CN109254340B - Infrared and ultraviolet cut-off composition, infrared and ultraviolet cut-off film and application of infrared and ultraviolet cut-off film - Google Patents
Infrared and ultraviolet cut-off composition, infrared and ultraviolet cut-off film and application of infrared and ultraviolet cut-off film Download PDFInfo
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Abstract
The invention provides an infrared and ultraviolet cut-off composition, an infrared and ultraviolet cut-off film and application of the infrared and ultraviolet cut-off film. The infrared and ultraviolet cut-off composition comprises the following components in parts by weight: 10-80 parts of functional monomer; 5-40 parts of functional oligomer; 20-90 parts of a diluting solvent; 0.1-5 parts of nano-scale inorganic metal oxide, wherein the nano-scale inorganic metal oxide is a metal oxide which can absorb light in a wavelength range of 200-400 nm and reflect infrared light or near-infrared light in a wavelength range of 700-1200 nm; 0.1-5 parts of blue dye; 0.1-5 parts of an initiator. Because the composition contains the blue dye and the nano inorganic metal oxide with infrared and/or near-infrared absorption, the infrared and ultraviolet cut-off functions can be realized in the same film layer, so that the number of film systems in the infrared and ultraviolet cut-off filter can be reduced, and the number of layers for designing the film systems and the manufacturing method are simplified.
Description
Technical Field
The invention relates to the field of optical materials, in particular to an infrared and ultraviolet cut-off composition, an infrared and ultraviolet cut-off film and application of the infrared and ultraviolet cut-off film.
Background
Ultraviolet rays can age high molecular organic matters, and the ultraviolet rays need to be prevented from being injected or emitted in some occasions; the infrared ray can be transmitted through the glass, the indoor temperature is raised in summer, and the heat for indoor heating flows to the outdoor in winter. It follows that there is a need for a structure that blocks ultraviolet and infrared rays to avoid material degradation and unnecessary heat exchange. Currently, an infrared/ultraviolet cut film is conventionally used, which is attached to a glass capable of transmitting light to prevent the transmission of ultraviolet rays and infrared rays.
The existing method for preparing the infrared and ultraviolet cut-off film is mainly to deposit inorganic oxide with the cut-off function on a substrate by a vapor deposition method, but on one hand, the harsh process conditions of the vapor deposition have higher requirements on the performance of the substrate, generally need to bear higher temperature and larger energy bombardment, and can damage the substrate; on the other hand, in order to reduce the viewing angle dependence of the final optical film product, a blue glass or a blue film is selected.
Disclosure of Invention
The invention mainly aims to provide an infrared and ultraviolet cut-off composition, an infrared and ultraviolet cut-off film and application of the infrared and ultraviolet cut-off film, and aims to solve the problems that the infrared and ultraviolet cut-off film in the prior art has strict requirements on process conditions, is complex in process and has more layers.
In order to achieve the above object, according to one aspect of the present invention, there is provided an ir-uv cut composition comprising, in parts by weight: 10-80 parts of functional monomer; 5-40 parts of functional oligomer; 20-90 parts of a diluting solvent; 0.1-5 parts of nano inorganic metal oxide, wherein the nano inorganic metal oxide can absorb ultraviolet light with the wavelength of 200-400 nm and can reflect infrared light or near infrared light with the wavelength of 700-1400 nm; 0.1-5 parts of blue dye; 0.1-5 parts of an initiator.
Further, the functional monomer is 20 to 50 parts by weight, preferably 30 to 40 parts by weight, and is selected from acrylic monomers, polyurethane monomers, amide monomers and epoxy monomers, and more preferably methacrylic acid derivatives, modified epoxy acrylate, urethane acrylate or aromatic urethane acrylate.
Further, the functional oligomer is 10 to 30 parts by weight, and the functional oligomer is an aliphatic urethane acrylate having a functionality of 6 or more or an aromatic urethane acrylate oligomer having a functionality of 6 or more.
Further, the nanoscale inorganic metal oxide is ITO or SnO2And/or CdIn2O4。
Further, the blue dye is selected from one or more of phthalocyanine compounds and porphin compounds.
Further, the weight part of the diluting solvent is 30-80 parts, more preferably 45-75 parts; the diluting solvent is ketone solvent, benzene solvent or ester solvent, preferably ethyl acetate, butyl acetate, butanone, acetone, toluene or xylene.
Further, the initiator is a photoinitiator and/or a thermal initiator.
According to another aspect of the present invention, there is provided an ir-uv cut film comprising a substrate layer and an ir-uv cut functional layer, wherein the ir-uv cut functional layer is formed by curing a composition, wherein the composition is any one of the ir-uv cut compositions.
Further, the thickness of the infrared and ultraviolet cut-off functional layer is 0.01-5 μm, preferably, the cut-off depth of the infrared and ultraviolet cut-off film is more than or equal to 0.01, and the cut-off range is 700-1400 nm and/or 200-400 nm; the substrate layer is preferably a polymer transparent film or glass, and more preferably a PET film, PEN film, PI film, COP film or PC film having a thickness of 18 to 250 μm.
Further, the infrared and ultraviolet cut-off film also comprises a film group formed by multiple layers of high-refractive-index material layers and multiple layers of low-refractive-index material layers, wherein the multiple layers of high-refractive-index material layers and the multiple layers of low-refractive-index material layers are arranged on the surface, far away from the base material layer, of the infrared and ultraviolet cut-off functional layer, the high-refractive-index material layers and the low-refractive-index material layers are arranged in a crossed mode, and the number of the film group is 10-40; preferably, the refractive index of the high-refractive-index material layer is 1.90-2.50; preferably, the refractive index of the low-refractive-index material layer is 1.35-1.60; preferred materials for the high refractive index material layer include ZnS, TiO2、Ti3O5、Nb2O5、Ta2O5And ZnO; preferred materials for the low refractive index material layer include cryolite, SiO2And MgF2One or more of; preferably, the physical thickness of the high-refractive-index material layer is 10 nm-300 nm; the physical thickness of the low refractive index material layer is preferably 10nm to 300 nm.
According to still another aspect of the present invention, an infrared/ultraviolet cut-off film is provided, which includes a substrate layer and an infrared/ultraviolet cut-off functional layer, wherein the infrared/ultraviolet cut-off functional layer includes a resin matrix, and a blue dye and a nano-inorganic metal oxide dispersed in the resin matrix, the nano-inorganic metal oxide can absorb ultraviolet light with a wavelength of 200 to 400nm and can reflect infrared light or near infrared light with a wavelength of 700 to 1400nm, the blue dye is contained in the infrared/ultraviolet cut-off film in an amount of 0.08 to 24.75 wt%, preferably 0.1 to 10 wt%, and the nano-inorganic metal oxide is contained in the infrared/ultraviolet cut-off film in an amount of 0.08 to 24.75 wt%, preferably 0.1 to 10 wt%.
Further, the resin matrix is any one of an acrylic resin matrix, a polyurethane resin matrix, an amide resin matrix, and an epoxy resin matrix.
Further, the nanoscale inorganic metal oxide is ITO or SnO2、CdIn2O4。
Further, the blue dye is selected from one or more of phthalocyanine compounds and porphin compounds.
Further, the thickness of the infrared and ultraviolet cut-off functional layer is 0.01-5 μm, preferably, the cut-off depth of the infrared and ultraviolet cut-off film is more than or equal to 0.01, and the cut-off range is 700-1400 nm and/or 200-400 nm; the substrate layer is preferably a polymer transparent film or glass, and more preferably a PET film, PEN film, PI film, COP film or PC film having a thickness of 18 to 250 μm.
Further, the infrared and ultraviolet cut-off film also comprises a film group formed by multiple layers of high-refractive-index material layers and multiple layers of low-refractive-index material layers, wherein the multiple layers of high-refractive-index material layers and the multiple layers of low-refractive-index material layers are arranged on the surface, far away from the base material layer, of the infrared and ultraviolet cut-off functional layer, the high-refractive-index material layers and the low-refractive-index material layers are arranged in a crossed mode, and the number of the film group is 10-40; preferably, the refractive index of the high-refractive-index material layer is 1.90-2.50; preferably, the refractive index of the low-refractive-index material layer is 1.35-1.60; preferred materials for the high refractive index material layer include ZnS, TiO2、Ti3O5、Nb2O5、Ta2O5And ZnO; preferred materials for the low refractive index material layer include cryolite, SiO2And MgF2One or more of; preferably, the physical thickness of the high-refractive-index material layer is 10 nm-300 nm; the physical thickness of the low refractive index material layer is preferably 10nm to 300 nm.
According to a further aspect of the present invention, there is provided a use of the infrared-ultraviolet cut film of any one of the above in a light filtering member, preferably a window or a filter.
By applying the technical scheme of the invention, the nanoscale inorganic metal oxide and blue dye are mixed with the organic material for use, namely the nanoscale inorganic metal oxide and blue dye are dispersed in the functional monomer, the functional polymer and the diluting solvent to form the organic mixture, and the infrared and ultraviolet cut-off film can be formed by setting the organic mixture into a thin layer and curing the organic mixture by means of coating and the like by utilizing the curing characteristic of the functional monomer and the functional polymer under the action of the initiator, so that the use of vapor deposition and a blue film is avoided, and the problems of harsh and complex process conditions caused by the use of the infrared and ultraviolet cut-off film are solved.
In addition, the composition formed by mixing the components according to the proportion can disperse as much nanoscale inorganic metal oxide and blue dye as possible, so that the formed infrared and ultraviolet cut-off film has a better infrared and ultraviolet cut-off function; meanwhile, the infrared and ultraviolet cut-off film formed by the composition has higher physical hardness (pencil hardness is GB/T6739-1996, 2B-3H) and smoother and uniform appearance.
Meanwhile, the composition contains the blue dye and the nanoscale inorganic metal oxide with infrared and/or near-infrared absorption, so that when the composition is used for manufacturing an infrared and ultraviolet cut-off film of an infrared and ultraviolet cut-off filter, the infrared and ultraviolet cut-off functions can be realized in the same film layer, the number of film systems in the infrared and ultraviolet cut-off filter can be reduced, and the number of designed layers of the film systems is simplified.
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.
As analyzed by the background art, the infrared-ultraviolet cut film in the prior art has severe requirements on process conditions and complicated process, and in order to solve the problem, the present application provides an infrared-ultraviolet cut composition, an infrared-ultraviolet cut film, and a window.
In one exemplary embodiment herein, there is provided an ir-uv cut composition comprising, in parts by weight: 10-80 parts of functional monomer; 5-40 parts of functional oligomer; 20-90 parts of a diluting solvent; 0.1-5 parts of nano inorganic metal oxide; 0.1-5 parts of blue dye; 0.1-5 parts of initiator, wherein the nanoscale inorganic metal oxide is a metal oxide which can absorb light in the wavelength range of 200-400 nm and reflect infrared light or near-infrared light in the wavelength range of 700-1200 nm.
The application adopts the mixed use of the nanoscale inorganic metal oxide and the blue dye and the organic material, namely the nanoscale inorganic metal oxide and the blue dye are dispersed in the functional monomer, the functional polymer and the diluting solvent to form the organic mixture, the characteristic that the functional monomer and the functional polymer are cured under the action of the initiator is utilized, the organic mixture is set into a thin layer by means of coating and the like to form the infrared and ultraviolet cut-off film after being cured, the use of excessive vapor deposition and the blue film is avoided, the problems of harsh and complex process conditions caused by the above are solved, and the damage to the substrate layer and the embrittlement of the infrared and ultraviolet cut-off film are avoided.
In addition, the composition formed by mixing the components according to the proportion can disperse as much nanoscale inorganic metal oxide and blue dye as possible, so that the formed infrared and ultraviolet cut-off film has a better infrared and ultraviolet cut-off function; meanwhile, the infrared and ultraviolet cut-off film formed by the composition has higher physical hardness (pencil hardness is GB/T6739-1996, 2B-3H) and smoother and uniform appearance.
Meanwhile, the composition contains the blue dye and the nanoscale inorganic metal oxide with infrared and/or near-infrared absorption, so that when the composition is used for manufacturing an infrared and ultraviolet cut-off film of an infrared and ultraviolet cut-off filter, the infrared and ultraviolet cut-off functions can be realized in the same film layer, the number of film systems in the infrared and ultraviolet cut-off filter can be reduced, and the number of designed layers of the film systems is simplified.
In order to further optimize the physical hardness and wear resistance of the ir-uv cut film formed from the ir-uv cut composition, the functional monomer is preferably 20 to 50 parts by weight, more preferably 30 to 40 parts by weight, and is selected from acrylic monomers, polyurethane monomers, amide monomers, and epoxy monomers, and more preferably methacrylic acid derivatives, modified epoxy acrylates, urethane acrylates, or aromatic urethane acrylates. Preferably, the functional oligomer is 10 to 30 parts by weight, and the functional oligomer is an aliphatic urethane acrylate having a functionality of 6 or more or an aromatic urethane acrylate oligomer having a functionality of 6 or more. By utilizing the matching of the functional monomer and the functional polymer, the physical hardness and the appearance uniformity of the film layer are improved.
The nanoscale inorganic metal oxide useful in the present application may be selected from materials having infrared absorbing function in the prior art, preferably the nanoscale inorganic metal oxide is ITO or SnO2And/or CdIn2O4。
The blue dye used in the present application may be selected from materials having uv absorption function in the prior art, and preferably the blue dye is selected from one or more of phthalocyanine compounds and porphin compounds.
The main function of the diluting solvent is to facilitate the mutual mixing of the components, the diluting solvent can be volatilized in the subsequent curing process, and in order to accelerate the curing rate and ensure the mixing effect, the weight part of the diluting solvent is preferably 30-80 parts, more preferably 45-75 parts; the diluting solvent is ketone solvent, benzene solvent or ester solvent, preferably ethyl acetate, butyl acetate, butanone, acetone, toluene or xylene.
The initiator in the above composition may be selected from photoinitiators and thermal initiators according to the specific type of monomers and oligomers selected, and may be accomplished by those skilled in the art in combination with the knowledge available in the art, and will not be described herein.
In another exemplary embodiment of the present disclosure, an ir-uv cut film is provided, which includes a substrate layer and an ir-uv cut functional layer, wherein the ir-uv cut functional layer is formed by curing a composition, which is any one of the ir-uv cut compositions described above in the present disclosure.
The infrared and ultraviolet cut-off functional layer can be formed by setting an organic mixture formed by the infrared and ultraviolet cut-off composition into a thin layer and curing the thin layer through means of coating, spraying, evaporation, printing and the like, so that excessive vapor deposition and blue film use are avoided, the problems of harsh and complex process conditions caused by the above are solved, and the damage to the substrate layer and the embrittlement of the infrared and ultraviolet cut-off film are avoided. In addition, the infrared and ultraviolet cut-off composition can disperse as many nanoscale inorganic metal oxides and blue dyes as possible, so that the formed infrared and ultraviolet cut-off functional layer has an ideal infrared and ultraviolet cut-off function; meanwhile, the infrared and ultraviolet cut-off functional layer formed by the composition has high physical hardness (pencil hardness is GB/T6739-1996, 2B-3H) and smooth and uniform appearance. Meanwhile, the composition contains blue dye and nano inorganic metal oxide with infrared and/or near-infrared absorption, so that the obtained infrared and ultraviolet cut-off functional layer can be realized in the same film layer, and the number of the film layers forming the infrared and ultraviolet cut-off film can be reduced.
The thickness of the infrared and ultraviolet cut-off functional layer is preferably 0.01-5 mu m, the cut-off depth of the infrared and ultraviolet cut-off film is preferably more than or equal to 0.01, and the cut-off range is 700-1400 nm and/or 200-400 nm. The substrate layer is preferably a polymer transparent film or glass, and further preferably a PET film, a PEN film, a PI film, a COP film or a PC film with the thickness of 18-250 μm, so as to ensure the flexibility of the infrared and ultraviolet cut-off film.
Preferably, the infrared and ultraviolet cut-off film further comprises a film group formed by multiple layers of high refractive index material layers and multiple layers of low refractive index material layers, wherein the multiple layers of high refractive index material layers and the multiple layers of low refractive index material layers are arranged on the surface, far away from the base material layer, of the infrared and ultraviolet cut-off functional layer, the high refractive index material layers and the low refractive index material layers are arranged in a crossed mode, and the number of the film group is 10-40; preferably, the refractive index of the high-refractive-index material layer is 1.90-2.50; preferably, the refractive index of the low-refractive-index material layer is 1.35-1.60; preferred materials for the high refractive index material layer include ZnS, TiO2、Ti3O5、Nb2O5、Ta2O5And ZnO; preferably, the material of the low refractive index material layer comprisesCryolite, SiO2And MgF2One or more of; preferably, the physical thickness of the high-refractive-index material layer is 10 nm-300 nm; the physical thickness of the low refractive index material layer is preferably 10nm to 300 nm. By means of the crossed arrangement of the high-refractive-index material layers and the low-refractive-index material layers, the stability and efficiency of infrared cut-off and ultraviolet cut-off are improved.
The refractive index matching film group with high and low matching is an interference film, and the transmission rate of the interference film in a near infrared light wavelength range can be better controlled by the interference film. The film group is formed by alternately arranging high refractive index material layers and low refractive index material layers, the material of the high refractive index material layers is generally a material having a refractive index of more than 1.7, and the refractive index range of 1.7 to 2.5 is generally selected, preferably 1.90 to 2.50, for example, a material containing titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc sulfide, indium oxide as a main component and a small amount of titanium oxide, tin oxide, cesium oxide, or the like. The material of the low refractive index material layer is generally a material having a refractive index of less than 1.6, and the refractive index is generally selected to be in a range of 1.2 to 1.6, preferably 1.35 to 1.6, for example, silicon oxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, sodium aluminum hexafluoride, and the like.
In another exemplary embodiment of the present application, an ir-uv cut film is provided, which includes a substrate layer and an ir-uv cut functional layer, wherein the ir-uv cut functional layer includes a resin matrix and a blue dye and a nano-inorganic metal oxide dispersed in the resin matrix, the nano-inorganic metal oxide can absorb ultraviolet light with a wavelength of 200 to 400nm and can reflect infrared light or near infrared light with a wavelength of 700 to 1400nm, the weight content of the blue dye in the ir-uv cut film is 0.08 to 24.75%, preferably 0.1 to 10%, and the weight content of the nano-inorganic metal oxide is 0.08 to 24.75%, preferably 0.1 to 10%.
Because the infrared and ultraviolet cut-off functional layer simultaneously contains the blue dye and the nano inorganic metal oxide with infrared and/or near infrared absorption, the infrared and ultraviolet cut-off function can be realized in the same film layer, the number of film systems in the infrared and ultraviolet cut-off filter can be further reduced, and the number of layers for designing the film systems is simplified. Excessive vapor deposition and blue film use are avoided, the problems of harsh and complex process conditions caused by the excessive vapor deposition and blue film use are solved, and damage to the substrate layer and embrittlement of the infrared and ultraviolet cut-off film are avoided. In addition, the blue dye and the nano inorganic metal oxide with the contents can be well dispersed in the matrix, so that the formed infrared and ultraviolet cut-off film has ideal infrared and ultraviolet cut-off function; meanwhile, the infrared and ultraviolet cut-off film has higher physical hardness (pencil hardness is GB/T6739-1996, 2B-3H) and smoother and uniform appearance. Further, the infrared and ultraviolet cut-off functional layer simultaneously contains blue dye and nano inorganic metal oxide with infrared and/or near infrared absorption, so that the obtained infrared and ultraviolet cut-off functional layer can be realized in the same film layer, and the number of the film layers forming the infrared and ultraviolet cut-off film can be reduced.
The weight contents of the blue dye and the nano-scale inorganic oxide can be calculated according to the mixture ratio of each component in the raw materials.
Further, the resin matrix is preferably any one of an acrylic resin matrix, a polyurethane resin matrix, an amide resin matrix, and an epoxy resin matrix. The resins can be obtained by curing corresponding monomers, oligomers, initiators and a proper amount of diluting solvents in the presence of the resins, and the specific curing method can refer to the prior art and is not described herein again.
The nanoscale inorganic metal oxide useful in the present application may be selected from materials having infrared absorbing function in the prior art, preferably the nanoscale inorganic metal oxide is ITO or SnO2、CdIn2O4。
The blue dye used in the present application may be selected from materials having uv absorption function in the prior art, and preferably the blue dye is selected from one or more of phthalocyanine compounds and porphin compounds.
The thickness of the infrared and ultraviolet cut-off functional layer is preferably 0.01-5 mu m, the cut-off depth of the infrared and ultraviolet cut-off film is preferably more than or equal to 0.01, and the cut-off range is 700-1400 nm and/or 200-400 nm. The substrate layer is preferably a polymer transparent film or glass, and more preferably a PET film, PEN film, PI film, COP film or PC film having a thickness of 18 to 250 μm.
Preferably, the infrared and ultraviolet cut-off film further comprises a film group formed by multiple layers of high refractive index material layers and multiple layers of low refractive index material layers, wherein the multiple layers of high refractive index material layers and the multiple layers of low refractive index material layers are arranged on the surface, far away from the base material layer, of the infrared and ultraviolet cut-off functional layer, the high refractive index material layers and the low refractive index material layers are arranged in a crossed mode, and the number of the film group is 10-40; preferably, the refractive index of the high-refractive-index material layer is 1.90-2.50; preferably, the refractive index of the low-refractive-index material layer is 1.35-1.60; preferred materials for the high refractive index material layer include ZnS, TiO2、Ti3O5、Nb2O5、Ta2O5And ZnO; preferred materials for the low refractive index material layer include cryolite, SiO2And MgF2One or more of; preferably, the physical thickness of the high-refractive-index material layer is 10 nm-300 nm; the physical thickness of the low refractive index material layer is preferably 10nm to 300 nm. By means of the crossed arrangement of the high-refractive-index material layers and the low-refractive-index material layers, the stability and efficiency of infrared cut-off and ultraviolet cut-off are improved.
The refractive index matching film group with high and low matching is an interference film, and the transmission rate of the interference film in a near infrared light wavelength range can be better controlled by the interference film. The film group is formed by alternately arranging high refractive index material layers and low refractive index material layers, the material of the high refractive index material layers is generally a material having a refractive index of more than 1.7, and the refractive index range of 1.7 to 2.5 is generally selected, preferably 1.90 to 2.50, for example, a material containing titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc sulfide, indium oxide as a main component and a small amount of titanium oxide, tin oxide, cesium oxide, or the like. The material of the low refractive index material layer is generally a material having a refractive index of less than 1.6, and the refractive index is generally selected to be in a range of 1.2 to 1.6, preferably 1.35 to 1.6, for example, silicon oxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, sodium aluminum hexafluoride, and the like.
In yet another exemplary embodiment of the present application, there is provided a use of any one of the infrared-ultraviolet cut films described above in a light filtering member, preferably a window or a filter.
The window with the infrared and ultraviolet cut-off film and the infrared and ultraviolet cut-off function of the optical filter are good, the corresponding manufacturing process is simple, and the manufacturing cost is low. Meanwhile, the infrared and ultraviolet cut-off function is concentrated in the same film layer, so that the stacking number of functional layers of the infrared and ultraviolet cut-off film is reduced.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
The blue dyes used in the examples and comparative examples are described in table 1. The infrared-ultraviolet cut composition of example 1 was formulated in accordance with the formulation (in parts by weight) in table 2.
TABLE 1
TABLE 2
After the components in each of examples and comparative examples were thoroughly mixed, the mixture was coated on an optical grade PET film having a thickness of 100 μm by a wire bar, dried at 80 ℃ for 3 minutes, and irradiated with light at an energy of 300mj/cm2Irradiating the substrate for 2 minutes to obtain a base film with the thickness of 3 mu m (the coating is an infrared and ultraviolet cut-off functional layer);
adopting an evaporation coating method to sequentially and alternately coat TiO on the coating of the base film of each embodiment2Layer (refractive index of 2.36) and low refractive index material SiO2Layer (refractive index 1.52) of TiO2Layer and SiO2The total number of layers is 10, and the initial layer deposited on the base film is TiO2Layer, the second layer is SiO2Layers, which were alternately deposited in this order and had thicknesses of 10.24nm, 34.77nm, 103.72nm, 160.17nm, 93.16nm, 153.35nm, 98.46nm, 166.36nm, 101.66nm, and 157.37nm in this order, were formed into infrared-ultraviolet cut films of each example and comparative example.
Example 9
The difference from example 1 is that a high refractive index material layer and a low refractive index material layer are not provided.
Comparative example 6
Sequentially alternating TiO on an optical grade PET film with the thickness of 100 mu m2Layer (refractive index of 2.36) and low refractive index material SiO2Layer (refractive index 1.52) of TiO2Layer and SiO2A total of 40 layers, with the initial layer deposited on the base film being TiO2Layer, the second layer is SiO2And the layers are alternately deposited in sequence, and the thicknesses are 10.24nm, 34.77nm, 103.72nm, 160.17nm, 93.16nm, 153.35nm, 98.46nm, 166.36nm, 101.66nm and 157.37nm in sequence, so that the infrared and ultraviolet cut-off film is obtained.
Comparative example 7
Sequentially alternating TiO on an optical grade PET film with the thickness of 100 mu m2Layer (refractive index of 2.36) and low refractive index material SiO2Layer (refractive index 1.52) of TiO2Layer and SiO2A total of 40 layers, with the initial layer deposited on the base film being TiO2Layer, the second layer is SiO2Layers, both deposited alternately in sequence and having a thickness in sequence of 10.24nm, 34.77nm, 103.72nm, 160.17nm, 93.16nm, 153.35nm, 98.46nm, 166.36nm, 101.66nm, 157.37nm, 89.81nm, 145.33nm, 84.64nm, 142.17nm, 82.38nm, 141.53nm, 81.40nm, 141.53nm, 84.07nm, 142.96nm, 95.76nm, 80.64nm, 5.11nm, 44.04nm, 5.02nm, 187.75nm, 99.85nm, 149.51nm, 90.88nm, 164.21nm, 110.06nm, 182.45nm, 110.47nm, 176.59nm, 112.86nm, 180.53nm, 109.86nm, 177.21nm, 109.74nm and 175.55nm to obtain the infrared and ultraviolet cut-off film.
Each prepared film was tested, and the test method of each relevant property was as follows:
film transmittance (corresponding cut-off depth): measuring the transmitted light spectrum of the obtained diaphragm within the range of 250-2500 nm by using a Lambda950 spectrophotometer, and respectively measuring the cut-off depths of ultraviolet and infrared by respectively measuring the transmittance at 350nm and the transmittance at 1300nm (taking round as a standard integer);
coating hardness: the hardness of the coating was measured according to the method of standard GB/T6739-1996, using a Millimarc1216 pencil hardness tester;
appearance of the coating: the coating appearance was visually observed and evaluated according to the following criteria:
the appearance of the coating does not show crystal points or particles are counted as √
Appearance of the coating layer with only a few crystal points or particles was rated as ∘
The appearance of the coating shows a great deal of particle agglomeration is counted as
TABLE 2
As can be seen from the data in table 2, the infrared cut effect, the ultraviolet cut effect, the hardness, and the appearance of each example of the present application are better than those of each cut film of the comparative example. And the infrared cut-off film layer has a simple structure and does not need repeated arrangement of multiple film layers. Wherein, lower light transmittance means higher cut-off depth, for example, when the light transmittance is 5%, the corresponding cut-off depth is 0.95; in addition, as can be seen from comparison of example 1, comparative example 1 and comparative example 5, when the nano-sized inorganic metal oxide or blue dye is used in an excessive amount, dispersion unevenness in the resin is caused, the exertion of the ultraviolet and infrared cut-off effects thereof is affected, and the appearance of the hard film layer is deteriorated. According to the comparison between the example 1 and the example 9, the infrared and ultraviolet cut-off effect of the infrared and ultraviolet cut-off film is obviously improved after the high and low refractive index layers are added; as can be seen from comparison of example 1, comparative example 6 and comparative example 7, the ir-uv cut functional layer provided with the inorganic metal oxide and the blue dye of the present application has a superior ir-uv cut effect.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the application adopts the mixed use of nano-scale inorganic metal oxide and blue dye and organic material, namely nano-scale inorganic metal oxide and blue dye are dispersed in functional monomer, functional polymer and diluting solvent to form organic mixture, the characteristic of curing under the action of initiator by functional monomer and functional polymer is utilized, the infrared ultraviolet cut-off film can be formed after the organic mixture is set into thin layer curing by means such as coating, the use of vapor deposition and blue film is avoided, and then the problems of harsh and complex process conditions caused by the method are solved, and the damage to the substrate layer and the embrittlement of the infrared ultraviolet cut-off film are avoided.
In addition, the composition formed by mixing the components according to the proportion can disperse as much nanoscale inorganic metal oxide and blue dye as possible, so that the formed infrared and ultraviolet cut-off film has a better infrared and ultraviolet cut-off function; meanwhile, the infrared and ultraviolet cut-off film formed by the composition has higher physical hardness (pencil hardness is GB/T6739-1996, 2B-3H) and smoother and uniform appearance.
Meanwhile, the composition simultaneously contains the blue dye and the nano inorganic metal oxide with infrared and/or near-infrared absorption, so when the composition is used for manufacturing a film layer, the infrared and ultraviolet cut-off functions can be realized in the same film layer, and the number of the film layers forming the infrared cut-off function film can be further reduced.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (26)
1. An infrared-ultraviolet cut composition, characterized in that the infrared-ultraviolet cut composition comprises, in parts by weight:
10-80 parts of functional monomers, wherein the functional monomers are selected from acrylic monomers, polyurethane monomers, amide monomers and epoxy monomers;
5-40 parts of functional oligomer, wherein the functional oligomer is aliphatic urethane acrylate with the functionality of 6 or more or aromatic urethane acrylate oligomer with the functionality of 6 or more;
20-90 parts of a diluting solvent;
0.1-5 parts of nano inorganic metal oxide, wherein the nano inorganic metal oxide can absorb ultraviolet light with the wavelength range of 200-400 nm and can reflect infrared light or near infrared light with the wavelength range of 700-1400 nm;
0.1-5 parts of blue dye;
0.1-5 parts of an initiator.
2. The ir-uv cut composition according to claim 1, wherein the functional monomer is 20 to 50 parts by weight.
3. The ir-uv cut composition according to claim 2, wherein the functional monomer is 30 to 40 parts by weight.
4. The ir-uv cut composition according to claim 2, wherein the functional monomer is a methacrylic acid derivative, a modified epoxy acrylate, a urethane acrylate or an aromatic urethane acrylate.
5. The ir-uv cut composition according to claim 1, wherein the functional oligomer is present in an amount of 10 to 30 parts by weight.
6. The ir-uv cut composition according to claim 1, wherein the nanoscale inorganic metal oxide is ITO, SnO2And/or CdIn2O4。
7. The ir-uv cut composition according to claim 1, wherein the blue dye is selected from one or more of the phthalocyanine group and the porphin group.
8. The ir-uv cut composition according to claim 1, wherein the diluting solvent is present in an amount of 30 to 80 parts by weight.
9. The ir-uv cut composition according to claim 8, wherein the diluting solvent is present in an amount of 45 to 75 parts by weight.
10. The ir-uv cut composition according to claim 8, characterized in that the diluting solvent is a ketone solvent, a benzene solvent or an ester solvent.
11. The ir-uv cut composition according to claim 8, characterized in that the diluting solvent is ethyl acetate, butyl acetate, butanone, acetone, toluene or xylene.
12. The ir-uv cut composition according to claim 1, wherein the initiator is a photoinitiator and/or a thermal initiator.
13. An infrared-ultraviolet cut film comprising a substrate layer and an infrared-ultraviolet cut functional layer, wherein the infrared-ultraviolet cut functional layer is formed by curing a composition, and the composition is the infrared-ultraviolet cut composition according to any one of claims 1 to 12.
14. The infrared-ultraviolet cut film according to claim 13, wherein the infrared-ultraviolet cut functional layer has a thickness of 0.01 to 5 μm.
15. The ir-uv cut film according to claim 14, wherein the ir-uv cut film has a cut depth of 0.01 or more, a cut range of 700 to 1400nm and/or 200 to 400 nm.
16. The ir-uv cut film according to claim 14, wherein the substrate layer is a polymer transparent film or glass.
17. The infrared/ultraviolet cut film according to claim 15, wherein the base material layer is a PET film, a PEN film, a PI film, a COP film, or a PC film having a thickness of 18 to 250 μm.
18. The infrared-ultraviolet cut film as claimed in claim 13, further comprising a film group formed by multiple layers of high refractive index material layers and multiple layers of low refractive index material layers, wherein the multiple layers of high refractive index material layers and the multiple layers of low refractive index material layers are arranged on the surface of the infrared-ultraviolet cut functional layer, the surface is far away from the substrate layer, the high refractive index material layers and the low refractive index material layers are arranged in a crossed manner, and the number of the film group is 10-40.
19. The ir-uv cut film according to claim 18, wherein the high refractive index material layer has a refractive index of 1.7 to 2.50.
20. The ir-uv cut film according to claim 19, wherein the high refractive index material layer has a refractive index of 1.90 to 2.50.
21. The infrared-ultraviolet cut film according to claim 18, wherein the low refractive index material layer has a refractive index of 1.2 to 1.6.
22. The infrared-ultraviolet cut film of claim 21, wherein the low refractive index material layer has a refractive index of 1.35 to 1.60.
23. The ir-uv cut film according to claim 18, wherein the material of the high refractive index material layer comprises ZnS, TiO2、Ti3O5、Nb2O5、Ta2O5And ZnO.
24. The ir-uv cut film according to claim 18, wherein the material of the low refractive index material layer comprises cryolite, SiO2And MgF2One or more of (a).
25. The ir-uv cut film according to claim 18, wherein the physical thickness of the high refractive index material layer is 10nm to 300 nm.
26. The ir-uv cut film according to claim 18, wherein the low refractive index material layer has a physical thickness of 10nm to 300 nm.
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| CN113451414B (en) * | 2020-06-18 | 2022-07-29 | 重庆康佳光电技术研究院有限公司 | Thin film transistor device and preparation method thereof |
| CN113451413B (en) * | 2020-06-18 | 2022-07-08 | 重庆康佳光电技术研究院有限公司 | A kind of thin film transistor device and preparation method thereof |
| CN116410656B (en) * | 2021-12-30 | 2024-07-30 | 上海飞凯材料科技股份有限公司 | Light-shielding composition, preparation method thereof and display device |
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