CN108047473B - Anti-static optical hardening film - Google Patents
Anti-static optical hardening film Download PDFInfo
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Abstract
An antistatic optical hardening film comprises a support, an antistatic layer coated on the surface of the support and a hardening layer arranged on the antistatic layer. The antistatic layer is formed by curing a coating liquid containing polyurethane resin and carbon nanotubes; the hardened layer is formed by curing a coating liquid consisting of the following components in parts by weight: the polyurethane-acrylate composite material comprises a polyurethane-acrylate oligomer, a diluent, isocyanate, a photoinitiator, a leveling auxiliary agent and an organic solvent. The antistatic optical hardening film provided by the invention has the advantages of excellent optical performance, good interlayer adhesion and excellent antistatic performance, and the antistatic performance cannot be degenerated due to the change of an external environment.
Description
Technical Field
The present invention relates to a film, particularly to an antistatic optical hardening film for protecting various displays and touch screens.
Background
Plastic films are widely used because of their excellent properties in terms of processability, quality, cost, etc., but because of their high volume resistivity, static electricity is easily generated, which causes problems such as adhesion of foreign matters and dust, adhesion of films to each other, and poor printing, it is necessary to improve the surface characteristics of the films before use. Usually, an antistatic material is added to the cut sheet or a primer layer containing an antistatic material is applied to the surface of the film, and the antistatic material used is generally a surfactant such as a metal oxide, a lithium salt, or an ammonium salt. The light transmittance and color of the film can be influenced by adding the metal oxide, so that the application range of the film is limited; the addition of surfactants such as lithium salt and ammonium salt has poor antistatic durability, sensitivity to environmental temperature and humidity, poor heat resistance, easy seepage on the surface of the film, and appearance defects such as adhesion and the like. More importantly, the film prepared by the method has an antistatic function, but the film has low surface hardness and poor scratch resistance, and the application range of the film is limited.
The method for adding the antistatic auxiliary agent into the coating can achieve the antistatic function, but has the problem of poor transparency and antistatic property after temperature resistance and humidity resistance tests. In the chinese patent CN102991056A, the coating is made to have antistatic property by adding conductive particles, but the conductive particles such as antimony doped tin dioxide and indium doped tin dioxide affect the appearance of the transparent coating, and cause appearance defects such as crystal points and impurity points.
In view of the above, it is a problem to be solved by those skilled in the art how to provide an antistatic optical cured film having excellent optical properties and durable antistatic properties.
Disclosure of Invention
The invention aims to solve the technical problem of providing an anti-static optical hardening film aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
an antistatic optical hardening film comprises a support body, an antistatic layer and a hardening layer, wherein the antistatic layer is coated on the surface of the support body and is formed by curing a coating liquid containing polyurethane resin and carbon nano tubes; coating a hardened layer on the surface of the antistatic layer, wherein the hardened layer is formed by curing a coating liquid consisting of the following components in parts by weight:
10 to 20 parts by weight of urethane acrylate oligomer,
10 to 20 parts by weight of a diluent,
5 to 10 parts by weight of isocyanate,
0.1 to 5 parts by weight of a photoinitiator,
0.2 to 2 weight portions of leveling assistant,
45 to 65 parts by weight of an organic solvent,
the polyurethane acrylate oligomer is selected from aliphatic polyurethane acrylate with the functionality of 4 and below 4; the diluent is bifunctional or trifunctional acrylate monomer.
In the antistatic optical hardening film, the carbon nanotubes in the antistatic layer are single-walled carbon nanotubes functionalized by hydroxyl groups.
In the antistatic optical hardening film, the pencil hardness of the hardening layer is 1H-3H.
The antistatic optical hardening film is characterized in that the isocyanate is one of isophorone diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene-1, 6-diisocyanate and hydrogenated diphenylmethane diisocyanate.
In the antistatic optical hardening film, the thickness of the antistatic layer is 300 nm-600 nm; the thickness of the hardening layer is 1-5 μm.
The support is one of a polycarbonate film, a polyethylene terephthalate film and a polymethyl methacrylate film; the thickness of the support is 23 μm to 250 μm.
The curing process of the anti-static optical hardening film comprises the steps of drying a solvent in a drying oven at the temperature of 100-120 ℃ for 5-10 min; then ultraviolet light is carried out for curing, and the irradiation energy of the ultraviolet light is 500mJ/cm2～1000mJ/cm2。
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the polyurethane acrylate oligomer with the functionality of 4 and below 4, and the bifunctional or trifunctional acrylate monomer are selected, so that the crosslinking density and the curing degree of the hardened layer can be controlled, the carbon nanotube conductive material in the anti-static layer can penetrate through the hardened layer, and the surface of the hardened layer has the anti-static property; and the optical performance and the scratch resistance of the hardened layer are excellent, and the antistatic performance is not weakened along with adverse factors such as temperature and humidity, solvent wiping and the like.
2. The bifunctionality or trifunctional acrylate monomer used in the invention can enable the hardened layer and the antistatic layer to have good cohesive force, and overcomes the problem of poor adhesive force caused by the shrinkage of a UV curing coating. In addition, the hydroxyl functionalized single-walled carbon nanotube selected by the invention can chemically react with isocyanate in the hardened layer to fix the carbon nanotube in the coating, and meanwhile, the adhesive force of the hardened layer and the antistatic layer is increased.
Drawings
FIG. 1 is a block diagram of the present invention.
In the drawings, each reference numeral indicates 1: a support; 2: an antistatic layer; 3: and hardening the layer.
Detailed Description
Suitable supports for the present invention include plastic films or sheets such as polyethylene terephthalate, polycarbonate, and polymethyl methacrylate.
The support suitable for the present invention is a transparent substrate having a thickness of 23 μm to 250 μm, preferably 50 μm to 188 μm.
The hardened layer is formed by curing a coating liquid which comprises a polyurethane acrylate oligomer, a diluent, isocyanate, a photoinitiator, a leveling auxiliary agent, an organic solvent and the like. The polyurethane acrylic resin suitable for the present invention is an aliphatic polyurethane acrylate having a functionality of 4 or less, and the diluent is a bifunctional or trifunctional acrylate monomer. The lower functionality resins and monomers are selected to control the crosslink density of the coating after curing. If resin and monomer with high functionality are selected, the ultraviolet cured coating has high crosslinking density, the hardness and scratch resistance of the surface of the coating are good, but the coating with high crosslinking density blocks the penetration and penetration of carbon nanotubes in the anti-static layer, and finally the surface resistance of the film is high and the anti-static performance is poor. In order to ensure scratch resistance on the coating surface, resins with too low functionality or more flexible groups cannot be selected. Meanwhile, the thickness of the antistatic layer also affects the antistatic performance of the surface of the hardened layer, and the scratch resistance of the hardened layer needs to be considered, and the thickness of the hardened layer suitable for the invention is 1-5 μm. In addition, in order to ensure that a proper degree of curing is achieved, a proper ultraviolet curing energy needs to be selected.
In the formula provided by the invention, the dosage of the polyurethane acrylate oligomer is controlled to be 10-20 parts by weight, and the dosage of the diluent is controlled to be 10-20 parts by weight; the ultraviolet light used in the curing process of the coating liquid for a hardened layer in the invention can be obtained from a high-pressure mercury lamp, and the irradiation energy of the ultraviolet light suitable for the formulation is 500mJ/cm2～1000mJ/cm2(ii) a The pencil hardness of the hardened layer is 1H-3H.
The antistatic layer is formed by curing a coating liquid consisting of polyurethane resin and carbon nanotubes, and the thickness of the antistatic layer is 300 nm-600 nm. In order to ensure that the antistatic layer and the hardened layer have good interlayer adhesion, more importantly, the carbon nano tube is fixed in the coating layer, and the carbon nano tube is suitable for selecting the single-walled carbon nano tube with functionalized hydroxyl; the isocyanate selected in the hardening layer can chemically react with the carbon nano tube in the process of drying the solvent in the hardening layer, so that the carbon nano tube is completely fixed in the coating, and the antistatic performance cannot decline along with external conditions such as time, temperature, humidity, acid and alkali and the like. Considering the curing condition of isocyanate, the temperature of the drying solvent of the hardening layer is selected to be 100-120 ℃ for 5-10 min
The isocyanate in the invention is one of isophorone diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene-1, 6-diisocyanate and hydrogenated diphenylmethane diisocyanate, and the addition amount is 5-10 parts by weight.
The coating liquid for the antistatic layer consists of polyurethane resin, a cross-linking agent, a carbon nano tube, an auxiliary agent and deionized water; the addition amount of the polyurethane is 2 to 15 parts by weight, the addition amount of the cross-linking agent is 0.5 to 2 parts by weight, the addition amount of the carbon nano tube is 2 to 10 parts by weight, the addition amount of the auxiliary agent is 0.5 to 5 parts by weight, and the addition amount of the deionized water is 68 to 95 parts by weight.
The photoinitiator in the present invention can be selected from the initiators known in the art of ultraviolet light curing, such as 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-methyl phenyl propane-1-one (1173), benzoin dimethyl ether (651), 2, 4, 6 (trimethylbenzoyl) diphenyl phosphine oxide (TPO), etc.
As the solvent is added as needed to the coating liquid of the hardened layer, a conventional organic solvent can be used without any limitation, for example: alcohols such as methanol, ethanol, propanol; ketones such as acetone, butanone, methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, ethyl propionate. Ketones and esters with high solubility are preferred.
The assistant in the invention can be selected from organic siloxane or organosilicon modified acrylic leveling agent known in the field of ultraviolet light curing, such as BYK-307, BYK-354 and BYK-377 in Germany Bike chemistry, Levaslip407, Levaslip410 and Levaslip432 in Germany chemistry, and the like.
The present invention will be further described with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
10g of urethane acrylate resin (functionality 4, trade name: CN8007NS, Saedoma), 20g of diluent (trifunctional monomer, trade name: SR9035, Saedoma), 9.2g of isocyanate (isophorone diisocyanate, IPDI, Wittings.), 0.1g of photoinitiator (trade name: 1173, manufactured by Tianjin Tianjiao chemical Co., Ltd.), 1g of leveling assistant (BYK-307) and 59.7g of acetone were placed in a stirring pot, and a coating solution was obtained after stirring uniformly for later use.
Coating an antistatic coating liquid on a polycarbonate film with the thickness of 23 mu m, and curing to form an antistatic layer; the antistatic coating liquid was prepared by uniformly stirring 2g of a polyurethane resin (trade name: UCECOAT 7655, Zhan New resins Co., Ltd.), 2g of a hydroxyl-functionalized single-walled carbon nanotube (trade name: HQNANO-CNTS-002C, Suzhou carbofeng graphene science Co., Ltd.), 0.5g of a crosslinking agent (trade name: 710, Changzhou blue Asia New materials science Co., Ltd.), 0.5g of an auxiliary agent (BYK-307, Bikechemistry) and 95g of deionized water.
Coating the above coating liquid on antistatic layer, placing in oven at 100 deg.C for 10min, and then using ultraviolet light energy of 500mJ/cm2Carrying out UV curing on the coating by using the ultraviolet light to obtain a hardened layer; the antistatic layer had a thickness of 600nm and the cured layer had a thickness of 4 μm, and the evaluation results are shown in Table 1.
Example 2
20g of urethane acrylate resin (functionality: 2, trade name: CN983NS, available from Saedoma corporation), 10g of diluent (bifunctional monomer, trade name: SR508NS, available from Saedoma corporation), 10g of isocyanate (1, 5-naphthalene diisocyanate NDI, COVESTRO corporation), 5g of photoinitiator (trade name: 184, available from Tianjin Jiaozi chemical Co., Ltd.), 0.2g of leveling assistant (BYK-354, available from Bijinska chemical Co., Ltd.), and 54.8g of ethyl acetate were placed in a stirring pot, and stirred uniformly to obtain a coating solution for later use.
Coating an antistatic coating liquid on a 250-micron polyethylene terephthalate film, and curing to form an antistatic layer; the antistatic coating liquid was prepared by uniformly stirring 8g of a polyurethane resin (trade name: UCECOAT 7655, Zhan New resins Co., Ltd.), 6g of a hydroxyl-functionalized single-walled carbon nanotube (trade name: HQNANO-CNTS-002C, Suzhou carbone graphene science Co., Ltd.), 1.0g of a crosslinking agent (trade name: 710, Changzhou blue Asia New materials science Co., Ltd.), 3g of an auxiliary agent (BYK-307, Bika chemical Co., Ltd.), and 82g of deionized water.
Coating the above coating liquid on antistatic layer, placing in oven at 120 deg.C for 5min, and then using ultraviolet energy of 1000mJ/cm2Carrying out UV curing on the coating by using the ultraviolet light to obtain a hardened layer; the antistatic layer was 300nm in thickness and the cured layer was 1 μm in thickness, and the evaluation results are shown in Table 1.
Example 3
12g of urethane acrylate resin (functionality: 3, trade name: CN8009NS, Saedoma), 18g of diluent (bifunctional monomer, Saedoma, trade name: SR205NS), 5g of isocyanate (hydrogenated diphenylmethane diisocyanate H12MDI, winning and creating company), 3g of photoinitiator (product name: 651, manufactured by Tianjin Tianjiao chemical Co., Ltd.), 2g of leveling assistant (Delaut chemical, Levaslip407) and 60g of ethyl acetate were placed in a stirring pot, and stirred uniformly to obtain a coating solution for later use.
Coating an antistatic coating liquid on a polymethyl methacrylate film with the thickness of 125 mu m, and curing to form an antistatic layer; the antistatic coating liquid was prepared by uniformly stirring 15g of a polyurethane resin (trade name: UCECOAT 7655, Zhan New resins Co., Ltd.), 10g of a hydroxyl-functionalized single-walled carbon nanotube (trade name: HQNANO-CNTS-002C, Suzhou carbone graphene science Co., Ltd.), 2.0g of a crosslinking agent (trade name: 710, Changzhou blue Asia New Material science Co., Ltd.), 5g of an auxiliary agent (BYK-307, Bikechemistry) and 68g of deionized water.
Coating the above coating liquid on antistatic layer, placing in oven at 105 deg.C for 8min, and then using ultraviolet energy of 600mJ/cm2Carrying out UV curing on the coating by using the ultraviolet light to obtain a hardened layer; the antistatic layer had a thickness of 400nm and the cured layer had a thickness of 5 μm, and the evaluation results are shown in Table 1.
Example 4
19g of urethane acrylate resin (functionality: 4, product name: DR-U052, Changxing chemical), 20g of diluent (trifunctional monomer, Changxing chemical, product name: EM331), 10g of isocyanate (hexamethylene-1, 6-diisocyanate HDI, COVESTRO), 4.5g of photoinitiator (product name: TPO, manufactured by Tianjin Tianjiao chemical Co., Ltd.), 1.5g of leveling assistant (Demodex chemical, Levaslip410) and 45g of butyl acetate were placed in a stirring pot, and a coating solution was obtained after stirring uniformly for later use.
Coating an antistatic coating liquid on a polycarbonate film with the thickness of 50 mu m, and curing to form an antistatic layer; the antistatic coating liquid was prepared by uniformly stirring 6g of a polyurethane resin (trade name: UCECOAT 7655, Zhan New resins Co., Ltd.), 4g of a hydroxyl-functionalized single-walled carbon nanotube (trade name: HQNANO-CNTS-002C, Suzhou carbofeng graphene science Co., Ltd.), 0.8g of a crosslinking agent (trade name: 710, Changzhou blue Asia New materials science Co., Ltd.), 2g of an auxiliary agent (BYK-307, Bikechemistry) and 87.2g of deionized water.
Coating the above coating liquid on antistatic layer, placing in oven at 110 deg.C for 6min, and then using ultraviolet energy of 900mJ/cm2Carrying out UV curing on the coating by using the ultraviolet light to obtain a hardened layer; the antistatic layer had a thickness of 500nm and the cured layer had a thickness of 2 μm, and the evaluation results are shown in Table 1.
Example 5
15g of urethane acrylate resin (functionality 2, Changxing chemical, trade name: 6152B-80), 12g of diluent (bifunctional monomer, Changxing chemical, trade name: EM3261), 6g of isocyanate (isophorone diisocyanate, IPDI, winning and creating company), 1.4g of photoinitiator (trade name: 184, manufactured by Tianjin Tianjiao chemical Co., Ltd.), 0.6g of leveling aid (BYK-377) and 65g of ethanol were placed in a stirring pot, and a coating solution was obtained after uniform stirring and was ready for use.
Coating an antistatic coating liquid on a 188-micron polyethylene terephthalate film, and curing to form an antistatic layer; the antistatic coating liquid was prepared by uniformly stirring 10g of a polyurethane resin (trade name: UCECOAT 7655, Zhan New resins Co., Ltd.), 8g of a hydroxyl-functionalized single-walled carbon nanotube (trade name: HQNANO-CNTS-002C, Suzhou carbofeng graphene science Co., Ltd.), 1.5g of a crosslinking agent (trade name: 710, Changzhou blue Asia New Material science Co., Ltd.), 4g of an auxiliary agent (BYK-307, Bika chemical Co., Ltd.), and 76.5g of deionized water.
Will be at the topCoating the coating liquid on an antistatic layer, placing in an oven at 115 deg.C for 7min, and then using ultraviolet light energy of 800mJ/cm2Carrying out UV curing on the coating by using the ultraviolet light to obtain a hardened layer; the antistatic layer was 450nm thick and the cured layer was 3 μm thick, and the evaluation results are shown in Table 1.
Comparative example 1
10g of urethane acrylate resin (functionality 6, trade name: CN8011NS, Saedoma), 20g of diluent (trifunctional monomer, trade name: SR9035, Sandoma), 9g of isocyanate (isophorone diisocyanate, IPDI, Wittings.), 2g of photoinitiator (trade name: 1173, manufactured by Tianjin Tianjiao chemical Co., Ltd.), 1g of leveling aid (BYK-307) and 58g of acetone were placed in a stirring pot, and a coating solution was obtained after stirring uniformly for later use.
Coating an antistatic coating liquid on a polycarbonate film with the thickness of 23 mu m, and curing to form an antistatic layer; the antistatic coating liquid was prepared by uniformly stirring 2g of a polyurethane resin (trade name: UCECOAT 7655, Zhan New resins Co., Ltd.), 2g of a hydroxyl-functionalized single-walled carbon nanotube (trade name: HQNANO-CNTS-002C, Suzhou carbofeng graphene science Co., Ltd.), 0.5g of a crosslinking agent (trade name: 710, Changzhou blue Asia New materials science Co., Ltd.), 0.5g of an auxiliary agent (BYK-307, Bikechemistry) and 95g of deionized water.
Coating the above coating liquid on antistatic layer, placing in oven at 100 deg.C for 10min, and then using ultraviolet light energy of 500mJ/cm2Carrying out UV curing on the coating by using the ultraviolet light to obtain a hardened layer; the antistatic layer had a thickness of 600nm and the cured layer had a thickness of 4 μm, and the evaluation results are shown in Table 1.
Comparative example 2
20g of urethane acrylate resin (functionality: 2, trade name: CN983NS, available from Saedoma corporation), 10g of diluent (pentafunctional monomer, trade name: SR399NS, available from Saedoma corporation), 10g of isocyanate (1, 5-naphthalene diisocyanate NDI, available from COVESTRO corporation), 5g of photoinitiator (trade name: 184, available from Tianjin Kai chemical Co., Ltd.), 0.2g of leveling assistant (BYK-354, available from Bijinska chemical Co., Ltd.), and 54.8g of ethyl acetate were placed in a stirring pot, and stirred uniformly to obtain a coating solution for later use.
Coating an antistatic coating liquid on a 250-micron polyethylene terephthalate film, and curing to form an antistatic layer; the antistatic coating liquid was prepared by uniformly stirring 8g of a polyurethane resin (trade name: UCECOAT 7655, Zhan New resins Co., Ltd.), 6g of a hydroxyl-functionalized single-walled carbon nanotube (trade name: HQNANO-CNTS-002C, Suzhou carbone graphene science Co., Ltd.), 1.0g of a crosslinking agent (trade name: 710, Changzhou blue Asia New materials science Co., Ltd.), 3g of an auxiliary agent (BYK-307, Bika chemical Co., Ltd.), and 82g of deionized water.
Coating the above coating liquid on antistatic layer, placing in oven at 120 deg.C for 5min, and then using ultraviolet energy of 1000mJ/cm2Carrying out UV curing on the coating by using the ultraviolet light to obtain a hardened layer; the antistatic layer was 300nm in thickness and the cured layer was 1 μm in thickness, and the evaluation results are shown in Table 1.
Comparative example 3
12g of urethane acrylate resin (functionality 6, trade name: CN8011NS, Saedoma), 18g of diluent (pentafunctional monomer, trade name: SR399NS, Saedoma), 5g of isocyanate (hydrogenated diphenylmethane diisocyanate H12MDI, winning and creating company), 3g of photoinitiator (product name: 651, manufactured by Tianjin Tianjiao chemical Co., Ltd.), 2g of leveling assistant (modernia, Levaslip407) and 60g of ethyl acetate were placed in a stirring pot, and stirred uniformly to obtain a coating solution for later use.
Coating an antistatic coating liquid on a polymethyl methacrylate film with the thickness of 125 mu m, and curing to form an antistatic layer; the antistatic coating liquid was prepared by uniformly stirring 15g of a polyurethane resin (trade name: UCECOAT 7655, Zhan New resins Co., Ltd.), 10g of a hydroxyl-functionalized single-walled carbon nanotube (trade name: HQNANO-CNTS-002C, Suzhou carbone graphene science Co., Ltd.), 2.0g of a crosslinking agent (trade name: 710, Changzhou blue Asia New Material science Co., Ltd.), 5g of an auxiliary agent (BYK-307, Bikechemistry) and 68g of deionized water.
Coating the above coating liquid on antistatic layer, placing in oven at 105 deg.C for 8min, and then using ultraviolet energy of 600mJ/cm2Carrying out UV curing on the coating by using the ultraviolet light to obtain a hardened layer; the antistatic layer had a thickness of 400nm and the cured layer had a thickness of 5 μm, and the evaluation results are shown in Table 1.
Comparative example 4
19g of urethane acrylate resin (functionality of 4, product name: DR-U052, Changhing chemical), 20g of diluent (trifunctional monomer, Changhing chemical, product name: EM331), 4.5g of photoinitiator (product name: TPO, manufactured by Tianjin Tianjiao chemical Co., Ltd.), 1.5g of leveling aid (gentle chemical, Levaslip410) and 55g of butyl acetate were placed in a stirred pot, and stirred uniformly to obtain a coating solution for later use.
Coating an antistatic coating liquid on a polycarbonate film with the thickness of 50 mu m, and curing to form an antistatic layer; the antistatic coating liquid was prepared by uniformly stirring 6g of a polyurethane resin (trade name: UCECOAT 7655, Zhan New resins Co., Ltd.), 4g of a hydroxyl-functionalized single-walled carbon nanotube (trade name: HQNANO-CNTS-002C, Suzhou carbofeng graphene science Co., Ltd.), 0.8g of a crosslinking agent (trade name: 710, Changzhou blue Asia New materials science Co., Ltd.), 2g of an auxiliary agent (BYK-307, Bikechemistry) and 87.2g of deionized water.
Coating the above coating liquid on antistatic layer, placing in oven at 110 deg.C for 6min, and then using ultraviolet energy of 900mJ/cm2Carrying out UV curing on the coating by using the ultraviolet light to obtain a hardened layer; the antistatic layer had a thickness of 500nm and the cured layer had a thickness of 2 μm, and the evaluation results are shown in Table 1.
Comparative example 5
15g of urethane acrylate resin (functionality 2, Changxing chemical, trade name: 6152B-80), 12g of diluent (bifunctional monomer, Changxing chemical, trade name: EM3261), 6g of isocyanate (isophorone diisocyanate, IPDI, winning and creating company), 1.4g of photoinitiator (trade name: 184, manufactured by Tianjin Tianjiao chemical Co., Ltd.), 0.6g of leveling aid (BYK-377) and 65g of ethanol were placed in a stirring pot, and a coating solution was obtained after uniform stirring and was ready for use.
Coating an antistatic coating liquid on a 188-micron polyethylene terephthalate film, and curing to form an antistatic layer; the antistatic coating liquid was prepared by uniformly stirring 10g of a polyurethane resin (trade name: UCECOAT 7655, Zhan New resins Co., Ltd.), 8g of a single-walled carbon nanotube (trade name: HQNANO-CNTs-002, Suzhou carbofeng graphene science Co., Ltd.), 1.5g of a crosslinking agent (trade name: 710, Changzhou blue Asia New materials science Co., Ltd.), 4g of an auxiliary agent (BYK-307, Bicko chemical) and 76.5g of deionized water.
Coating the above coating liquid on antistatic layer, placing in oven at 115 deg.C for 7min, and then using ultraviolet light energy of 800mJ/cm2Carrying out UV curing on the coating by using the ultraviolet light to obtain a hardened layer; the antistatic layer was 450nm thick and the cured layer was 3 μm thick, and the evaluation results are shown in Table 1.
Table 1: test data table of antistatic optical hardening film in each example and comparative example
The surface resistance value is an important index for the antistatic performance of the reaction film material, and the antistatic function can be achieved generally when the surface resistance value is less than or equal to 12 times, but generally, the lower the resistance value is, the more excellent the antistatic performance is. As can be seen from the table, the high functionality urethane acrylate resin or diluent selected in comparative examples 1, 2 and 3 has high curing degree and high crosslinking density of the coating after UV curing, so that the resistance value of the final coating is higher and the antistatic performance is deviated. It can be seen from comparative examples 4 and 5 that the reactive cross-linked structure can maintain good interlayer adhesion between the antistatic layer and the hardened layer, and the carbon nanotubes are fixed in the coating, so that the antistatic performance is long-lasting and effective. In addition, the light transmittance is more than 90%, the haze is less than 1%, and the antistatic hardened film with the structure has excellent optical performance.
The test methods for the properties in the table are as follows:
(1) measurement of light transmittance and haze
Using a haze meter [ Nippon Denshoku Kogyo; the model is as follows: NDH2000N ], light transmittance and haze were measured.
(2) Pencil hardness test
Film hardness tester using pencil scratch [ manufactured by shanghai pushen chemical machinery ltd; the model is as follows: "BY" ] measuring pencil hardness.
(3) Coating adhesion testing method
Referring to the standard GB/T9286, the hard coating surface of the hard coating film was cut into 100 cross-sectional lines each having a size of 1mm by 1mm using a cutter, and then a professional test tape (3M company) type 3M-610 was adhered to the cross-hatched hard coating surface with a force of 2.0 Kg. After 3min the 3M tape was peeled off the surface at an angle of 180 °. The coating adhesion was evaluated by counting the number of cross-sectional lines of the hard coating remaining on the substrate, and was graded from low to high by 5 grades, 1B, 2B, 3B, 4B and 5B.
(5) Surface resistance value testing method
Using a high impedance meter [ Shanghai sixth electric meter plant; the model is as follows: PC68 measurement of surface resistance of hardened film
The above description is only some examples of the present invention, and is not intended to limit the scope of the present invention. All equivalent changes and modifications made according to the core technology of the present invention shall be covered by the scope of the present invention.
Claims (6)
1. An antistatic optical hardening film comprises a support body, an antistatic layer and a hardening layer, and is characterized in that the antistatic layer is coated on the surface of the support body and is formed by curing a coating liquid containing polyurethane resin and carbon nano tubes; coating a hardened layer on the surface of the antistatic layer, wherein the hardened layer is formed by curing a coating liquid consisting of the following components in parts by weight:
10 to 20 parts by weight of urethane acrylate oligomer,
10 to 20 parts by weight of a diluent,
5 to 10 parts by weight of isocyanate,
0.1 to 5 parts by weight of a photoinitiator,
0.2 to 2 weight portions of leveling assistant,
45-65 parts of organic solvent;
the polyurethane acrylate oligomer is selected from aliphatic polyurethane acrylate with the functionality of below 4; the diluent is bifunctional or trifunctional acrylate monomer;
the carbon nano tube in the antistatic layer is a single-walled carbon nano tube with functionalized hydroxyl.
2. The antistatic optical hardening film according to claim 1, wherein the pencil hardness of the hardened layer is 1H to 3H.
3. The antistatic optical hardening film according to claim 1, wherein the isocyanate is one of isophorone diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene-1, 6-diisocyanate or hydrogenated diphenylmethane diisocyanate.
4. The antistatic optical hardening film according to claim 1, wherein the antistatic layer has a thickness of 300nm to 600 nm; the thickness of the hardening layer is 1-5 μm.
5. The antistatic optical hardening film according to claim 1, wherein the support is one of a polycarbonate film, a polyethylene terephthalate film, and a polymethyl methacrylate film; the thickness of the support is 23 μm to 250 μm.
6. The antistatic optical hardening film according to claim 1, wherein the hardening layer is cured by drying a solvent in a drying oven at 100-120 ℃ for 5-10 min; then ultraviolet light is carried out for curing, and the irradiation energy of the ultraviolet light is 500mJ/cm2～1000mJ/cm2。
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| CN110437730A (en) * | 2019-07-26 | 2019-11-12 | 四川羽玺新材料股份有限公司 | A kind of light weather-proof optical grade PET cured film |
| CN110698976A (en) * | 2019-11-21 | 2020-01-17 | 深圳市益达兴科技股份有限公司 | Process for producing coating with polyurethane acrylate resin |
| CN111875833A (en) * | 2020-06-16 | 2020-11-03 | 宁波惠之星新材料科技有限公司 | High-water-contact antistatic hardened film and preparation method thereof |
| CN112280085A (en) * | 2020-09-24 | 2021-01-29 | 浙江日久新材料科技有限公司 | Low-roughness MLCC functional release film capable of being used in tape casting and preparation method thereof |
| CN115521705B (en) * | 2022-10-26 | 2023-12-08 | 合肥乐凯科技产业有限公司 | Antistatic hardening film and preparation method thereof |
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| CN103642384A (en) * | 2013-12-06 | 2014-03-19 | 苏州贤聚科技有限公司 | Intrinsic anti-static hardened film and preparation method thereof |
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| CN103642384A (en) * | 2013-12-06 | 2014-03-19 | 苏州贤聚科技有限公司 | Intrinsic anti-static hardened film and preparation method thereof |
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