CN112778561B - Antibacterial flexible cover plate and preparation method thereof - Google Patents
Antibacterial flexible cover plate and preparation method thereof Download PDFInfo
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- CN112778561B CN112778561B CN202011620450.2A CN202011620450A CN112778561B CN 112778561 B CN112778561 B CN 112778561B CN 202011620450 A CN202011620450 A CN 202011620450A CN 112778561 B CN112778561 B CN 112778561B
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- 238000011049 filling Methods 0.000 claims abstract description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 17
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 34
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses an antibacterial flexible cover plate which sequentially comprises a transparent flexible substrate, a first hardened layer, a nanopore array antibacterial layer and a second hardened layer; the transparent flexible substrate is one of a transparent polyimide film, polyacrylonitrile or PET; the first hardened layer and the second hardened layer are made of flexible cover plate hardening liquid; the nanopore array antibacterial layer is prepared by filling resin materials into a nanopore array, wherein the resin materials are prepared from urethane acrylate resin, amino/mercapto functional group-containing resin, silver ion solution and a solvent with swelling effect; also discloses a preparation method. According to the invention, the nano-pore array is filled with the antibacterial material, so that the interlayer binding force is enhanced; the ultra-large specific surface area of the nano-pores increases the leaching rate of silver ions and controls the leaching speed of the silver ions; the light transmittance of the antibacterial layer main body resin is increased; all the manufacturing processes are realized through roll-to-roll and coating processes, the process quality is stable, the investment of special equipment is reduced, the cost is reduced, and the product price is more competitive.
Description
Technical Field
The invention relates to the technical field of flexible display screens, in particular to an antibacterial flexible cover plate and a preparation method thereof.
Background
Studies have shown that people touch a cell phone thousands of times a day, with values varying from person to person, and an average of about 150 times per day, including face contact during phone calls. Microbiologists found that there were 7000 bacteria including enterococcus and pseudomonas on the surface of the cell phone through random sampling study. Most of these bacteria come from contact with the human hand or face, except for the adsorption of the cell phone itself from the environment, and microbiologists recommend cleaning the cell phone with an antibacterial wet wipe every day. This is difficult to achieve, and worse still, the particular temperature conditions of the handset cause it to become a hotbed for bacterial growth, and then to be carried along with contact with the hands to other surfaces, such as keyboards, dishware or children's hands and faces; the same situation will occur on the surface of wearable electronics in the future. The adhesion and propagation of bacteria on the surfaces of various materials can cause a series of serious consequences, the antibacterial performance of the surfaces of the materials is not only a research hotspot, but also receives the market attention, and the development of a flexible cover plate structure with the antibacterial function has important application value. Due to the particularity of the flexible cover plate, the hardness of the surface cannot be guaranteed by adopting the traditional antibacterial coating, the traditional antibacterial coating is easy to lose efficacy, and meanwhile, the light transmittance is easily influenced, so that the limited sterilization function is realized, and meanwhile, the performance of the flexible cover plate is kept.
Disclosure of Invention
In order to solve the above difficulties, the present invention provides an antibacterial flexible cover sheet which takes into account the performance of the flexible cover sheet and provides an effective sterilization function.
In order to achieve the purpose, the invention adopts the following technical scheme:
an antibacterial flexible cover plate sequentially comprises a transparent flexible substrate, a first hardened layer, a nanopore array antibacterial layer and a second hardened layer; the transparent flexible substrate is one of a transparent polyimide film, polyacrylonitrile or polyethylene terephthalate; the first hardened layer and the second hardened layer are made of flexible cover plate hardening liquid; the nano-pore array antibacterial layer is prepared by filling resin materials into the nano-pore array, and the resin materials are polyurethane acrylate resin and amino/sulfydryl (-NH) 3 v-SH) functional group resin, silver ion solution and solvent with swelling function.
The thickness of the first hardening layer of the antibacterial flexible cover plate is 5-15 mu m, and the thickness of the second hardening layer is 1-2 mu m; the depth of the nano hole is less than the thickness of the first hardening layer.
The thickness of the first hardening layer of the antibacterial flexible cover plate is preferably 8 micrometers; the nanopore depth is preferably 6 μm.
The antibacterial flexible cover plate comprises a flexible cover plate hardening liquid and a flexible cover plate hardening liquid, wherein the flexible cover plate hardening liquid is prepared from the following components in a mass ratio of 100: 0-20 parts of urethane acrylate resin and silicon dioxide. The hardening degree can be controlled by adjusting the using amount of the silicon dioxide, so that the elastic modulus of the hardened layer is adjusted, the toughness of the hardened layer is improved, and the impact resistance and the bending resistance are improved. When the hardened layer and the antibacterial layer are made of the same main resin material, the two layers have good binding force; the antibacterial layer introduces amino/mercapto groups inside the pores in order to be able to sufficiently adsorb silver ions.
In the antibacterial flexible cover plate, in the resin material filled in the nanopore array antibacterial layer, the molar ratio of the urethane acrylate resin to the amino/mercapto functional group-containing resin is 2: 1; the silver ion solution is silver nitrate solution, and the concentration is 1 g/L; the solvent with swelling function is alcohol, isopropanol or acetone, and the adding amount of the solvent is 10-30% of the mass of the solvent water in the silver nitrate solution.
The refractive index of the nano-pore array antibacterial layer is consistent with that of the first hardened layer, the elastic modulus of the nano-pore array antibacterial layer is less than that of the first hardened layer, and the surface energy of the nano-pore array antibacterial layer is higher than that of the first hardened layer. The silica in the hardened layer affects the refractive index to some extent, and the refractive index can be appropriately adjusted by adjusting the content of silica and the absorptivity of silver ions. The antibacterial layer has a low elastic modulus for increasing elasticity, and the nanopores are in a compressed state when bent and are not easily delaminated. Because of the existence of amino/sulfydryl in the antibacterial layer, the antibacterial layer is more hydrophilic and has higher surface energy.
The preparation method of the antibacterial flexible cover plate comprises the following steps:
(1) preparing a first hardened layer: coating the flexible cover plate hardening liquid on one side of the transparent flexible substrate, and semi-curing to obtain a first hardening layer;
(2) preparing a nanopore array antibacterial layer: imprinting a nanopore array on the semi-solidified first hardened layer by using a template with a bulge; then filling a resin material prepared from polyurethane acrylate resin, amino/mercapto functional group-containing resin, silver ion solution and a solvent with swelling effect into the nanopore array structure, curing, and immersing into the silver ion solution to obtain a nanopore array antibacterial layer;
(3) preparing a second hardened layer: and coating the flexible cover plate hardening liquid on the nano-pore array antibacterial layer to be cured into a second hardened layer, thus obtaining the antibacterial flexible cover plate.
In the preparation method of the antibacterial flexible cover plate, in the step (2), the template with the protrusions is a V-shaped protruding nickel template; the specific stamping method comprises the following steps: and (3) attaching the V-shaped protruding nickel template to a round metal roller for imprinting by adopting a roll-to-roll mode.
According to the preparation method of the antibacterial flexible cover plate, in the step (2), the filling adopts a coating mode; and after solidification, immersing the silver ion solution for 2-5 min.
According to the preparation method of the antibacterial flexible cover plate, the semi-curing in the step (1) is the first-step curing of step-by-step curing or stepped curing; the curing mode in the steps (1) to (3) is thermal curing or UV curing, and the thermal curing temperature is 80-100 ℃.
Compared with the prior art, the invention has the advantages that:
1. the filling of the nanopore array with a functional material can reduce the potential for delamination: if the traditional antibacterial coating is adopted, the bonding force between layers is low; and through the nanopore array structure, a plurality of nano holes are dug in the hardened structure, the contact area between the coatings is increased, and the binding force between the layers is enhanced, so that the antibacterial flexible cover plate has a simple structure, the number of layers and the thickness are reduced, and compared with the technical scheme disclosed by CN103072348B, the adhesive layer is removed, but the binding force between the layers is still stable.
2. The adsorption capacity and the leaching rate of silver ions can be increased through the three-dimensional structure and the ultra-large specific surface area of the nano-pores, the leaching speed of the silver ions is controlled, and the antibacterial reaction area can be increased; in addition, when the functional groups for adsorbing silver ions are filled, a solvent with a swelling effect is added, so that the adsorption depth can be increased, and the antibacterial capacity can be improved.
The V-shaped nano holes have an anti-reflection effect, so that the transparency can be improved to a certain extent, and the light transmission performance is not influenced while the hardness of the cover plate is ensured.
4. The first hardened layer and the second hardened layer are made of the same material, the adhesion force is good, and the stability of the antibacterial structure layer can be protected; the resin material filled in the antibacterial layer has good elasticity, and can improve the toughness of the hardened layer so as to increase the shock resistance of the coating and increase the bending resistance; and the main material filled with resin is consistent with the main material of the hardened layer, so that the light transmittance is increased, the compatibility of the material is improved, and the stability and the adhesion capability of each layer of the cover plate are enhanced.
5. All the manufacturing processes of the invention can be realized by roll-to-roll and coating processes, and special equipment is not required to be purchased during operation, so that the stability of the process quality is ensured, the investment cost is greatly reduced, the product price is lower, and the product has higher competitiveness.
Drawings
FIG. 1 is a schematic structural view of an antibacterial flexible cover plate according to the present invention; wherein: 1-a transparent flexible substrate; 2-a first hardened layer; 3-a nanopore array antibacterial layer; 4-a second hardened layer;
fig. 2 is a schematic view of a preparation process of the antibacterial flexible cover plate of the invention: step 1-transparent flexible substrate; step 2-coating a first hardening layer; step 3-preparing a nanopore array; step 4-resin material filling the nanopore array; step 5-immersing in silver ion solution; step 6-apply a second hardened layer.
Fig. 3 is a schematic diagram of a V-shaped nanopore array imprinting method.
Detailed Description
sequentially forming transparent flexible polyimide film substrates; a first hardened layer having a thickness of 8 μm; the nano-pore array antibacterial layer has the depth of 6 mu m; a second hardened layer having a thickness of 1 μm; the first hardened layer and the second hardened layer are made of 100 parts by mass of urethane acrylate (PUA) resin and 15 parts by mass of silica; the nano-pore array antibacterial layer is prepared by filling resin materials into a nano-pore array, wherein the resin materials are prepared from 10 mol parts of polyurethane acrylate resin, 5 mol parts of amino functional group-containing resin, 1g/L silver nitrate solution and isopropanol serving as a swelling solvent, and the addition amount of the isopropanol is 10% of the mass of the solvent water in the silver nitrate solution.
Example 2: as shown in fig. 1, an antibacterial flexible cover sheet:
sequentially forming transparent flexible polyacrylonitrile substrates; a first hardened layer having a thickness of 15 μm; the nano-pore array antibacterial layer is provided with nano-pores with the depth of 13 mu m; a second hardened layer having a thickness of 2 μm; the first hardened layer and the second hardened layer are made of 100 parts by mass of urethane acrylate (PUA) resin and 20 parts by mass of silica; the nano-pore array antibacterial layer is prepared by filling resin materials into a nano-pore array, wherein the resin materials are prepared from 20 mol parts of urethane acrylate resin, 10 mol parts of resin containing mercapto functional groups, 1g/L silver nitrate solution and acetone serving as a swelling solvent, and the addition amount of the acetone is 30% of the mass of solvent water in the silver nitrate solution.
Example 3: as shown in fig. 1, an antibacterial flexible cover sheet:
sequentially forming transparent flexible polyethylene terephthalate substrates; a first hardened layer having a thickness of 5 μm; the nano-pore array antibacterial layer is provided with nano-pores with the depth of 3 mu m; a second hardened layer having a thickness of 2 μm; the first hardened layer and the second hardened layer are made of 100 parts by mass of urethane acrylate (PUA) resin and 10 parts by mass of silica; the nano-pore array antibacterial layer is prepared by filling resin materials into a nano-pore array, wherein the resin materials are prepared from 20 mol parts of polyurethane acrylate resin, 10 mol parts of amino functional group-containing resin, 1g/L silver nitrate solution and swelling solvent alcohol, and the adding amount of the alcohol is 20% of the mass of the solvent water in the silver nitrate solution.
Example 4: as shown in fig. 1, an antibacterial flexible cover sheet:
sequentially forming transparent flexible polyethylene terephthalate substrates; a first hardened layer having a thickness of 12 μm; the nano-pore array antibacterial layer has the depth of 6 mu m; a second hardened layer having a thickness of 1 μm; the first hardened layer and the second hardened layer are made of hardened liquid consisting of oligomeric siloxane containing epoxy groups, oxetane monomer, initiator and solvent; the nano-pore array antibacterial layer is prepared by filling resin materials into a nano-pore array, wherein the resin materials are prepared from 30 mol parts of polyurethane acrylate resin, 15 mol parts of amino functional group-containing resin, 1g/L silver nitrate solution and isopropanol serving as a swelling solvent, and the addition amount of the isopropanol is 15% of the mass of the solvent water in the silver nitrate solution.
Example 5: as shown in fig. 1, an antibacterial flexible cover sheet:
sequentially forming transparent flexible polyacrylonitrile substrates; a first hardened layer having a thickness of 8 μm; the nano-pore array antibacterial layer is provided with nano-pores with the depth of 6 mu m; a second hardened layer having a thickness of 1 μm; the first hardened layer and the second hardened layer are made of flexible cover plate hardening liquid; the nano-pore array antibacterial layer is prepared by filling resin materials into a nano-pore array, wherein the resin materials are prepared from 30 mol parts of polyurethane acrylate resin, 15 mol parts of amino functional group-containing resin, 1g/L silver nitrate solution and acetone serving as a swelling solvent.
Example 6: as shown in fig. 2 and 3, the method for preparing the antibacterial flexible cover plate of examples 1 to 3 includes the steps of:
(1) preparing a first hardened layer: uniformly mixing polyurethane acrylate resin and silicon dioxide according to a ratio, coating the mixture on one side of a transparent flexible substrate, and semi-curing at the temperature of 80 ℃ to obtain a first hardened layer;
(2) preparing a nano-pore array antibacterial layer: adhering a V-shaped protruding nickel template to a round metal roller in a roll-to-roll mode, and imprinting a nanopore array on the semi-solidified first hardened layer; then filling a resin material prepared from polyurethane acrylate resin, amino/mercapto functional group-containing resin, silver ion solution and a solvent with swelling effect according to a ratio into the nanopore array structure by using a scraper, and immersing into a silver nitrate solution with the concentration of 1g/L for 5min after curing to obtain a nanopore array antibacterial layer;
(3) preparing a second hardened layer: and uniformly mixing the polyurethane acrylate resin and the silicon dioxide according to the proportion, coating the mixture on the nano-pore array antibacterial layer, and curing the mixture at the temperature of 100 ℃ to form a second hardened layer, thus obtaining the antibacterial flexible cover plate.
Example 7: as shown in fig. 2 and 3, the method for preparing the antibacterial flexible cover plate of embodiment 4 includes the following steps:
(1) preparing a first hardened layer: coating a hardening solution consisting of oligosiloxane containing epoxy groups, oxetane monomer, initiator and solvent on one side of a transparent flexible substrate, and semi-curing in a UV curing mode to obtain a first hardening layer;
(2) preparing a nano-pore array antibacterial layer: imprinting a nanopore array on the semi-solidified first hardened layer by using a V-shaped raised nickel template in a roll-to-roll mode; then filling a resin material prepared from polyurethane acrylate resin, amino functional group-containing resin, silver ion solution and a solvent with swelling function according to a ratio into the nanopore array structure by using a scraper, and immersing the cured resin material into a silver nitrate solution with the concentration of 1g/L for 4min to obtain a nanopore array antibacterial layer;
(3) preparing a second hardened layer: and coating a hardening liquid consisting of epoxy-containing oligosiloxane, an oxetane monomer, an initiator and a solvent on the nano-pore array antibacterial layer to be cured into a second hardening layer, thus obtaining the antibacterial flexible cover plate.
Example 8: as shown in fig. 2 and 3, the method for preparing the antibacterial flexible cover plate of example 5 includes the following steps:
(1) preparing a first hardened layer: coating the flexible cover plate hardening liquid on one side of the transparent flexible substrate, and semi-curing to obtain a first hardening layer;
(2) preparing a nanopore array antibacterial layer: imprinting a nanopore array on the semi-solidified first hardened layer by using a template with protrusions in a roll-to-roll mode; then filling a resin material prepared from polyurethane acrylate resin, amino functional group-containing resin, silver ion solution and a solvent with swelling effect according to a ratio into the nanopore array structure, and immersing the nanopore array structure into a silver nitrate solution with the concentration of 1g/L for 2min after curing to obtain a nanopore array antibacterial layer;
(3) preparing a second hardened layer: and coating the flexible cover plate hardening liquid on the nano-pore array antibacterial layer to be cured into a second hardened layer, thus obtaining the antibacterial flexible cover plate.
To verify the effect of the product of the present invention, the inventors conducted an antibacterial effect experiment using the product of example 1 and a comparative product, the contents of which are as follows:
firstly, an antibacterial effect experiment:
1. experimental bacterial types:
staphylococcus aureus (gram-positive bacteria) and Escherichia coli (gram-negative bacteria) are representative.
2. The experimental contents are as follows:
reference is made to the national standard GB/T31402-2015 test method for the antibacterial property of the surface of plastic
3. And (3) calculating the sterilization rate:
according to the sanitation industry standard & lt & ltantibacterial and bacteriostatic effect evaluation method & gt WS/T650-2019:
X＝(A-B)/A*100％
x is the bactericidal rate, A is the amount of bacteria recovered from the control sample, and B is the amount of bacteria recovered from the test sample.
4. Experimental materials:
antibiotic flexible apron: sequentially forming transparent flexible polyimide film substrates; a first hardened layer having a thickness of 9 μm; the depth of the nanometer hole is 6 mu m; a second hardened layer having a thickness of 1 μm; the first hardened layer and the second hardened layer are made by uniformly mixing 100 parts by mass of urethane acrylate (PUA) resin and 15 parts by mass of silicon dioxide; the nano-pore array antibacterial layer is prepared by filling resin materials into a nano-pore array, wherein the resin materials are prepared from 20 mol parts of urethane acrylate resin, 10 mol parts of amino functional group-containing resin, a solvent with swelling effect, namely isopropanol, and a silver nitrate solution with the concentration of 1 g/L; prepared according to the preparation method of example 6.
Comparative example: the antibacterial flexible cover plate is not provided with a second hardened layer; prepared by the method of steps (1) to (2) of example 6.
5. The experimental results are as follows:
1) the antibiotic flexible apron of this application: the first hardened coating thickness was 9 microns; the thickness of the second hardened coating was 1 micron.
Performing experiments according to the test method for the antibacterial performance of the surface of the plastic to obtain the sterilization rate;
2) comparative example: the thickness of the first hardened layer was 9 μm; the second hardened layer was 0 μm thick (the second hardened coating was not prepared).
Performing experiments according to the test method for the antibacterial performance of the surface of the plastic to obtain the sterilization rate;
the results of comparing the sterilization rates of the above two antibacterial flexible cover plates are shown in table 1.
Table 1 two antimicrobial flexible cover plate sterilization rate results
| Staphylococcus aureus bactericidal rate | Sterilizing rate of Escherichia coli | |
| Comparative example antibacterial flexible cover plate | 99.9％ | 99.9％ |
| This application antibiotic flexible apron | 96％ | 96％ |
From the above results of sterilization rate, it is clear that the sterilization rate is not much reduced after the second cured layer is applied. The second sclerosis layer has guaranteed surface hardness, simultaneously, also lets antibacterial coating not directly receive external force and damages, has guaranteed its stability, though the bactericidal rate reduces slightly, but its is thinner, can let antibacterial active ingredient slowly permeate, prevents that silver ion from losing activity too fast, has prolonged antibacterial coating's live time.
Claims (7)
1. An antibiotic flexible cover plate which is characterized in that: the transparent flexible substrate, the first hardened layer, the nanopore array antibacterial layer and the second hardened layer are sequentially arranged; the transparent flexible substrate is one of a transparent polyimide film, polyacrylonitrile or polyethylene terephthalate; the first hardened layer and the second hardened layer are made of flexible cover plate hardening liquid; the nanopore array antibacterial layer is prepared by filling resin materials into a nanopore array, wherein the resin materials are prepared from urethane acrylate resin, amino/mercapto functional group-containing resin, silver ion solution and a solvent with swelling effect; the thickness of the first hardening layer is 5-15 μm, and the thickness of the second hardening layer is 1-2 μm; the depth of the nano hole is less than the thickness of the first hardening layer; the mass ratio of the flexible cover plate hardening liquid is 100: 0-20 parts of urethane acrylate resin and silicon dioxide; in the resin material filled in the nanopore array antibacterial layer, the molar ratio of the urethane acrylate resin to the amino/mercapto functional group-containing resin is 2: 1; the silver ion solution is silver nitrate solution, and the concentration is 1 g/L; the solvent with swelling function is alcohol, isopropanol or acetone, and the adding amount of the solvent is 10-30% of the mass of the solvent water in the silver nitrate solution.
2. The antimicrobial flexible cover sheet of claim 1, wherein: the thickness of the first hardening layer is 8 mu m; the depth of the nano-pores is 6 μm.
3. The antimicrobial flexible cover sheet of claim 1, wherein: the refractive index of the nano-pore array antibacterial layer is consistent with that of the first hardened layer, the elastic modulus of the nano-pore array antibacterial layer is less than that of the first hardened layer, and the surface energy of the nano-pore array antibacterial layer is higher than that of the first hardened layer.
4. A method of manufacturing an antimicrobial flexible cover sheet according to any of claims 1 to 3, comprising the steps of:
(1) preparing a first hardened layer: coating the flexible cover plate hardening liquid on one side of the transparent flexible substrate, and semi-curing to obtain a first hardening layer;
(2) preparing a nanopore array antibacterial layer: imprinting a nanopore array on the semi-solidified first hardened layer by using a template with a bulge; then filling a resin material prepared from urethane acrylate resin, amino/mercapto functional group-containing resin, silver ion solution and a solvent with swelling effect into the nanopore array structure, curing, and immersing into the silver ion solution to obtain a nanopore array antibacterial layer;
(3) preparing a second hardened layer: and coating the flexible cover plate hardening liquid on the nano-pore array antibacterial layer to be cured into a second hardened layer, thus obtaining the antibacterial flexible cover plate.
5. The method for preparing the antibacterial flexible cover plate according to claim 4 is characterized in that: in the step (2), the template with the protrusions is a V-shaped protruding nickel template; the specific stamping method comprises the following steps: and (3) attaching the V-shaped convex nickel template to a round metal roller for imprinting by adopting a roll-to-roll mode.
6. The method for preparing the antibacterial flexible cover plate according to claim 4, characterized in that: in the step (2), the filling adopts a coating mode; and after curing, immersing the silver ion solution for 2-5 min.
7. The method for preparing the antibacterial flexible cover plate according to claim 4 is characterized in that: the semi-curing in the step (1) is a first-step curing of step-by-step curing or step-by-step curing; the curing mode in the steps (1) to (3) is thermal curing or UV curing, and the thermal curing temperature is 80-100 ℃.
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Denomination of invention: An antibacterial flexible cover plate and its preparation method Granted publication date: 20220902 Pledgee: Bank of China Co.,Ltd. Changzhou New North Branch Pledgor: Jiangsu Chengrui Technology Co.,Ltd. Registration number: Y2024980026338 |