CN113307997A - High-strength high-light-transmittance flexible substrate film and application thereof - Google Patents
High-strength high-light-transmittance flexible substrate film and application thereof Download PDFInfo
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- 238000002834 transmittance Methods 0.000 title claims abstract description 34
- 239000000758 substrate Substances 0.000 title claims abstract description 31
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 49
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 49
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 15
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000661 sodium alginate Substances 0.000 description 6
- 235000010413 sodium alginate Nutrition 0.000 description 6
- 229940005550 sodium alginate Drugs 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920001661 Chitosan Polymers 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000011846 petroleum-based material Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
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Abstract
The invention discloses a high-strength high-light-transmittance flexible substrate film and application thereof, wherein the substrate film is a polyisocyanate-sodium carboxymethylcellulose blend film, and the preparation method comprises the steps of dissolving sodium carboxymethylcellulose powder in a solvent system, uniformly stirring, and removing bubbles to obtain a sodium carboxymethylcellulose solution; dripping the water-soluble polyisocyanate solution into the sodium carboxymethylcellulose solution, uniformly stirring, and removing bubbles to obtain a blending solution of sodium carboxymethyl cellulose and water-soluble polyisocyanate; and pouring the blending solution into a culture dish, drying at constant temperature for 12h to complete crosslinking, and stripping the solution from the culture dish to obtain the polyisocyanate-sodium carboxymethylcellulose blending film. The flexible substrate film prepared by the invention has higher breaking strength and good light transmittance, and the preparation method of the film is simple, nontoxic and harmless, meets the requirements of environmental protection and energy conservation, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of transparent conductive films, in particular to a high-strength high-light-transmittance flexible substrate film and application thereof.
Background
The flexible transparent conductive film is an indispensable component in electronic devices such as tablet computers, smart phones, organic light emitting diodes and electronic skins, and generally comprises a film conductive layer and a substrate film. As a base film of the flexible transparent conductive film, in addition to high light transmittance, good flexibility and mechanical strength are required. Commonly used base film materials can be classified into two broad categories, one is petroleum-based materials such as polyethylene terephthalate (PET), Polyimide (PI), Polydimethylsiloxane (PDMS), and the like, and the other is biomass materials such as nanocellulose (CNF), Chitosan (CS), Sodium Alginate (SA), and the like. Although the flexible transparent conductive film prepared by using the petroleum-based material shows better comprehensive performance, with the increasing exhaustion of global petroleum resources and the increasing serious pollution caused by difficult degradation of the petroleum-based material, researchers begin to put the attention to the biomass material with wide sources and low price. For example, "chitosan flexible transparent conductive film based on silver nanowire conductive network" with patent number CN201710836660.7, and "sodium alginate based transparent conductive film and preparation method thereof" with patent number CN201410019636.0 respectively disclose flexible transparent conductive films prepared by using chitosan and sodium alginate as base films. However, the substrate film prepared from the biomass material has weak mechanical mechanics and is difficult to meet the practical use. The biomass material is crosslinked by adopting a proper crosslinking agent, so that the mechanical property of the biomass can be effectively improved. For example, the patent No. CN201811331533.2 discloses a method for preparing a cross-linked modified sodium alginate film, which uses calcium chloride to cross-link sodium alginate and effectively improves the mechanical property of sodium alginate.
Sodium carboxymethylcellulose is a derivative of carboxymethylation of cellulose, is a natural polysaccharide polymer with the largest yield and the widest application, contains rich hydroxyl groups, has good biodegradability, biocompatibility and film-forming property, is widely applied to the industries of food, medicine, petroleum, textile and the like due to safety and non-toxicity, and is also used for developing various functional sodium carboxymethylcellulose thin films, but the sodium carboxymethylcellulose thin films have the advantages of common quality, brittle film, poor moisture and heat stability.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides the flexible substrate film with high strength and high light transmittance and the application thereof.
The technical scheme adopted for realizing the above purpose of the invention is as follows:
a high-strength high-light-transmittance flexible substrate film is provided, which is a polyisocyanate-sodium carboxymethylcellulose blend film and is prepared by the following method:
(1) dissolving sodium carboxymethylcellulose powder in a solvent system, uniformly stirring, and removing bubbles to obtain a sodium carboxymethylcellulose solution;
(2) dripping the water-soluble polyisocyanate solution into the sodium carboxymethylcellulose solution, uniformly stirring, and removing bubbles to obtain a blending solution of sodium carboxymethyl cellulose and water-soluble polyisocyanate;
(3) pouring the blending solution into a culture dish, drying at constant temperature to complete crosslinking, and stripping the solution from the culture dish to obtain the polyisocyanate-sodium carboxymethylcellulose blending film.
Furthermore, the sodium carboxymethylcellulose powder is dissolved by adopting water as a solvent system, the mass percent concentration of the prepared sodium carboxymethylcellulose solution is 2-5%, and preferably, the mass percent concentration of the sodium carboxymethylcellulose solution is 2%.
Further, the mass percentage concentration of the water-soluble polyisocyanate is 1-5%.
Further, the stirring temperature of the sodium carboxymethyl cellulose solution in the step (1) is 60-80 ℃, and the stirring time is 1-3 h.
Further, the stirring time in the step (2) is 1-2 h.
Further, the drying temperature in the step (3) is 40-60 ℃, and the drying time is 12-14h, preferably, the drying temperature is 50 ℃, and the drying time is 12 h.
Further, the flexible substrate conductive film is applied to electronic devices.
Compared with the prior art, the invention has the beneficial effects and advantages that:
1. the flexible substrate film has the advantages of wide raw material source, low price and simple film preparation method, adopts water-soluble polyisocyanate as a cross-linking agent to carry out cross-linking reaction with sodium carboxymethyl cellulose, contains a large amount of isocyanate, is cross-linked with the sodium carboxymethyl cellulose, and is beneficial to improving the mechanical property of the film; meanwhile, the film is nontoxic and harmless, has low energy consumption, meets the requirements of environmental protection and energy conservation, and has higher light transmittance and better mechanical property.
2. The flexible substrate film has the advantages of high strength, good light transmittance and good toughness, the breaking strength is up to 75Mpa, the optical light transmittance is up to 91%, and the elongation at break is up to 10%.
3. The flexible substrate film disclosed by the invention adopts water as a solvent, can be prepared at a lower temperature, is lower in cost and has a better application prospect in the aspect of electronic equipment.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a graph of the optical transmittance at 550nm of a high-strength, high-transmittance flexible base film prepared in examples 1-3 and comparative example 1 using a spectrophotometer;
FIG. 2 is a stress-tensile strength graph of a high strength, high light transmittance flexible substrate film prepared in examples 1 to 3 and comparative example 1 under an external force.
Detailed Description
The following examples are provided to illustrate the technical solutions of the present invention more clearly, and should not be construed as limiting the scope of the present invention.
Example 1
(1) Weighing 10g of sodium carboxymethylcellulose powder, dissolving in 500g of deionized water, placing at 60 ℃, stirring for 1h until the solution is uniform and transparent, and placing at room temperature after stirring to remove bubbles to obtain a 2 wt% sodium carboxymethylcellulose solution.
(2) 1 wt% of water-soluble polyisocyanate is weighed and added into the sodium carboxymethyl cellulose solution in the step (1) dropwise, and the mixture is stirred for 1 hour at room temperature. And after stirring, standing at room temperature for a period of time to remove bubbles, thereby obtaining the blend solution of sodium carboxymethylcellulose and water-soluble polyisocyanate.
(3) Pouring the blending solution into a culture dish, putting the culture dish into an air-blowing drying oven, finishing the crosslinking reaction for 12 hours at the temperature of 50 ℃, and stripping the crosslinking reaction from the culture dish to obtain the polyisocyanate-sodium carboxymethylcellulose blending film, namely the flexible substrate film.
Example 2
(1) Weighing 10g of sodium carboxymethylcellulose powder, dissolving in 500g of deionized water, placing at 70 ℃, stirring for 2 hours until the solution is uniform and transparent, and placing at room temperature after stirring to remove bubbles to obtain a 2 wt% sodium carboxymethylcellulose solution.
(2) 3 percent of water-soluble polyisocyanate is weighed and added into the sodium carboxymethyl cellulose solution in the step (1) dropwise, and stirred for 1.5h at room temperature. And after stirring, standing at room temperature for a period of time to remove bubbles, thereby obtaining the blend solution of sodium carboxymethylcellulose and water-soluble polyisocyanate.
(3) Pouring the blending solution into a culture dish, putting the culture dish into an air-blowing drying oven, finishing the crosslinking reaction for 12 hours at the temperature of 50 ℃, and stripping the crosslinking reaction from the culture dish to obtain the polyisocyanate-sodium carboxymethylcellulose blending film, namely the flexible substrate film.
Example 3
(1) Weighing 10g of sodium carboxymethylcellulose powder, dissolving in 500g of deionized water, placing at 80 ℃, stirring for 3h until the solution is uniform and transparent, and placing at room temperature after stirring to remove bubbles to obtain a 2 wt% sodium carboxymethylcellulose solution.
(2) 5% of water-soluble polyisocyanate is weighed and dripped into the sodium carboxymethyl cellulose solution in the step (1), and stirred for 2h at room temperature. And after stirring, standing at room temperature for a period of time to remove bubbles, thereby obtaining the blend solution of sodium carboxymethylcellulose and water-soluble polyisocyanate.
(3) Pouring the blending solution into a culture dish, putting the culture dish into an air-blowing drying oven, finishing the crosslinking reaction for 12 hours at the temperature of 50 ℃, and stripping the crosslinking reaction from the culture dish to obtain the polyisocyanate-sodium carboxymethylcellulose blending film, namely the flexible substrate film.
Comparative example 1
(1) Weighing 10g of sodium carboxymethylcellulose powder, dissolving in 500g of deionized water, placing at 70 ℃, stirring for 2 hours until the solution is uniform and transparent, and placing at room temperature after stirring to remove bubbles to obtain a 2 wt% sodium carboxymethylcellulose solution.
(2) Pouring the sodium carboxymethyl cellulose solution into a culture dish, putting the culture dish into a forced air drying oven, keeping the temperature at 50 ℃ for 12 hours, and peeling the culture dish to obtain the sodium carboxymethyl cellulose membrane.
Example 4
The high-strength and high-transmittance flexible base films prepared in examples 1 to 3 and the flexible base film prepared in comparative example 1 were subjected to an optical transmittance test, specifically, the film was measured using a spectrophotometer under a visible light condition of 0 to 800nm, and the transmittance at each wavelength was measured, with the results shown in fig. 1.
As can be seen from fig. 1, the optical transmittances of examples 1 to 3 and comparative example 1 respectively show a tendency of increasing with increasing wavelength, the greater the light transmittance, the better the light transmittance, under the condition of 550nm, the optical transmittance reached by the flexible substrate film prepared in example 1 is 90%, the optical transmittance reached by the flexible substrate conductive film prepared in example 2 is 88%, the optical transmittance reached by the flexible substrate conductive film prepared in example 3 is 87%, and the optical transmittance reached by the flexible substrate conductive film prepared in comparative example 1 is 93%.
Example 5
The high-strength and high-transmittance flexible base films prepared in examples 1 to 3 and the flexible base film in comparative example 1 were subjected to a breaking strength test, a tensile and compressive test was performed using a film breaking strength tester, and the results are shown in fig. 2.
As can be seen from fig. 2, as the pressure increases, the breaking strength of the flexible base film prepared in example 1 is 41Mpa, and the breaking elongation is 6%, the breaking strength of the flexible base film prepared in example 2 is 64Mpa, and the breaking elongation is 10%, the breaking strength of the flexible base film prepared in example 3 is 75Mpa, and the breaking elongation is 10%, and the breaking strength of the flexible base film prepared in comparative example 1 is 30Mpa, and the breaking elongation is 3.5%, and it can be seen that the greater the breaking strength is, the higher the strength of the prepared flexible base conductive film is.
The high-strength high-light-transmittance flexible substrate film has good light transmittance and good mechanical property, and the substrate film made of sodium carboxymethyl cellulose has good bending resistance, so that large-scale industrial production can be carried out.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The high-strength high-light-transmittance flexible substrate film is characterized by being a polyisocyanate-sodium carboxymethylcellulose blend film prepared by the following method:
(1) dissolving sodium carboxymethylcellulose powder in a solvent system, uniformly stirring, and removing bubbles to obtain a sodium carboxymethylcellulose solution;
(2) dripping the water-soluble polyisocyanate solution into the sodium carboxymethylcellulose solution, uniformly stirring, and removing bubbles to obtain a blending solution of sodium carboxymethyl cellulose and water-soluble polyisocyanate;
(3) pouring the blending solution into a culture dish, drying at constant temperature to complete crosslinking, and stripping the solution from the culture dish to obtain the polyisocyanate-sodium carboxymethylcellulose blending film.
2. A high strength, high light transmittance flexible substrate film as recited in claim 1, wherein said solvent system is water, and said solution of sodium carboxymethylcellulose has a concentration of 2% to 5% by mass.
3. A high strength, high light transmittance flexible substrate film as recited in claim 1, wherein said water-soluble polyisocyanate is present at a concentration of 1% to 5% by mass.
4. A high strength, high light transmittance flexible substrate film according to claim 1, wherein the stirring temperature of the sodium carboxymethyl cellulose solution in step (1) is 60-80 ℃ and the stirring time is 1-3 h.
5. A high strength, high light transmittance flexible substrate film according to claim 1, wherein the stirring time in step (2) is 1-2 h.
6. A high strength, high light transmittance flexible substrate film according to claim 1, wherein the drying temperature in step (3) is 40-60 ℃ and the drying time is 12-14 h.
7. Use of a high strength, high light transmittance flexible substrate film as defined in any one of claims 1 to 6 in an electronic device.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110570429.4A CN113307997A (en) | 2021-05-25 | 2021-05-25 | High-strength high-light-transmittance flexible substrate film and application thereof |
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| CN202110570429.4A CN113307997A (en) | 2021-05-25 | 2021-05-25 | High-strength high-light-transmittance flexible substrate film and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105940326A (en) * | 2014-01-29 | 2016-09-14 | 柯尼卡美能达株式会社 | Optical film |
| CN110294853A (en) * | 2019-06-28 | 2019-10-01 | 陕西科技大学 | A kind of HEC/PVA interpenetrating networks film and preparation method thereof |
| CN110643076A (en) * | 2019-08-14 | 2020-01-03 | 浙江海洋大学 | Preparation method of transparent substrate film of flexible electronic device |
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- 2021-05-25 CN CN202110570429.4A patent/CN113307997A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105940326A (en) * | 2014-01-29 | 2016-09-14 | 柯尼卡美能达株式会社 | Optical film |
| CN110294853A (en) * | 2019-06-28 | 2019-10-01 | 陕西科技大学 | A kind of HEC/PVA interpenetrating networks film and preparation method thereof |
| CN110643076A (en) * | 2019-08-14 | 2020-01-03 | 浙江海洋大学 | Preparation method of transparent substrate film of flexible electronic device |
Non-Patent Citations (3)
| Title |
|---|
| （日）中野凖三 等: "《木材化学》", 28 February 1989, 中国林业出版社 * |
| 何小维等: "《功能性碳水化合物及其应用技术丛书 医药用碳水化合物》", 31 January 2016, 中国轻工业出版社 * |
| 朱松文等: "《服装材料学》", 28 February 2001, 中国纺织出版社 * |
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