is 900w, and the frequency of ultrasonic treatment is 20KHZ. Filtering, and vacuum drying at 60 ℃ to obtain the modified nano-cellulose.
Adding the modified nano-cellulose into 0.6moL/L of 1.5kg NaOH solution, then adding 75g of urea, and standing for 20min. Then adding 1.5kg of mica sheets and heating for 1h at 70 ℃; and (4) drying the solid obtained after filtering in vacuum at 50 ℃ to obtain the modified blocking filler.
Example 2
5kg of HDPE,3kg of PET and 2.0kg of modified barrier filler prepared by the method in example 1, 75g of stearic acid and 75g of antioxidant are uniformly mixed, and are subjected to vacuum drying at 65 ℃, blending and extrusion to obtain plastic particles, the plastic particles are placed in an internal mixer at 170 ℃ for mixing for 25min, and are granulated after cooling, and the plastic particles are extruded in a double-screw extruder to obtain the high-barrier material.
Example 3
6kg of HDPE,2kg of PET and 3kg of modified barrier filler prepared by the method in example 1, 50g of stearic acid and 100g of antioxidant are uniformly mixed, and are subjected to vacuum drying at 70 ℃, blending and extrusion to obtain plastic particles, the plastic particles are placed in an internal mixer at 160 ℃ and are subjected to mixing for 30min, and the plastic particles are cooled, granulated and extruded in a double-screw extruder to obtain the plastic particles, namely the high-barrier material.
Example 4
4kg of HDPE,4kg of PET,1.0kg of modified barrier filler prepared by the method in example 1, 100g of stearic acid and 50g of antioxidant are uniformly mixed, vacuum-dried at 60 ℃, blended and extruded to obtain plastic particles, the plastic particles are placed in an internal mixer at 180 ℃ for mixing for 20min, cooled and cut into particles, and the plastic particles are extruded in a double-screw extruder to obtain the high-barrier material.
Comparative example 1
1.5kg of nano-cellulose is dispersed in 10L of deionized water, and 7.5g of KH-550 is added for ultrasonic treatment for 20min. The power of the ultrasonic treatment is 900w, and the frequency of the ultrasonic treatment is 20KHZ. Filtering, and vacuum drying at 60 ℃ to obtain the modified nano-cellulose.
Adding the modified nano-cellulose into 0.6moL/L of 1.5kg NaOH solution, adding 75g of urea, and standing for 20min. Then adding 1.5kg of mica sheets and heating for 1h at 70 ℃; and (4) drying the solid obtained after filtering in vacuum at 50 ℃ to obtain the modified blocking filler.
Comparative example 2
1.5kg of nano-cellulose is dispersed in 10L of deionized water, and 60g of polydimethylsiloxane oil is added for ultrasonic treatment for 20min. The power of the ultrasonic treatment was 900w, and the frequency of the ultrasonic treatment was 20KHZ.
Adding the modified nano-cellulose into 0.6moL/L of 1.5kg NaOH solution, adding 75g of urea, and standing for 20min. Then adding 1.5kg of mica sheets and heating for 1h at 70 ℃; and (4) drying the solid obtained after filtering in vacuum at 50 ℃ to obtain the modified blocking filler.
Comparative example 3
Dispersing 1.5kg of nano-cellulose in 10L of deionized water, adding 7.5g of KH-550, and performing ultrasonic treatment for 20min; then 75g of polydimethylsiloxane oil is added for ultrasonic treatment for 20min. The ultrasonic treatment power is 900w, and the ultrasonic treatment frequency is 20KHZ. Filtering, and vacuum drying at 60 ℃ to obtain the modified nano-cellulose.
Adding the modified nano-cellulose into 0.6moL/L of 1.5kg NaOH solution, and standing for 20min. Then adding 1.5kg of mica sheets and heating for 1h at 70 ℃; and (4) drying the solid obtained after filtering in vacuum at 50 ℃ to obtain the modified blocking filler.
Comparative example 4
Dispersing 1.5kg of nano-cellulose in 10L of deionized water, adding 7.5g of KH-550, and performing ultrasonic treatment for 20min; then 75g of polydimethylsiloxane oil is added for ultrasonic treatment for 20min. The power of ultrasonic treatment is 900w, and the frequency of ultrasonic treatment is 20KHZ. Filtering, and vacuum drying at 60 ℃ to obtain the modified nano-cellulose.
Adding 75g of urea into the modified nano-cellulose, and standing for 20min. Then adding 1.5kg of mica sheets and heating for 1h at 70 ℃; and (4) drying the solid obtained after filtering in vacuum at 50 ℃ to obtain the modified blocking filler.
Comparative example 5
Uniformly mixing 5kg of HDPE,3kg of PET,1.5kg of modified blocking filler prepared by the method of the comparative example 1, 75g of stearic acid and 75g of antioxidant; vacuum drying at 65 ℃, blending and extruding to obtain plastic particles, mixing in an internal mixer at 170 ℃ for 25min, cooling, granulating, and extruding in a double-screw extruder to obtain the plastic particles, namely the high-barrier material.
Comparative example 6
Uniformly mixing 5kg of HDPE,3kg of PET,1.5kg of modified blocking filler prepared by the method of the comparative example 2, 75g of stearic acid, 75g of antioxidant and 7.5g of silane coupling agent; vacuum drying at 65 ℃, blending and extruding to obtain plastic particles, mixing in an internal mixer at 170 ℃ for 25min, cooling, granulating, and extruding in a double-screw extruder to obtain the plastic particles, namely the high-barrier material.
Comparative example 7
Uniformly mixing 5kg of HDPE,3kg of PET,1.5kg of modified blocking filler prepared by the method of the comparative example 3, 75g of stearic acid and 75g of antioxidant; vacuum drying at 65 ℃, blending and extruding to obtain plastic particles, mixing in an internal mixer at 170 ℃ for 25min, cooling, granulating, and extruding in a double-screw extruder to obtain the plastic particles, namely the high-barrier material.
Comparative example 8
Uniformly mixing 5kg of HDPE,3kg of PET,1.5kg of the modified barrier filler prepared by the method of the comparative example 4, 75g of stearic acid and 75g of antioxidant; vacuum drying at 65 ℃, blending and extruding to obtain plastic particles, mixing in an internal mixer at 170 ℃ for 25min, cooling, granulating, and extruding in a double-screw extruder to obtain the plastic particles, namely the high-barrier material.
Comparative example 9
Uniformly mixing 5kg of HDPE,3kg of PET,0.75kg of mica sheet, 0.75kg of nanocellulose, 75g of stearic acid, 75g of antioxidant and 35g of silane coupling agent; vacuum drying at 65 ℃, blending and extruding to obtain plastic particles, mixing in an internal mixer at 170 ℃ for 25min, cooling, granulating, and extruding in a double-screw extruder to obtain the plastic particles, namely the high-barrier material.
Comparative example 10
Uniformly mixing 5kg of HDPE,3kg of PET,1.5kg of mica sheet, 75g of stearic acid and 75g of antioxidant; vacuum drying at 65 ℃, blending and extruding to obtain plastic particles, mixing in an internal mixer at 170 ℃ for 25min, cooling, granulating, and extruding in a double-screw extruder to obtain the plastic particles, namely the high-barrier material.
Test examples
The physical and mechanical properties of the high barrier materials prepared in examples 2 to 4 and comparative examples 5 to 10 were measured, and the results are shown in table 1. Wherein, the tensile strength, the elongation at break and the flexural modulus are all detected by a universal material testing machine; the water vapor transmission rate is detected by a food package and plastic film water vapor transmission rate tester; the oxygen barrier properties were tested at 50 ℃ according to GB/T28799.2; the light resistance is detected by a light transmittance tester.
TABLE 1
As can be seen from Table 1, the tensile strength, flexural modulus, water vapor and oxygen transmission rate and the like of the high-barrier materials prepared in the examples 2 to 4 are superior to those of the comparative examples 5 to 10, which shows that the high-barrier materials prepared by the invention have excellent barrier property, impact resistance and the like, and the barrier materials are added with nanocellulose and have degradability; is suitable for producing high-barrier bottles.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. The high-barrier material is characterized by comprising the following raw materials in parts by weight:
40-60 parts of HDPE, 20-40 parts of PET, 10-30 parts of modified blocking filler, 0.5-1 part of stabilizer and 0.5-1 part of antioxidant;
the modified blocking filler is prepared from nano cellulose and mica sheets according to the weight ratio of 1:1, and the mass ratio of the components is obtained.
2. The high barrier material of claim 1, wherein the modified barrier filler is prepared by a method comprising:
(1) Dispersing nano-cellulose in deionized water, adding a silane coupling agent for ultrasonic treatment, then adding a hydrophobic agent, and continuing ultrasonic treatment; filtering and drying to obtain modified nano-cellulose;
(2) Adding the modified nano-cellulose into alkali liquor, uniformly mixing, adding urea, and standing; finally, adding mica sheets for heating treatment; and filtering and drying to obtain the modified barrier filler.
3. The high barrier material according to claim 2, wherein in the step (1), the amount of the hydrophobic agent is 3-7% of the mass of the nanocellulose; the dosage of the silane coupling agent accounts for 0.3 to 0.7 percent of the mass of the nano-cellulose; the ultrasonic treatment time is 10-30 min, the ultrasonic treatment power is 900w, and the ultrasonic treatment frequency is 20KHZ.
4. The high barrier material of claim 3, wherein the hydrophobic agent is selected from the group consisting of dimethicone; the silane coupling agent is KH-550.
5. The high barrier material of claim 2, wherein the alkali solution is selected from NaOH solution or KOH solution, and the concentration of the alkali solution is 0.1-1.0 moL/L; the mass ratio of the alkali liquor to the urea to the modified nano-cellulose is 1: (0.01-0.1): 1; the standing treatment time is 10-30 min.
6. The high barrier material of claim 2, wherein the mica platelets are sericite platelets; the temperature of the heating treatment is 60-80 ℃, and the time is 0.5-1 h.
7. The high barrier material of claim 1, wherein the stabilizer is stearic acid; the antioxidant is antioxidant 1010.
8. The method for preparing the high-barrier material of any one of claims 1 to 7, characterized in that the preparation method comprises the following steps: weighing the raw materials in parts by weight, uniformly mixing, drying in vacuum, placing in an internal mixer for mixing, cooling, granulating, and extruding in a double-screw extruder to obtain plastic particles, namely the high-barrier material.
9. The method according to claim 8, wherein the temperature of the vacuum drying is 60 to 70 ℃; the temperature of the internal mixer is 150-180 ℃, and the internal mixing time is 20-30 min.
10. Use of the high barrier material according to any one of claims 1 to 7 for the preparation of a high barrier bottle.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105263708A (en) * | 2013-03-14 | 2016-01-20 | 智能星球技术公司 | Repulpable and recyclable composite packaging articles and related methods |
| US20170037155A1 (en) * | 2015-08-06 | 2017-02-09 | American University | Thermally stable, dispersible cellulose nanocrystals |
| JP2020007492A (en) * | 2018-07-11 | 2020-01-16 | 旭化成株式会社 | Cellulose-containing resin composition |
| CN112912430A (en) * | 2018-10-22 | 2021-06-04 | 东洋制罐集团控股株式会社 | Gas barrier composition |
| JP2021113309A (en) * | 2020-01-16 | 2021-08-05 | 東洋製罐グループホールディングス株式会社 | Cellulose nanocrystal-containing coating liquid |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105263708A (en) * | 2013-03-14 | 2016-01-20 | 智能星球技术公司 | Repulpable and recyclable composite packaging articles and related methods |
| US20170037155A1 (en) * | 2015-08-06 | 2017-02-09 | American University | Thermally stable, dispersible cellulose nanocrystals |
| JP2020007492A (en) * | 2018-07-11 | 2020-01-16 | 旭化成株式会社 | Cellulose-containing resin composition |
| CN112912430A (en) * | 2018-10-22 | 2021-06-04 | 东洋制罐集团控股株式会社 | Gas barrier composition |
| JP2021113309A (en) * | 2020-01-16 | 2021-08-05 | 東洋製罐グループホールディングス株式会社 | Cellulose nanocrystal-containing coating liquid |
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Denomination of invention: A high barrier material and its preparation method Granted publication date: 20230512 Pledgee: Shandong Ningyang Rural Commercial Bank Co.,Ltd. Pledgor: Tai'an Xinming Plastic Industry Co.,Ltd. Registration number: Y2024980005728 |