CN211319756U - Flexible conductive film - Google Patents

Flexible conductive film Download PDF

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Publication number
CN211319756U
CN211319756U CN201922119832.6U CN201922119832U CN211319756U CN 211319756 U CN211319756 U CN 211319756U CN 201922119832 U CN201922119832 U CN 201922119832U CN 211319756 U CN211319756 U CN 211319756U
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refractive index
coating
conductive film
range
flexible conductive
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耿龙飞
徐金龙
葛建峰
孔祥永
尹晓峰
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Great Rich Technology Co Ltd
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Hunan Zhongtian Bishui Membrane Technology Co ltd
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Abstract

The utility model provides a flexible conducting film, include: a transparent polyimide flexible substrate with first optical surface and second optical surface, first optical surface one side is equipped with first sclerosis coating, one side of second optical surface is equipped with first refractive index layer, nanometer silver line conducting layer and second refractive index layer, the utility model provides an etching line region and non-etching line region chromatic aberration great, the etching line is very heavy to the human eye seems, causes the very poor technical problem of consumer experience.

Description

Flexible conductive film
Technical Field
The utility model relates to an optical film, concretely relates to transparent polyimide film.
Background
In recent years, with the popularization of intelligent electronic products, electronic devices that are convenient to carry have become an essential part of people's lives. For example, in the market, electronic devices with various sizes and characteristics are full of life, people have higher and higher requirements on intelligent electronic devices, and particularly, consumers desire that the screen of the intelligent electronic device is large enough for better visual user experience, and meanwhile, the intelligent electronic device is convenient to carry and use. In order to solve the purpose that the screen is large enough and portable, people usually think of how to fold the intelligent electronic device for the purpose of portability, but there is a problem how to fold the display screen and ensure that the display function is not affected. The flexible display screen provides possibility for the intelligent electronic device to be foldable, however, a conductive film with strong bending resistance is required to be used in the flexible foldable equipment, a nano silver wire polyimide conductive film used by the conductive film can be bent in the current display screen, and as the nano silver wire polyimide conductive film has a formula and a product structure design defect, a larger chromatic aberration exists between an etched line area and a non-etched line area after laser, the etching line is very heavy when human eyes get up, and poor visual experience is brought to consumers.
SUMMERY OF THE UTILITY MODEL
The main object of the utility model is to provide a flexible conducting film solves etching line region and non-etching line region colour difference great, and the people's eye seems to etch the line very heavy, causes the very poor technical problem of consumer experience.
In order to realize the purpose, the utility model adopts the technical scheme that:
a flexible conductive film, comprising: the transparent polyimide flexible substrate is provided with a first optical surface and a second optical surface, a first hardened coating is arranged on one side of the first optical surface, and a first refractive index layer, a nano silver wire conducting layer and a second refractive index layer are arranged on one side of the second optical surface.
Further, the coating thickness range of the first low refractive index layer is 80-120nm, and the refractive index range is 1.2-1.45; outside this thickness range, the film material appears to be purplish or greenish; the refractive index range of the coating is 1.2-1.45, the lowest refractive index of organic resin (containing inorganic particles) which can be produced in mass production in the current market is more than or equal to 1.2, the refractive index is less than or equal to 1.45, and the larger the refractive index of the material surface is, the larger the reflectivity is.
Further, the glue in the first refractive index coating comprises:
organic resin: 5 to 20 percent of
Inorganic particles: 0.5 to 10 percent
Leveling agent: 0.5 to 5 percent
Initiator: 1 to 3 percent of
Solvent: 62 to 93 percent;
the organic resin is selected from: one or more of dipentaerythritol tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and urethane acrylate; the inorganic particles are hollow silica particles subjected to surface treatment, and the specific treatment comprises the following steps: purchasing 2 g of hollow silica nanoparticles (average diameter 15nm) from the market, putting the hollow silica nanoparticles into 50mL of anhydrous xylene solvent, adding 1mL of tridecafluorooctyl siloxane and 2mL of propenyl siloxane organic matter, refluxing for 5 hours, further grafting a hydrophobic group of tridecafluorooctyl and the organic matter containing unsaturated bonds to the surface of the silica particles, and finally drying at 120 ℃ for 10 hours to obtain the surface-treated silica particles .
Further, the thickness of the second low-refractive-index layer is 80-120nm, the refractive index is 1.2-1.45, and the thin film material looks purple or green when the thickness of the second low-refractive-index layer is not within the thickness range; the refractive index range of the coating is 1.2-1.45, the lowest refractive index of organic resin (containing inorganic particles) which can be produced in mass production in the current market is more than or equal to 1.2, the refractive index is less than or equal to 1.45, and the larger the refractive index of the material surface is, the larger the reflectivity is.
Further, the glue in the second refractive index coating comprises:
organic resin: 5 to 20 percent of
Inorganic particles: 0.5 to 10 percent
Leveling agent: 0.5 to 5 percent
Initiator: 1 to 3 percent of
Solvent: 62 to 93 percent;
the organic resin is selected from: one or more of dipentaerythritol tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and urethane acrylate; the inorganic particles are surface-treated hollow silica particles, and the preparation method of the surface-treated hollow silica particles is the same as that of the first refractive index layer.
Further, the nano silver wire conducting layer comprises a nano silver wire with the diameter ranging from 10 nm to 20nm and the length ranging from 50 μm to 200 μm, the larger the diameter is, the smaller the length is, the larger the silver wire packing density is, the larger the non-laser area reflectivity R2 in fig. 1 is, the heavier the etching line is, on the contrary, the smaller the diameter is, the larger the length is, the more favorable the problem of the heavy etching line is, the too small diameter and the too long length of the silver wire bring serious challenges to the production and synthesis of the actual silver wire, and the nano silver wire synthesis method comprises the following steps: respectively adding 1-butyl-3-methylimidazolium platinum chloride (0.0215g/1mL of glycol solution), triphenylphosphine (0.005g/1mL of glycol solution) and PVP-520000 solution (0.3g/10mL of glycol solution) into 100mL of glycol solution at room temperature, slowly stirring for 30min, slowly adding silver nitrate solution (0.23g/10mL of glycol solution) while stirring, slowly heating to 80 ℃ after continuously stirring for 40min, keeping for 5min, slowly heating to 150 ℃ for 5min, finally heating to 180 ℃ for 20min, naturally cooling to 160 ℃, stopping stirring for a period of time, cooling to room temperature, and keeping argon protection in the whole process; and removing PVP and other additives through multiple times of high-speed centrifugation, and cleaning and drying to obtain the nano silver wire with the diameter range of 10-20nm and the length range of 50-200 mu m.
Further, the thickness range of the transparent polyimide flexible substrate is 10-50 μm, and the refractive index range is 1.6-1.7.
Further, the thickness of the first hardened coating ranges from 1 to 5 μm, and the refractive index ranges from 1.45 to 1.55.
Further, the glue in the first hardened coating layer comprises:
organic resin: 10 to 40 percent of
Inorganic particles: 4 to 10 percent of
Leveling agent: 1-10%
A slipping auxiliary agent: 1 to 5 percent
Initiator: 1 to 3 percent of
Solvent: 49-83 percent;
the organic resin is selected from: pentaerythritol tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and urethane acrylate, wherein the inorganic particles are surface-treated silica particles, specifically, 2 g of silica nanoparticles (average diameter 25nm) are purchased from the market, put into 50mL of anhydrous xylene solvent, 2mL of tridecafluorooctylsiloxane and 2mL of acryl siloxane organic compound are added, refluxed for 5 hours, and then hydrophobic group tridecafluorooctyl and organic compound containing unsaturated bond are grafted onto the surface of the silica particles, and finally dried at 120 ℃ for 10 hours to obtain silica particles treated with fluorine-containing compound, and the larger the diameter of the treated particles, the poorer the optical effect of the film containing the hard coat layer is, and the surface of the particles is not surface-treated, the particles are easy to agglomerate in the actual use process; by adding the slipping auxiliary agent, the surface energy of the coating surface can be reduced, so that the Water Contact Angle (WCA) of the coating surface is improved, the uncovering force of a rear-end pad pasting and film tearing process is reduced, and the problem that a polyimide film with the thickness of 10-50 mu m is easy to crack in the film tearing process is solved.
Has the advantages that:
the first low refractive index layer is coated on the nano silver wire conducting layer, the reflectivity R1 of the light on the outer surface is reduced, the lower layer of the etching area of the nano silver wire conducting layer, the high and low refractive index matching of the second low refractive index layer and the colorless transparent polyimide, the reflectivity R2 of the light is lower, the difference between R1 and R2 is smaller (see figure 1), and the problem of larger chromatic aberration is further improved, the diameter of the nano silver wire prepared by the utility model is thinner, the length is long enough, the stacking density between the nano silver wires is reduced, and the problem of larger chromatic aberration or heavier etching wire is improved under the combined action of the two, the surfaces of particles in the medium-hardening coating glue and the low refractive index glue are jointly decorated by fluorine-containing groups and organic bonds containing unsaturated organic bonds, the aggregation among the particles is reduced, the fluorine-containing compounds further reduce the refractive index of the coating, and the reflectivity of the, unsaturated bonds on the surfaces of the particles participate in chemical reactions among organic resins, so that the capacity of resisting the outside of the coating surface is improved.
Drawings
Fig. 1 is a schematic diagram depicting the reflectances R1 and R2.
Fig. 2 is a schematic structural diagram of example 1, wherein 1 is a transparent polyimide substrate, 2 a first hardened coating, 3 a second low refractive index layer, 4 a nano silver wire conductive layer, 5 a first low refractive index layer.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
Example 1
Coating a first hardening coating glue on a first optical surface of a colorless and transparent polyimide substrate (a Korean Kolon substrate) with the thickness of 20 mu m and the refractive index of 1.63, performing thermal drying and UV curing to form a first hardening coating, coating a second low-refractive-index coating glue on a second optical surface of the colorless and transparent polyimide substrate, performing thermal drying and UV curing to form a second low-refractive-index coating, coating a nano silver wire coating liquid on the second low-refractive-index coating, performing thermal drying to form a nano silver wire conductive layer, coating the first low-refractive-index coating glue on the nano silver wire layer, performing thermal drying and UV curing to form a first low-refractive-index coating, and obtaining the flexible nano silver polyimide conductive film.
The first hardened coating layer is 1 mu m in coating thickness and 1.50 in refractive index, and the glue in the first hardened coating layer comprises organic resin with pentaerythritol tetra (meth) acrylate content of 10%, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate content of 5% and urethane acrylate content of 15%; the content of the silica particles subjected to surface treatment is 10%; the content of the leveling agent BYK-3760 is 2 percent; 3% of a slipping auxiliary agent, namely organic silicon modified polyurethane acrylate; initiator 184 content 2%; the initiator TPO content is 1%; and 52% of organic solvent.
The surface treatment of the silica particles in the first hardened coating is as follows:
2 g of silica nanoparticles (average diameter 25nm) were purchased from the market, and placed in 50mL of anhydrous xylene solvent, 2mL of tridecafluorooctylsiloxane and 2mL of acryl siloxane organic substance were added, and refluxed for 5 hours, and further a hydrophobic group tridecafluorooctyl group and an organic substance having an unsaturated bond were grafted onto the surface of the silica particles, and finally dried at 120 ℃ for 10 hours to obtain fluorine compound-treated silica particles.
The second low-refractive-index coating is 100nm in coating thickness, the thin film material looks bright, the coating refractive index is 1.35, and glue in the second low-refractive-index coating comprises: 5% of dipentaerythritol tetra (meth) acrylate, 2% of tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate and 3% of urethane acrylate; the content of the leveling agent BYK-3760 is 2%, and the leveling agent can enable glue to be well wetted on the surface of a base material and reduce the number of coating crystal points; initiator 184 content 2%; the initiator TPO content is 1%; 85% of organic solvent.
The silica particles in the second low refractive index coating are treated as follows:
2 g of hollow silica nanoparticles (average diameter 15nm) were purchased from the market, put in 50mL of anhydrous m-xylene solvent, added with 1mL of tridecafluorooctylsiloxane and 2mL of acryl siloxane organic substance, refluxed for 5 hours, further grafted with a hydrophobic group of tridecafluorooctyl and an organic substance containing an unsaturated bond onto the surface of the silica particles, and finally dried at 120 ℃ for 10 hours to obtain surface-treated silica particles.
The conductive layer of the nano silver wire (sheet resistance 80 omega /), the average diameter of the nano silver wire is 20nm, and the average length of the nano silver wire is 70 mu m.
The synthesis method of the nano silver wire comprises the following steps:
respectively adding 1-butyl-3-methylimidazolium platinum chloride (0.0215g/1mL of glycol solution), triphenylphosphine (0.005g/1mL of glycol solution) and PVP-520000 solution (0.3g/10mL of glycol solution) into 100mL of glycol solution at room temperature, slowly stirring for 30min, slowly adding silver nitrate solution (0.23g/10mL of glycol solution) while stirring, slowly heating to 80 ℃ after continuously stirring for 40min, keeping for 5min, slowly heating to 150 ℃ for 5min, finally heating to 180 ℃ for 20min, naturally cooling to 160 ℃, stopping stirring for a period of time, cooling to room temperature, and keeping argon protection in the whole process; and removing PVP and other additives through multiple times of high-speed centrifugation, and cleaning and drying to obtain the nano silver wire with the diameter range of 10-20nm and the length range of 50-200 mu m.
The first low refractive index coating, refractive index 1.35, optical thickness 100nm, outside this thickness range, the film material appears violet or green, the coating refractive index is 1.37, the glue in the first refractive index coating comprises: 5% of dipentaerythritol tetra (meth) acrylate, 2% of tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate and 3% of urethane acrylate; the content of the leveling agent BYK-3760 is 2 percent; initiator 184 content 2%; the initiator TPO content is 1%; 85% of organic solvent.
The silica particles in the first low refractive index coating are treated as follows:
2 g of hollow silica nanoparticles (average diameter 15nm) were purchased from the market, put in 50mL of anhydrous m-xylene solvent, added with 1mL of tridecafluorooctylsiloxane and 2mL of acryl siloxane organic substance, refluxed for 5 hours, further grafted with a hydrophobic group of tridecafluorooctyl and an organic substance containing an unsaturated bond onto the surface of the silica particles, and finally dried at 120 ℃ for 10 hours to obtain surface-treated silica particles.
The test results of the flexible conductive film prepared by the method described in example 1, that is, the etched line region and the non-etched line region have light color difference, which is hardly visible to human eyes and acceptable, and the slight degree of transmittance, haze and color difference are shown in table one
Example 2
Unlike example 1, the first low refractive index coating, refractive index 1.2.
After the flexible conductive film prepared by the method described in embodiment 2 is subjected to laser, the color difference between the etched line region and the non-etched line region is very light, which is hardly visible and acceptable to human eyes, and the test results of the slight degree of transmittance, haze, color difference and the like are shown in table one.
Example 3
Unlike example 1, the first low refractive index coating, refractive index 1.45.
After the flexible conductive film prepared by the method described in embodiment 3 is subjected to laser, the color difference between the etched line region and the non-etched line region is very light, which is hardly visible and acceptable to human eyes, and the test results of the slight degree of transmittance, haze, color difference and the like are shown in table one.
Example 4
Unlike example 1, the second low index coating, refractive index 1.2.
After the flexible conductive film prepared by the method described in embodiment 4 is subjected to laser, the color difference between the etched line region and the non-etched line region is very light, which is hardly visible and acceptable to human eyes, and the test results of the slight degree of transmittance, haze, color difference and the like are shown in table one.
Example 5
Unlike example 1, the second low index coating, refractive index 1.45.
After the flexible conductive film prepared by the method described in embodiment 5 is subjected to laser, the color difference between the etched line region and the non-etched line region is very light, which is hardly visible and acceptable to human eyes, and the test results of the slight degree of transmittance, haze, color difference and the like are shown in table one.
Example 6
Unlike example 1, the colorless transparent polyimide substrate had a refractive index of 1.6.
After the flexible conductive film prepared by the method described in embodiment 6 is subjected to laser, the color difference between the etched line region and the non-etched line region is very light, which is hardly visible and acceptable to human eyes, and the test results of the slight degree of transmittance, haze, color difference and the like are shown in table one.
Example 7
Unlike example 1, the colorless transparent polyimide substrate had a refractive index of 1.7.
After the flexible conductive film prepared by the method described in embodiment 7 is subjected to laser, the color difference between the etched line region and the non-etched line region is very light, which is hardly visible and acceptable to human eyes, and the test results of the slight degree of transmittance, haze, color difference and the like are shown in table one.
Example 8
Unlike example 1, the first refractive index coating was 80nm in optical thickness and the second refractive index coating was 80nm in optical thickness.
After the flexible conductive film prepared by the method described in embodiment 8 is subjected to laser, the color difference between the etched line region and the non-etched line region is very light, which is hardly visible and acceptable to human eyes, and the test results of the slight degree of transmittance, haze, color difference and the like are shown in table one.
Example 9
Unlike example 1, the first refractive index coating was 120nm in optical thickness and the second refractive index coating was 120nm in optical thickness.
After the flexible conductive film prepared by the method described in embodiment 9 is subjected to laser, the color difference between the etched line region and the non-etched line region is very light, which is hardly visible to human eyes, and acceptable, and the test results of the slight degree of transmittance, haze, and color difference are shown in table one.
Example 10
Unlike example 1, the nano silver wires had an average diameter of 20nm and an average length of 200 μm.
After the flexible conductive film prepared by the method described in embodiment 10 is subjected to laser, the color difference between the etched line region and the non-etched line region is very light, which is hardly visible and acceptable to human eyes, and the test results of the slight degree of transmittance, haze, color difference and the like are shown in table one.
Comparative example 1
Unlike example 1, there was no first low refractive index coating.
After the flexible conductive film prepared by the method described in comparative example 1 is subjected to laser, the etched line area and the non-etched line area have heavy chromatic aberration, the etched line is clearly seen by human eyes, and the test results are shown in table one, wherein the test results comprise unacceptable transmittance, haze, slight degree of chromatic aberration and the like.
Comparative example 2
Unlike example 1, no second low refractive index coating was included
After the flexible conductive film prepared by the method described in comparative example 2 is subjected to laser, the etched line area and the non-etched line area have heavy chromatic aberration, the etched line is clearly seen by human eyes, and the test results are shown in table one, such as unacceptable transmittance, haze and slight degree of chromatic aberration.
Comparative example 3
Unlike example 1, the first low refractive index was 1.52, and the second low refractive index was 1.52.
After the flexible conductive film prepared by the method described in comparative example 3 is subjected to laser, the etched line region and the non-etched line region have heavy chromatic aberration, the etched line is clearly seen by human eyes and is unacceptable, meanwhile, the color of the whole film surface looks red or green, and the test results of the slight degrees of transmittance, haze and chromatic aberration and the like are shown in table one.
Comparative example 4
Unlike example 1, the colorless transparent polyimide had a refractive index of 1.56.
After the flexible conductive film prepared by the method described in comparative example 4 is subjected to laser, the etched line area and the non-etched line area have heavy chromatic aberration, the etched line is clearly seen by human eyes, and the test results are shown in table one, such as unacceptable transmittance, haze and slight degree of chromatic aberration.
Comparative example 5
Unlike example 1, the colorless transparent polyimide had a refractive index of 1.72.
After the flexible conductive film prepared by the method described in comparative example 5 is subjected to laser, the etched line area and the non-etched line area have heavy chromatic aberration, the etched line is clearly seen by human eyes, and the test results are shown in table one, such as unacceptable transmittance, haze and slight degree of chromatic aberration.
Comparative example 6
Unlike example 1, the first low refractive index coating thickness was 50nm and the second low refractive index coating thickness was 50 nm.
After the flexible conductive film prepared by the method described in comparative example 6 is subjected to laser, the etched line area and the non-etched line area have heavy chromatic aberration, the etched line is clearly seen by human eyes, and the test results are shown in table one, such as unacceptable transmittance, haze and slight degree of chromatic aberration.
Comparative example 7
Unlike example 1, the first low refractive index coating thickness was 200nm and the second low refractive index coating thickness was 200 nm.
After the flexible conductive film prepared by the method described in comparative example 7 is subjected to laser, the etched line area and the non-etched line area have heavy chromatic aberration, the etched line is clearly seen by human eyes, and the test results are shown in table one, such as unacceptable transmittance, haze and slight degree of chromatic aberration.
Comparative example 8
Unlike example 1, the silver nanowires had an average diameter of 40nm and an average length of 10 μm.
After the flexible conductive film prepared by the method described in comparative example 8 is subjected to laser, the etched line area and the non-etched line area have heavy chromatic aberration, the etched line is clearly seen by human eyes, and the test results are shown in table one, such as unacceptable transmittance, haze and slight degree of chromatic aberration.
Figure DEST_PATH_GDA0002522295260000081
TABLE 1
The light weight of the etched line is, from good to poor, formed as;
the membrane surface appearance was from good to poor diamond-solid-;
r1: the radius is 1 mm;
r3: the radius is 3 mm;
and (3) internal bending: bending the conductive layer of the nano silver wire for 10 ten thousand times;
and (3) bending outwards: bent 10 ten thousand times toward the first HC cured coating.

Claims (6)

1. A flexible conductive film, comprising: the transparent polyimide flexible substrate is provided with a first optical surface and a second optical surface, a first hardened coating is arranged on one side of the first optical surface, and a first refractive index layer, a nano silver wire conducting layer and a second refractive index layer are arranged on one side of the second optical surface.
2. The flexible conductive film of claim 1, wherein the first index layer has a coating thickness in the range of 80-120nm and an index of refraction in the range of 1.2-1.45.
3. The flexible conductive film of claim 1, wherein the second refractive index layer has a coating thickness in the range of 80-120nm and a refractive index in the range of 1.2-1.45.
4. The flexible conductive film of claim 1, wherein the nanosilver wire conductive layer comprises nanosilver wires having a diameter in the range of 10-20nm and a length in the range of 50-200 μm.
5. The flexible conductive film of claim 1, wherein the transparent polyimide flexible substrate has a thickness in the range of 10 to 50 μm and a refractive index in the range of 1.6 to 1.7.
6. The flexible conductive film of claim 1, wherein the first hardened coating has a coating thickness in the range of 1-5 μm and a refractive index in the range of 1.45-1.55.
CN201922119832.6U 2019-11-29 2019-11-29 Flexible conductive film Active CN211319756U (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110993151A (en) * 2019-11-29 2020-04-10 湖南中天碧水膜科技有限公司 Flexible conductive film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110993151A (en) * 2019-11-29 2020-04-10 湖南中天碧水膜科技有限公司 Flexible conductive film

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Effective date of registration: 20220902

Address after: No. 26, Tonggang Road, Changjing Town, Jiangyin City, Wuxi City, Jiangsu Province, 214431

Patentee after: JIANGYIN TONGLI OPTOELECTRONIC TECHNOLOGY Co.,Ltd.

Address before: No. 346, 3rd floor, East complex, square, high speed railway south station, Wanbao Avenue, Louxing District, Loudi City, Hunan Province, 417000

Patentee before: Hunan Zhongtian Bishui Membrane Technology Co.,Ltd.