CN113604088A - Antistatic coating, high-adhesion and high-stability antistatic release film and preparation method - Google Patents
Antistatic coating, high-adhesion and high-stability antistatic release film and preparation method Download PDFInfo
- Publication number
- CN113604088A CN113604088A CN202110957591.1A CN202110957591A CN113604088A CN 113604088 A CN113604088 A CN 113604088A CN 202110957591 A CN202110957591 A CN 202110957591A CN 113604088 A CN113604088 A CN 113604088A
- Authority
- CN
- China
- Prior art keywords
- antistatic
- coating
- release
- film
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D183/04—Polysiloxanes
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- 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
- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- 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
- C08J2483/00—Characterised by the use of 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; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Abstract
The invention discloses an antistatic coating, an antistatic release film with high adhesion and stability and a preparation method; the antistatic coating is water-based dispersion liquid or ethyl acetate dispersion liquid containing an antistatic material; the antistatic release film prepared by using the antistatic coating as an external additive or an internal additive has a lasting antistatic effect, and the surface resistance can reach 103Omega/sq, high adhesion, stable release force and good transparency, can reduceSuch as contamination caused by static electricity when the release film is separated from the adhesive, peeling failure, etc.
Description
Technical Field
The invention belongs to the technical field of thin film materials, relates to a release film material, and particularly relates to an antistatic coating for improving the antistatic performance of the release film material, an antistatic ionization type film material which is prepared by using the antistatic coating and has good stability and adhesion, and a preparation technology thereof, so that the antistatic effect during release film separation is realized, and the excellent adhesion effect between a cured layer and a substrate is improved.
Background
The release film refers to a film having a surface with separability, and the release film has no stickiness or slight stickiness when contacted with a specific material under limited conditions. The production of common release films generally comprises the surface treatment of polyester films, including the coating of silicon release agents and fluorine release agents or the preparation and generation of plasma treatment, and release film materials are widely applied to the industries of electronics, printed circuit boards, packaging, film switches, waterproof materials, adhesive products, die cutting and punching processing and the like.
In general, release films are required to have certain antistatic properties. This is because the polyester film itself has an electrostatic insulating property and is liable to carry electrostatic charge or discharge, resulting in accumulation of static electricity, which leads to problems such as failure in peeling the release film from the adhesive layer or contamination.
At present, the methods for preparing the antistatic release film on the market can be mainly divided into the following three methods:
(1) adding an antistatic agent, a filler and the like into a production formula of the PET original film to enable the PET original film to have an antistatic effect, and then coating a release layer on the surface layer of the PET thin film to prepare the antistatic PET release film. The antistatic film prepared by adding the antistatic agent and the filler has the advantages of simple and convenient process and long lasting effect, but the addition of the antistatic agent can influence the polymerization process of PET, thereby influencing the mechanical property of the PET film.
(2) And coating an antistatic layer on at least one surface of the PET substrate and preparing an antistatic release film from the release layer. By coating the antistatic coating, the antistatic performance of the release film can be improved, and the preparation process is simpler. However, the antistatic coating is easy to migrate, so that the stability of the antistatic performance is poor, and the adhesion between the release layer and the substrate is low. In addition, the production process needs to go through more than two off-line coating processes, and foreign matters and scratches are easy to appear during the coating processThe quality problem is solved, and the production cost is higher. Utility model No. 201820739434.7 discloses an antistatic release film, including the basic unit, be located the basic unit below from the type layer, be located the nanometer particle layer of basic unit top and be located the antistatic layer of nanometer particle layer top. The antistatic layer is composite SnO with negative electricity on the surface2-SiO2The nano granular layer has good antistatic effect. However, the antistatic coating is easy to migrate, the stability of antistatic performance is poor, the production process is subjected to more than two off-line coating processes, quality problems such as foreign matters, scratches and the like are easy to occur during the coating process, and the production cost is high.
(3) And preparing a conductive coating, and coating the surface of the PET substrate once to prepare the antistatic release film. The method has the advantages of only one-time coating in the production process of the release film, high production efficiency and good economical efficiency. But the compatibility requirement of the antistatic agent and the silicone oil is higher, part of the antistatic agent absorbs a large amount of water, the curing of the release layer is incomplete, the product quality is low, and the requirement of industrial production is difficult to meet. The invention patent with application number 202010013793.6 discloses an antistatic silicone release film, which comprises: the release film prepared by the method has high adhesiveness and excellent surface resistance, but has the problems of incomplete curing of the release layer, poor peeling force, low product quality and the like, and is difficult to meet the requirements of industrial production.
In conclusion, the release film materials on the market at present have poor antistatic effect, poor antistatic durability and difficulty in meeting the antistatic requirement, and the adhesion between the release layer and the substrate is poor, so that the stability of the release effect cannot be ensured, and the use requirements of the electrical industry, the electronic industry, the optical industry and the die cutting processing industry are difficult to meet.
Disclosure of Invention
The invention aims to provide a novel antistatic coating aiming at solving the problems of easy pollution, peeling failure, poor adhesion and the like caused by unstable antistatic performance of the existing release film, and the antistatic stability of the release film can be improved.
Another object of the present invention is to provide an antistatic release film prepared using the above antistatic coating material, which has a durable antistatic effect, high adhesion, a stable release effect, and excellent transparency.
The third object of the present invention is to provide a method for preparing the above release film.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
The antistatic coating provided by the invention is a water-based dispersion liquid or an ethyl acetate dispersion liquid containing an antistatic material; the antistatic material in the antistatic coating accounts for 0.005-0.05 wt%; the antistatic material includes, but is not limited to, one or more of conductive carbon-based materials, conductive polymer resins, metal compounds, and the like; the conductive carbon-based material includes, but is not limited to, one or more of single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), multi-walled carbon nanotubes (MWCNTs), Graphite (GR), carbon black material (CB), and the like. The conductive polymer resin includes, but is not limited to, one or more of thiophene, pyrrole, aniline, and the like. The metal compound includes, but is not limited to, one or more of copper particles, silver nanowires, indium tin oxide, titanium oxide, and the like.
In a preferred implementation manner, the antistatic coating may further include a dispersant or/and a stabilizer, wherein the weight percentage of the dispersant in the antistatic coating is 0.005% to 0.1%, and the weight percentage of the stabilizer in the antistatic coating is 0.005% to 0.1%. The dispersant includes, but is not limited to, one or more of TNRDIS, Disponer 983, FA 196, FX 9086, sodium glycocholate and derivatives thereof, sodium glycodeoxycholate and derivatives thereof, sodium chenodeoxycholate and derivatives thereof, sodium taurocholate and derivatives thereof, sodium deoxycholate and derivatives thereof, polyvinylpyrrolidone and derivatives thereof, polyvinyl caprolactam and derivatives thereof, polyvinyl acetamide and derivatives thereof (average molecular weight 8000-700000), sodium dodecyl benzene sulfonate, and the like. The stabilizer includes but is not limited to one or more of macromolecular type stabilizer DNA, RNA, cellulose and its derivative, sodium carboxymethyl cellulose and the like.
The antistatic layer prepared based on the antistatic coating has the following advantages: the carbon nanotube material has excellent conductivity, the formed structure is stable, the process that the antistatic coating migrates to a release layer can not exist, and the release film is ensured to have a lasting antistatic effect; good adhesion, namely strong adhesion between the antistatic layer and the film substrate and between the antistatic layer and the release layer, and tight interface contact, so that the cured layer can hardly be separated by friction, and the stability of the release effect is ensured; (iii) good conductivity, the surface resistance of the film coated with the antistatic layer is about 103～104Omega/sq, less than 1012Omega/sq, meets the use requirement of the antistatic film and has good antistatic effect; and fourthly, the antistatic coating is good in transparency, the conductive carbon material is preferably 0.05 percent by weight, the influence on the light transmittance of the transparent PET base material film is small on the aspect of ensuring good antistatic performance, and the light transmittance is over 85 percent.
The antistatic release film with good stability and adhesiveness provided by the invention has two structures: one is that at least one surface of the film substrate is coated with an antistatic layer and a release layer in sequence; the other is to coat an antistatic release layer on at least one surface of the film substrate.
The film substrate includes, but is not limited to, films made of PET, PE, BOPP, CPP, and the like.
For the first antistatic release film, the antistatic layer is prepared by coating antistatic coating on a film substrate, and the thickness of the antistatic layer is about 2-10 μm; the release layer is prepared by coating release paint on the antistatic layer, and the thickness of the release layer is about 0.4-0.8 mu m. The release coating is prepared by uniformly mixing 100 parts of silane compounds, 1-2 parts of catalyst and 10-20 parts of solvent oil. The silane compounds include, but are not limited to, one or more of alkenyl polysiloxane, aminosilane, vinyl silane, isocyanato silane, and the like. The solvent oil includes, but is not limited to, one or more of benzene, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, isopropyl alcohol, 120# solvent oil, heptane, and the like. The catalyst is one of metal complexes of platinum, ruthenium, rhodium, iron, cobalt, nickel, copper, silver and the like.
The structural formula of the alkenyl polysiloxane is as follows:
wherein x is an integer of 10 to 500; r1Is a straight-chain alkyl group of 1 to 6 atoms, R1The hydrogen atom on the alkyl group may be substituted by a chlorine atom.
For the second antistatic release film, the antistatic release layer is prepared by coating antistatic release paint on a film substrate, and the thickness of the antistatic release layer is about 10-20 μm. The antistatic coating is obtained by uniformly mixing the uniformly dispersed antistatic coating with a silane compound, a catalyst, an anchoring agent, a cross-linking agent and solvent oil; the contents of the components are as follows: based on 100 parts by weight of silane compound, 50-100 parts of antistatic coating, 100-200 parts of solvent oil, 1.0-1.4 parts of anchoring agent, 1.2-1.6 parts of cross-linking agent and 1.4-1.8 parts of catalyst. The selection of the silane compound, the catalyst and the solvent oil is the same as that given in the mold release agent. The anchoring agent includes, but is not limited to, one or more of methyl vinyl MQV type silicone and the like. The cross-linking agent includes but is not limited to one or more of triethoxysilane, trimethoxysilane, dimethyldiethoxysilane.
The invention further provides preparation methods of the two antistatic release films.
The invention provides a preparation method of an antistatic release film, which belongs to an external additive type of antistatic coating, wherein an antistatic layer is coated on at least one surface of a film substrate, and a release layer is coated on the surface of the antistatic layer to prepare the antistatic release film; the method specifically comprises the following steps:
(1) preparing an antistatic coating, and uniformly dispersing the conductive carbon material in water to obtain a dispersion liquid with the weight percentage of the conductive carbon material being 0.005-0.05%, namely the antistatic coating;
(2) pretreating the film substrate, namely pretreating the surface to be coated of the film substrate to increase the surface adhesion of the film substrate;
(3) coating an antistatic layer, coating an antistatic coating on the film substrate, and drying after coating to form the antistatic layer;
(4) preparing a release coating, uniformly mixing the silane compound and the solvent oil according to the formula amount, adding the catalyst according to the formula amount, and continuously and uniformly mixing to obtain the release coating;
(5) coating a release coating, coating the release coating on the antistatic layer of the film, and drying after coating to form a release layer so as to obtain the final antistatic release film.
In the step (1), the dispersion liquid can obtain a good dispersion effect by one or more methods of ultrasonic treatment, three-roll milling, ball milling, Dyno-mill grinding, stirring, extrusion and the like. In order to improve the stable antistatic performance of the antistatic coating, a dispersant or/and a stabilizer in a formula amount may be further dispersed in water together with the conductive carbon-based material.
In the step (2), the method for pretreating the surface of the film substrate may be at least one or more of polishing treatment, sand blasting, etching with strong acid or strong base, corona treatment, addition of surface modifier (such as titanate coupling agent, silane coupling agent or aluminate coupling agent), surface graft modification (such as radiation, chemical treatment or plasma treatment), and addition of binder (such as polyacrylic acid, carboxymethyl cellulose or polyvinyl alcohol). For example, by performing corona treatment on the surface of the film base, it is possible to ensure that the contact angle between the antistatic layer and the film base material is 30 to 50 °, which can contribute to uniform coating of the antistatic layer and enhance the adhesiveness of the film surface.
In the step (3) above, the antistatic coating may be applied by one or more known methods selected from at least one of a bar coating method, a reverse roll coating method, a gravure roll coating method, a spray coating method, and a spin coating method, preferably from one side to the other side of the film substrate, to form an antistatic layer. The preferable drying method of the film coated with the antistatic layer is as follows: drying in a 65-75 ℃ oven, and controlling the total air flow in the oven to 22000-28000 m3And h, drying for 60-120s to ensure the forming of the antistatic layer. And drying the film coated with the antistatic layer, further washing the film with water, and treating the film in an acid solution with the concentration of 30-50% for 12-36 h. The acid used may be nitric acid, hydrochloric acid, etc. The surface resistance range of the acid-treated antistatic film is 102～103Omega/sq, to achieve better antistatic effect.
In the step (4), the silane compound and the solvent oil can be mixed by a conventional stirring mode, and the stirring time is 10-20 min. And stirring for 5-10 min after adding the catalyst.
The method for applying the release coating in the step (5) may refer to the method for applying the antistatic coating, and the application methods of the two may be the same or different. The preferable drying mode of the film coated with the release layer is as follows: drying in an oven at 85-95 ℃, and controlling the total air flow in the oven to 22000-28000 m3And h, drying time is 60-120s, so that the release layer is formed and the film substrate is not influenced.
According to the alkenyl polysiloxane with the structural formula (I), the release layer is crosslinked and cured according to the components to form the release layer, and the chemical structural formula of the effective component of the crosslinked product is as follows:
wherein y is an integer of 10 to 500.
According to the antistatic release film prepared by the method, the antistatic coating is used as the conductive carbon material, the carbon nanotube material has excellent conductivity, the structure is stable after molding, the process that the antistatic layer migrates to the release layer is avoided, and the release film is ensured to have a lasting antistatic effect. Meanwhile, the antistatic layer, the release layer and the film substrate have good adhesion, the thicknesses of the antistatic coating and the release coating are relatively thin in the coating process, the thickness of the prepared coating is within the range of 2-10 mu m, and the prepared release film still has good transparency based on the good transparency of the film substrate.
Coating is carried out on two surfaces of the film substrate, and the steps (1) to (5) are repeated, so that the double-sided antistatic film can be prepared.
The second preparation method of the antistatic release film provided by the invention belongs to an additive type in antistatic coating, and the antistatic release film is prepared by preparing the antistatic release coating containing the antistatic coating and coating at least one surface of a film substrate; the method specifically comprises the following steps:
firstly, preparing an antistatic coating, sequentially adding a silane compound, solvent oil, an anchoring agent, a cross-linking agent and a catalyst in a formula amount into a uniformly dispersed antistatic material ethyl acetate dispersion liquid according to the formula amount, and uniformly mixing to obtain the antistatic coating;
preprocessing the film substrate, namely preprocessing the surface of the film substrate to be coated to increase the surface adhesion of the film substrate;
thirdly, coating an antistatic release layer, coating the antistatic coating on a film substrate, and drying after coating to form the antistatic release layer so as to obtain the final antistatic release film.
In the step I, the added materials are uniformly stirred in a conventional stirring mode, and the materials are generally stirred for 10-20 min.
In the above step (ii), the surface of the film substrate is treated in the same manner as that given above, and will not be described in detail here.
In the third step, the preferable drying mode of the film coated with the antistatic release layer is as follows: drying in an oven at 85-95 ℃, and controlling the total air flow in the oven to 22000-28000 m3And h, drying time is 120-300 s, so that the antistatic release layer can be ensured to be completely and normally cured and molded, and the influence on the film substrate is avoided.
The antistatic release film prepared by the method has the characteristics of lasting stability, high adhesiveness, stable release force, good transparency and the like of the antistatic release film prepared by the first release film, and only needs one-time coating in the production process, so that the production efficiency is high, and the economical efficiency is good.
According toAccording to the invention, the antistatic release film provided by the invention comprises at least one release layer, at least one antistatic layer and a film substrate layer from top to bottom in sequence, and based on the good conductivity of the antistatic coating, the problem of poor antistatic effect of the existing PET release film is effectively solved, the release film prepared by the method has a lasting antistatic effect, and the surface resistance can reach 103Omega/sq, high adhesiveness, stable release force and good transparency, can reduce problems such as contamination caused by static electricity when the release film is separated from the adhesive, peeling failure, and the like.
Drawings
FIG. 1 is a schematic cross-sectional view of a first antistatic release film according to the present invention; wherein, the substrate is 110-PET film; 120-an antistatic layer; 130-release layer.
FIG. 2 is a schematic cross-sectional view of two sides of a first antistatic release film according to the present invention; 210-a PET film substrate; 220-an antistatic layer; 230-release layer.
FIG. 3 is a schematic cross-sectional view of a second antistatic release film according to the present invention; wherein, 310-PET film substrate; 320-an antistatic layer; 330-a release layer.
Interpretation of terms
The term "permanent antistatic effect" in the sense of the present invention means that the antistatic effect on the release film prepared in the present invention is stable, unaffected by the relative atmospheric humidity of the environment which may be changed, or less affected by the changed environment, over a period of at least 3 months, preferably at least 5 months, more preferably at least 10 months, very preferably 12 months.
Detailed Description
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 invention belongs. To avoid conflict, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention.
As used herein, the terms "comprises," "comprising," "includes," "including," "contains," "characterized by," "has," "possesses," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. In addition, unless expressly stated to the contrary, the term "or" means an inclusive "or" and not an exclusive "or".
The water used in the following examples is deionized water.
Example 1
The antistatic release film to be prepared in this embodiment, as shown in fig. 1, includes a PET film base layer 100 (having a thickness of 100 μm), an antistatic layer 120 disposed on the PET film base layer, and a release layer 130 disposed on the antistatic layer.
In this embodiment, the antistatic coating comprises, by weight: 0.05 part of single-walled carbon nanotube powder (Tuball), 100 parts of deionized water, 0.05 part of DNA (Sigma), 0.05 part of cellulose (Acros, MW 100000), 0.05 part of sodium deoxycholate (Acros Organics), 0.05 part of polyvinylpyrrolidone (Damas-beta, MW 10000).
In this embodiment, the release coating comprises the following components in parts by weight: 100 parts of alkenyl polysiloxane (Zhejiang Yaoyang new materials science and technology limited), 2 parts of platinum catalyst (Zhejiang Yaoyang new materials science and technology limited) and 15 parts of toluene solvent oil (Chengdu Changhu chemical reagent combined company).
The steps for preparing the antistatic release film in this example are as follows:
(1) preparing an antistatic coating, adding the single-walled carbon nanotube, sodium deoxycholate, DNA, cellulose and polyvinylpyrrolidone into a ball kettle according to the formula amount, and carrying out ball milling for 48 hours to uniformly disperse the single-walled carbon nanotube in deionized water to obtain an aqueous dispersion solution with the weight percentage of the single-walled carbon nanotube of about 0.05%, namely the antistatic coating.
(2) And (3) pretreating the film substrate, namely performing corona treatment on the surface to be coated of the PET film substrate at the production speed of 205m/min, the corona power of 5.1KW and the corona power density of 16.1KJ/m2 so as to increase the surface adhesion of the film substrate.
(3) Coating an antistatic layer, coating an antistatic coating on a film substrate from top to bottom by using a bar coating method, drying in an oven at 70 ℃ after coating, and controlling the total air flow in the oven to be 25000m3The drying time was 90 s. After drying the film coated with the antistatic layer, the film is further washed with water and then treated in a nitric acid solution with the concentration of 40% for 24 hours. After acid treatment, washing and drying are carried out to form the antistatic layer.
(4) Preparing a release coating, adding the formula amount of the silylene polysiloxane into toluene solvent oil, stirring for 15min, adding the formula amount of the platinum catalyst, and continuously stirring for 5min to obtain the release coating;
(5) coating a release coating, coating the release coating on a film substrate from top to bottom by using a bar coating method, drying the film substrate in an oven at 95 ℃ after coating, and controlling the total air flow in the oven to be 25000m3And h, drying for 90s to obtain the final antistatic release film.
The three antistatic release film samples obtained by repeating the steps (2), (3) and (5) three times except for the step (1) and the step (4) are configured once, and the thickness parameters are shown in table 1.
Table 1 thickness of antistatic release film prepared in example 1
| Sample (I) | PET film substrate (mum) | Antistatic layer (mum) | Release layer (mum) | Total thickness (mum) |
| Sample 1 | 100 | 3 | 0.4 | 103.4 |
| Sample 2 | 100 | 3 | 0.8 | 103.8 |
| Sample 3 | 100 | 7 | 0.6 | 107.6 |
Coating is carried out on two surfaces of the PET film substrate, and the steps (2), (3) and (5) are repeated to prepare the double-sided antistatic release film, as shown in figure 2, the double-sided antistatic release film comprises the PET film substrate 210, antistatic layers 220 positioned on two sides of the PET film substrate 210 and release layers 230 positioned outside the antistatic layers.
Comparative example 1
A release film was produced in the same preparation method as in example 1 except that only the release layer was coated, the antistatic layer was not coated, and the thickness of the release layer was 0.6 d.
Comparative example 2
An antistatic film was produced in the same manner as in example 1, except that only the antistatic layer was coated, the release layer was not coated, and the thickness of the antistatic layer was 3 μm.
The three samples prepared in example 1 and the comparative samples prepared in comparative examples 1 and 2 were tested as follows:
1. test for antistatic Properties
The surface resistance of the sample surface was measured using a surface resistance meter (MCP-T700, manufactured by Loresta-GX).
2. Measurement of film transparency
The transparency of the film was tested using an ultraviolet-visible spectrophotometer (UV-1800 PC, manufactured by MAPADA).
3. The adhesion between the thin film antistatic layer, the release layer and the base layer was measured.
Two intersecting straight lines each having a length of 40mm are scribed on the surface of the intact film by a one-hundred-grid method, i.e., by using a cutting tool, the intersecting angle is 30-45 degrees, and the film is cut through to the substrate. And adhering a cutting position by using a pressure sensitive adhesive tape, and inspecting the falling condition of the scribing and forking area for classification after tearing. Results the evaluation was as shown in Table 2.
TABLE 2 rating method for testing film adhesion by cross-cut method test
4. Measurement of film peeling Voltage
The surface static electricity after the film peeling was measured using a static electricity tester (FMX-003, manufactured by simcoin).
5. Durability of antistatic ability
The surface resistance of the cured layer was measured using a surface resistance meter (MCP-T700, manufactured by Loresta-GX). After the release film was prepared, it was placed in an environment of a changed environment relative to atmospheric humidity, stored for 3 months, 5 months, 12 months, and the surface resistance value was measured.
The surface resistance value of the release film material in a relatively changing environment is approximately the same as the initial measurement data when the release film material is stored for different time, and the release film material has a lasting antistatic effect.
Table 3 gives the relevant test results for the three samples prepared in example 1 and the comparative samples prepared in comparative example 1 and comparative example 2.
TABLE 3 results of Performance testing of three samples and two comparative samples
| Item | Surface resistance (omega/sq) | Light transmittance (%) | Peel off voltage (V) | Adhesion rating |
| Sample 1 | 1.136*10^4 | 85.3500 | 80-100 | Level 1 |
| Sample 2 | 1.007*10^4 | 85.7200 | 80-100 | Level 1 |
| Sample 3 | 7.393*10^3 | 84.0850 | 80-100 | Level 1 |
| Comparative example 1 | -- | 86.8514 | -- | Level 1 |
| Comparative example 2 | 1.646*10^3 | 85.0883 | 100-150 | Level 1 |
From the data analysis in table 3, the antistatic release film prepared by the method has excellent antistatic property and the surface resistance is 103-104Omega/sq, stable release force, excellent residual adhesion rate, good transparency, excellent surface adhesion and durable antistatic effect, and meets the production requirement.
Example 2
In this embodiment, the antistatic coating comprises, by weight: 0.05 part of multi-walled carbon nanotube powder (Nanocyl NC7000), 100 parts of deionized water, 0.05 part of dna (sigma), 0.05 part of cellulose (Acros, MW 100000), 0.05 part of sodium deoxycholate (Acros Organics), 0.05 part of polyvinylpyrrolidone (Damas-beta, MW 10000).
The preparation method of the antistatic coating comprises the following steps of adding the multi-walled carbon nanotubes, sodium deoxycholate, DNA, cellulose and polyvinylpyrrolidone in formula amounts into a ball kettle, and performing ball milling for 48 hours to uniformly disperse the single-walled carbon nanotubes in deionized water to obtain an aqueous dispersion solution with the weight percentage of the multi-walled carbon nanotubes of about 0.05%, namely the antistatic coating.
The steps of this example refer to steps (2) - (5) given in example 1.
The thickness of the antistatic release film prepared in this example was 3 μm, and the thickness of the release layer was 0.6 μm.
Comparative example 3
An antistatic film was produced in the same manner as in example 2, except that only the antistatic layer was coated and the release layer was not coated. The thickness of the antistatic layer was 3 μm.
The comparative samples of example 2 and comparative example 3 were tested as follows:
1. test for antistatic Properties
The surface resistance of the sample surface was measured using a surface resistance meter (MCP-T700, manufactured by Loresta-GX).
2. Measurement of film transparency
The transparency of the film was tested using an ultraviolet-visible spectrophotometer (UV-1800 PC, manufactured by MAPADA).
TABLE 4 test results of sample and comparative sample Properties
| Item | Surface resistance (omega/sq) | Light transmittance (%) |
| Examples | 3.077*104 | 82.7104 |
| Comparative example | 6.308*103 | 83.0234 |
From the data analysis in table 4, the antistatic release film prepared by the method has excellent antistatic property and the surface resistance is 103-104Omega/sq, and good transparency, and meets the production requirement.
Example 3
The antistatic release film to be prepared in this embodiment includes a PET film base layer 310 (with a thickness of 100 μm) and an antistatic release layer 130 disposed on the PET film base layer, as shown in fig. 3.
In this embodiment, the antistatic coating comprises, by weight: 0.05 part of multi-walled carbon nanotube powder (Nanocyl NC7000), 100 parts of ethyl acetate (metropolis chemical limited), 0.05 part of dispersant (YIME, trade name TNRDIS), 0.05 part of dna (sigma), 0.05 part of cellulose (Acros, MW 100000), 0.05 part of sodium deoxycholate (Acros Organics), 0.05 part of polyvinylpyrrolidone (Damas-beta, MW 10000).
In the embodiment, the antistatic release coating comprises the following components in parts by weight: 50 parts of antistatic coating, 100 parts of alkenyl polysiloxane (Zhejiang Yaoyang new materials science and technology limited), 1.6 parts of platinum catalyst (Zhejiang Yaoyang new materials science and technology limited), 200 parts of ethyl acetate solvent oil, 1.2 parts of methyl vinyl MQV type silicone resin (Zhejiang Yaoyang new materials science and technology limited) and 1.4 parts of dimethyl diethoxy silane (Zhejiang Yaoyang new materials science and technology limited).
The steps for preparing the antistatic release film in this example are as follows:
firstly, preparing an antistatic coating, adding a multi-walled carbon nanotube and a dispersant in a formula amount into ethyl acetate, carrying out ball milling dispersion for 48 hours, sequentially adding alkenyl polysiloxane, ethyl acetate, an anchoring agent, a cross-linking agent and a platinum catalyst in the ethyl acetate dispersion liquid of the dispersed single-walled carbon nanotube in the formula amount, and then stirring for 20min to obtain the antistatic coating.
Secondly, pretreating the film substrate, namely performing corona treatment on the surface to be coated of the PET film substrate at the production speed of 205m/min, the corona power of 5.1KW and the corona power density of 16.1KJ/m2 to increase the surface adhesive force of the film substrate.
Thirdly, coating an antistatic release layer, coating antistatic coating on the film substrate from top to bottom by using a bar coating method, drying the film substrate in an oven at 95 ℃ after coating, and controlling the total air volume in the oven to be 25000m3And h, drying for 210s to obtain the final antistatic release film.
Through the method, the thickness of the final antistatic release film is 110-120 μm, wherein the thickness of the antistatic release film is 10-20 μm.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (9)
1. The antistatic coating is characterized by being aqueous dispersion liquid or ethyl acetate dispersion liquid containing an antistatic material; the antistatic material in the antistatic coating accounts for 0.005-0.05 wt%; the antistatic material is one or more of conductive carbon materials, conductive polymer resin and metal compounds; the conductive carbon material is one or more of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, graphite and carbon black.
2. The antistatic coating of claim 1 further comprising a wetting agent and/or a stabilizer, wherein the weight percentage of the dispersant in the antistatic coating is 0.005% to 0.1%, and the weight percentage of the stabilizer in the antistatic coating is 0.005% to 0.1%.
3. Antistatic release film, its characterized in that has two kinds of structures: one is that at least one surface of the film substrate is coated with an antistatic layer and a release layer in sequence; the other is that at least one surface of the film substrate is coated with an antistatic release layer;
for the first antistatic release film, an antistatic layer is prepared by applying the antistatic coating as described in claim 1 or 2 on a film substrate; the release layer is prepared by coating release paint on the antistatic layer; the release coating is prepared by uniformly mixing 100 parts of silane compounds, 1-2 parts of catalyst and 10-20 parts of solvent oil;
for the second antistatic release film, the antistatic release layer is prepared by coating antistatic release paint on a film substrate; the antistatic coating is obtained by uniformly mixing the antistatic coating which is uniformly dispersed and is described in claim 1 or 2 with a silane compound, a catalyst, an anchoring agent, a cross-linking agent and a solvent oil; the contents of the components are as follows: 100 parts of silane compound, 50-100 parts of antistatic coating, 100-200 parts of solvent oil, 1.0-1.4 parts of anchoring agent, 1.2-1.6 parts of cross-linking agent and 1.4-1.8 parts of catalyst.
4. The antistatic release film according to claim 3, wherein the silane compound is one or more of an alkenyl polysiloxane, an aminosilane, a vinyl silane, and an isocyanato silane.
5. The antistatic release film with good stability and adhesion as claimed in claim 3, wherein the solvent oil is one or more of benzene, toluene, ethyl acetate, butyl acetate, butanone, isopropanol, 120# solvent oil and heptane.
6. The antistatic release film according to claim 3, wherein the catalyst is one of platinum, ruthenium, rhodium, iron, cobalt, nickel, copper, silver metal complexes.
7. The antistatic release film according to claim 3, wherein the anchoring agent is a methyl vinyl MQV type silicone; the cross-linking agent is one or more of triethoxysilane, trimethoxysilane and dimethyldiethoxysilane.
8. The method for preparing the antistatic release film according to any one of claims 3 to 7, characterized by comprising the steps of:
(1) preparing an antistatic coating, and uniformly dispersing the conductive carbon material in water to obtain a dispersion liquid with the weight percentage of the conductive carbon material being 0.005-0.05%, namely the antistatic coating;
(2) pretreating the film substrate, namely pretreating the surface to be coated of the film substrate to increase the surface adhesion of the film substrate;
(3) coating an antistatic layer, coating an antistatic coating on the film substrate, and drying after coating to form the antistatic layer;
(4) preparing a release coating, uniformly mixing the silane compound and the solvent oil according to the formula amount, adding the catalyst according to the formula amount, and continuously and uniformly mixing to obtain the release coating;
(5) coating a release coating, coating the release coating on the antistatic layer of the film, and drying after coating to form a release layer so as to obtain the final antistatic release film.
9. The method for preparing the antistatic release film according to any one of claims 3 to 7, characterized by comprising the steps of:
firstly, preparing an antistatic coating, sequentially adding a silane compound, solvent oil, an anchoring agent, a cross-linking agent and a catalyst in a formula amount into a uniformly dispersed antistatic material ethyl acetate dispersion liquid according to the formula amount, and uniformly mixing to obtain the antistatic coating;
preprocessing the film substrate, namely preprocessing the surface of the film substrate to be coated to increase the surface adhesion of the film substrate;
thirdly, coating an antistatic release layer, coating the antistatic coating on a film substrate, and drying after coating to form the antistatic release layer so as to obtain the final antistatic release film.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110957591.1A CN113604088A (en) | 2021-08-18 | 2021-08-18 | Antistatic coating, high-adhesion and high-stability antistatic release film and preparation method |
| JP2022078933A JP2023029210A (en) | 2021-08-18 | 2022-05-12 | Antistatic coating and high viscosity, stable antistatic release film, and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110957591.1A CN113604088A (en) | 2021-08-18 | 2021-08-18 | Antistatic coating, high-adhesion and high-stability antistatic release film and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113604088A true CN113604088A (en) | 2021-11-05 |
Family
ID=78341418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110957591.1A Pending CN113604088A (en) | 2021-08-18 | 2021-08-18 | Antistatic coating, high-adhesion and high-stability antistatic release film and preparation method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2023029210A (en) |
| CN (1) | CN113604088A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124749A (en) * | 2022-07-18 | 2022-09-30 | 浙江日久新材料科技有限公司 | Antistatic optical release film for OCA (optical clear adhesive) and preparation method thereof |
| CN115806688A (en) * | 2022-11-29 | 2023-03-17 | 惠州市金润佳光电科技有限公司 | Antistatic non-silicon release film and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101421104A (en) * | 2007-03-16 | 2009-04-29 | 东丽世韩有限公司 | Antistatic silicone release coating films |
| JP2010017931A (en) * | 2008-07-10 | 2010-01-28 | Toyobo Co Ltd | Mold releasing film |
| CN101952906A (en) * | 2008-03-25 | 2011-01-19 | 东丽株式会社 | Electrically conductive complex and process for production thereof |
| CN109734943A (en) * | 2018-12-29 | 2019-05-10 | 南京君弘新材料有限公司 | A kind of transparent double face anti-static release film and preparation method thereof |
| CN110387162A (en) * | 2018-04-20 | 2019-10-29 | 长濑化成株式会社 | Coating composition |
| WO2020009401A1 (en) * | 2018-07-04 | 2020-01-09 | 도레이첨단소재 주식회사 | Reusable release film |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6012437U (en) * | 1983-07-05 | 1985-01-28 | 東洋メタライジング株式会社 | Silicone coated plastic film with conductive layer |
| JPH106443A (en) * | 1996-06-26 | 1998-01-13 | Mitsubishi Materials Corp | Carrier film for molding ceramics green sheet |
| JP7174809B2 (en) * | 2020-06-09 | 2022-11-17 | Ｋｊ特殊紙株式会社 | antistatic sheet |
-
2021
- 2021-08-18 CN CN202110957591.1A patent/CN113604088A/en active Pending
-
2022
- 2022-05-12 JP JP2022078933A patent/JP2023029210A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101421104A (en) * | 2007-03-16 | 2009-04-29 | 东丽世韩有限公司 | Antistatic silicone release coating films |
| CN101952906A (en) * | 2008-03-25 | 2011-01-19 | 东丽株式会社 | Electrically conductive complex and process for production thereof |
| JP2010017931A (en) * | 2008-07-10 | 2010-01-28 | Toyobo Co Ltd | Mold releasing film |
| CN110387162A (en) * | 2018-04-20 | 2019-10-29 | 长濑化成株式会社 | Coating composition |
| WO2020009401A1 (en) * | 2018-07-04 | 2020-01-09 | 도레이첨단소재 주식회사 | Reusable release film |
| CN109734943A (en) * | 2018-12-29 | 2019-05-10 | 南京君弘新材料有限公司 | A kind of transparent double face anti-static release film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王文广: "《聚合物改性原理》", 31 March 2018 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124749A (en) * | 2022-07-18 | 2022-09-30 | 浙江日久新材料科技有限公司 | Antistatic optical release film for OCA (optical clear adhesive) and preparation method thereof |
| CN115806688A (en) * | 2022-11-29 | 2023-03-17 | 惠州市金润佳光电科技有限公司 | Antistatic non-silicon release film and preparation method thereof |
| CN115806688B (en) * | 2022-11-29 | 2023-07-25 | 惠州市金润佳光电科技有限公司 | Antistatic non-silicon release film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023029210A (en) | 2023-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113604088A (en) | Antistatic coating, high-adhesion and high-stability antistatic release film and preparation method | |
| CN111621201B (en) | Metallic nanowire inks for forming transparent conductive films with fused networks | |
| CN105451964B (en) | Poly- (methyl) acrylimide film, its easy caking property film and their manufacturing method | |
| KR101685210B1 (en) | Electrically conductive complex and process for production thereof | |
| KR100836177B1 (en) | Antistatic silicone release coating films | |
| US20120277360A1 (en) | Graphene Compositions | |
| KR20160117396A (en) | Conductive Paint Composition and the Method of Conductive Film Using Thereof | |
| US20110086206A1 (en) | Polymer compositions containing carbonaceous fillers | |
| WO2010115173A1 (en) | Polymer compositions containing graphene sheets and graphite | |
| CN109016769A (en) | A kind of anti-static silica gel protective film and preparation method thereof | |
| JP2014072041A (en) | Method for producing transparent conductive film, transparent conductive film and device element | |
| JP2009298625A (en) | Method for producing carbon nanotube film and carbon nanotube film | |
| JP2018048324A (en) | Emulsion for preparing transparent conductive coating | |
| CN110591462A (en) | Conductive coating and preparation method thereof | |
| KR20050070124A (en) | Ultraviolet-curable antistatic hard coating resin composition | |
| CN102030914A (en) | Method of manufacturing electrode substrate and electrode substrate manufactured by the method | |
| CN107615408B (en) | The manufacturing method and conductive film of conductive film | |
| KR101321097B1 (en) | Carbon nano tube transparent electrode, method for manufacturing the same, and coating composition for carbon nano tube transparent electrode | |
| TW201920508A (en) | Method for producing conductive film, conductive film and metal nanowire ink | |
| EP3294543B1 (en) | Carbon nanotube based hybrid films for mechanical reinforcement of multilayered, transparent-conductive, laminar stacks | |
| CN115678409A (en) | Anticorrosive antifouling antistatic coating and preparation method thereof | |
| KR100796157B1 (en) | Composition containing electrify prevention | |
| CN107793869A (en) | Graphene conductive coating with superelevation conductive capability | |
| CN114907716A (en) | Transparent three-proofing coating doped with graphene and preparation method thereof | |
| JP6559509B2 (en) | Antimony-doped tin oxide conductive film forming composition and antimony-doped tin oxide conductive film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |