Filter

Abstract

To set a specific near-infrared absorption layer on a filter, providing the filter that is able to efficiently absorb near-infrared, exhibit excellent visible light transmittance, and can reduce the burden of post-processing.SOLUTION: Provided is a filter 1, including a substrate layer 20 and a near-infrared absorption layer 10 on the substrate layer 20, wherein the near-infrared absorption layer 10 includes a copper complex, the copper complex is formed from a copper compound used for supplying copper ions, phosphoric acid represented by formula 1 herein, and at least one phosphorus-containing compound represented by formulas 2 to 4 herein, wherein the OD value of the filter 1 for the incident light wavelength from 930-950 nm is greater than 4.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] The present disclosure relates to filters, and in particular to filters that include a near-infrared absorbing layer that contains a copper complex. [Background technology]

[0002] Near-infrared absorbing filters are widely used in optical devices such as image sensors, but as the demands for image resolution and pattern optical quality increase day by day, current near-infrared absorbing filters are no longer able to meet these new requirements. Therefore, in order to meet the increasingly stringent requirements of today's increasingly high standards, it has become necessary to develop near-infrared absorbers that have good transmittance in the visible light region and good shielding properties in the near-infrared region (i.e., lower than the current transmittance of 8-15%).

[0003] Meanwhile, optical identification elements currently in widespread use generally use near-infrared light, particularly near-infrared light with a wavelength of 940 nm, as an identification light source. Therefore, devices equipped with an optical identification element and an image sensor must effectively block the identification light source using a filter in the image sensor.

[0004] The filtering effect of an absorption filter depends on the thickness of the material; the thinner the material, the better the light transmittance, and the thicker the material, the greater the light filtering effect. In the prior art, technical means have been reported for improving filtering effect by increasing the thickness of a material with near-infrared blocking ability, such as blue glass or a dye absorption layer, located on the filter, or by increasing the number and thickness of optical coatings, such as anti-reflection coatings. However, as portability (e.g., lighter, thinner, shorter, smaller) becomes more important, technical means for improving optical performance by increasing the thickness of materials or coatings no longer meet the demand.

[0005] In addition, while increasing the coating thickness can improve the filtering effect, as the coating thickness and complexity increase, the material workability and processing difficulty decrease, and the loss rate also increases, resulting in increased costs and reduced industrial applicability. The thicker the coating, the lower the image quality degradation, which does not meet the trend toward higher resolution. Summary of the Invention

[0006] In response to the above-mentioned problems, the present disclosure provides a filter including a substrate layer and a near-infrared absorbing layer on the substrate layer, The near-infrared absorbing layer contains a copper complex, and the copper complex is formed from a copper compound used to supply copper ions, a phosphonic acid represented by the following formula 1, and at least one phosphorus-containing compound represented by formulas 2 to 4: TIFF0007802865000001.tif10667 (wherein R, R1, R2, and R3 each independently represent a substituted or unsubstituted C1 to C 12 Alkyl or substituted or unsubstituted C6-C 12 It is aryl. The filter has an OD value of greater than 4 for incident light wavelengths of 930 nm to 950 nm.

[0007] In one embodiment, substituted or unsubstituted C1-C 12 Alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl, and is a substituted or unsubstituted C-C 12 Aryl is selected from the group consisting of phenyl, naphthyl, and chlorophenyl.

[0008] In one embodiment, the haze of the near infrared absorbing layer is 0.4% or less.

[0009] In one embodiment, the X-ray photoelectron spectrum of the near-infrared absorbing layer has at least one main peak when the binding energy is 930 electron volts (eV) to 940 eV. In another embodiment, the counts per second value of the at least one main peak in the X-ray photoelectron spectrum is 4500 or more.

[0010] In one embodiment, the near-infrared absorbing layer has a thickness of 25 μm to 150 μm.

[0011] In one embodiment, the filter has an OD value of greater than 4.5 for an incident light wavelength of 940 nm.

[0012] In one embodiment, the near-infrared absorbing layer further comprises an optical resin, and the copper complex is dispersed in the optical resin. In one embodiment, the optical resin is a thermoplastic resin and / or a photocurable resin. In one embodiment, the optical resin is selected from polycarbonates, polyesters, polycycloolefins, polyacrylic acids, siloxane resins, and polyimides.

[0013] In one embodiment, the filter further comprises a filter layer on the opposite side of the substrate layer from the near infrared absorbing layer.

[0014] In one embodiment, the filter further comprises a filter layer on the opposite side of the substrate layer from the near infrared absorbing layer.

[0015] In one embodiment, the filter layer further comprises a first absorbing dye layer and / or a second absorbing dye layer, wherein the first absorbing dye layer comprises a near-infrared absorbing dye and the second absorbing dye layer comprises a UV absorbing dye. absorption Contains dyes.

[0016] In one embodiment, the near-infrared absorbing dye is at least one selected from the group consisting of an azo compound, a diimine compound, a dithiophene metal complex, a squaraine compound, a cyanine compound, and a phthalocyanine compound.

[0017] In one embodiment, the ultraviolet absorbing dye is at least one selected from the group consisting of azomethine compounds, indole compounds, ketone compounds, benzimidazole compounds, and triazine compounds.

[0018] In one embodiment, the thickness of each of the first absorbing dye layer and the second absorbing dye layer is 0.5 μm to 10 μm, and the total thickness of the filter layer is 0.5 μm to 10 μm.

[0019] In one embodiment, the filter further comprises at least one anti-reflective layer on the outermost side of the filter.

[0020] In one embodiment, the material of at least one anti-reflection layer is at least one selected from TiO2, SiO2, Y2O3, MgF2, Al2O3, Nb2O5, AlF3, Bi2O3, Gd2O3, LaF3, PbTe, Sb2O3, SiO, SiN, Ta2Os, ZnS, ZnSe, ZrO2, and Na3AlF6, and the thickness is 0.5 μm to 10 μm.

[0021] In one embodiment, the filter further comprises a protective layer, and the material of the protective layer is an optical resin.

[0022] In one embodiment, the thickness of the protective layer is 10 μm to 30 μm, and the protective layer is located between the near-infrared absorbing layer and the anti-reflection layer.

[0023] In one embodiment, the total thickness of the filter is between 225 μm and 800 μm.

[0024] In one embodiment, the filter has a passband that overlaps the wavelength range of 350 nm to 850 nm, and the center wavelength of the passband is within the wavelength range of 350 nm to 850 nm.

[0025] In one embodiment, the haze of the filter is 0.5% or less.

[0026] In one embodiment, the filter has a maximum transmittance of 0.01% or less for incident light wavelengths in the range of 930 nm to 950 nm, a maximum transmittance of 0.005% or less for incident light wavelengths in the range of 930 nm to 950 nm, a minimum transmittance of 80% or more for incident light wavelengths in the range of 460 nm to 560 nm, and a minimum transmittance of 85% or more for incident light wavelengths in the range of 460 nm to 560 nm.

[0027] In one embodiment, when incident light is incident on the filter at angles of incidence of 0 degrees and 30 degrees, respectively, the center wavelength of the passband of the filter shifts by 1.4 nm or less, and when incident light is incident on the filter at angles of incidence of 0 degrees and 35 degrees, respectively, the center wavelength of the passband of the filter shifts by 1.9 nm or less.

[0028] The filter of the present disclosure, by incorporating a specific near-infrared absorbing layer, can efficiently absorb incident light with wavelengths of 800 nm to 1100 nm, and particularly, can effectively absorb incident light with a wavelength of 940 nm, while exhibiting high transmittance for visible light. Therefore, the present disclosure achieves excellent near-infrared blocking effect while maintaining high visible light transmittance without increasing the thickness of the product, the thickness of the coating, or its complexity. [Brief explanation of the drawings]

[0029] [Figure 1A] FIG. 1A is a schematic diagram of the structure of a filter of the present disclosure. [Figure 1B] FIG. 1B is a schematic diagram of the structure of the filter of the present disclosure. [Figure 1C] FIG. 1C is a schematic diagram of the structure of the filter of the present disclosure. [Figure 2] FIG. 2 is a schematic diagram of the structure of the filter of the present disclosure. [Figure 3] FIG. 3 is a schematic diagram of the structure of the filter of the present disclosure. [Figure 4] FIG. 4 is a schematic diagram of the structure of the filter of the present disclosure. [Figure 5] FIG. 5 is an X-ray photoelectron spectrum of the near-infrared absorbing layer in Production Example 1. [Figure 6] FIG. 6 is a graph showing the transmittance of the first filter layer and the second filter layer in Production Example 1. [Figure 7] FIG. 7 is a graph showing the transmittance of AF32 glass, and graphs showing the transmittance of the filter layer and the near-infrared absorbing layer in Production Example 1. [Figure 8] FIG. 8 is a graph showing the transmittance of three configurations in Production Example 1, including the substrate layer, the substrate layer+filter layer, and the substrate layer+near-infrared absorbing layer+filter layer. [Figure 9] FIG. 9 is a graph showing the transmittance of the filters of Example 1 and Comparative Example 1. [Figure 10] FIG. 10 is a graph showing the transmittance of the filters of Example 2 and Comparative Example 1. [Figure 11] FIG. 11 is a graph showing the transmittance of the filters of Example 3 and Comparative Example 1. [Figure 12] FIG. 12 is a graph showing the transmittance of the filters of Example 4 and Comparative Example 1. [Figure 13] FIG. 13 is a graph showing OD values ​​of the filters of Examples 1 to 4 with respect to incident light wavelengths of 930 nm to 950 nm. [Figure 14] FIG. 14 is a graph showing transmittance when light is incident on the filter of Example 1 at angles of incidence of 0 degrees, 30 degrees, and 35 degrees, respectively. [Figure 15] FIG. 15 is a graph showing transmittance when light is incident on the filter of Example 3 at angles of incidence of 0 degrees, 30 degrees, and 35 degrees, respectively. DETAILED DESCRIPTION OF THE INVENTION

[0030] Hereinafter, the embodiments of the present disclosure will be described with reference to specific examples, and those skilled in the art can easily understand the scope and advantages of the present disclosure based on the contents of this specification.

[0031] However, the structures, ratios, sizes, etc. shown in the drawings attached to this specification are intended to facilitate understanding and reading by those skilled in the art in accordance with the contents of the specification and are not intended to limit the conditions for enabling the present disclosure, and therefore have no substantial technical significance. Any structural modifications, changes in ratios, or adjustments in size should be considered to be within the scope of the technical content disclosed in this disclosure, as long as they do not affect the effects and objectives achieved by the present disclosure. At the same time, the terms "upper," "first," "second," etc. used in this specification are used for convenience of explanation only and do not limit the scope of the present disclosure, and therefore, as long as there are no substantial changes in the technical content, any changes or adjustments to their relative relationships should be considered to be within the scope of the present disclosure.

[0032] In this specification, when a particular feature is described as "including," "comprising," or "having," unless otherwise specified, it may include other features such as parts, components, structures, areas, parts, devices, systems, steps, or connection relationships, and does not exclude such other features.

[0033] Unless expressly stated otherwise herein, the singular forms "a," "an," and "the" herein include the plural forms and the terms "or" and "and / or" herein are used interchangeably.

[0034] The numerical ranges described herein are inclusive and combinable. Any numerical value included in a range described herein can be used as a minimum or maximum value to derive a further range. For example, a numerical range of "25 to 200" should be understood to include any further range between the endpoints of 25 and 200 (e.g., further ranges of 25 to 150, 30 to 200, 30 to 150, etc.). Furthermore, when a numerical value falls within each range described herein (e.g., between the maximum and minimum values), it should be considered to be within the scope of the present disclosure.

[0035] The present disclosure mainly provides a filter. Specifically, the filter of the present disclosure includes a substrate layer and a near-infrared absorbing layer on the substrate layer.

[0036] The near-infrared absorbing layer of the present disclosure can be prepared from a near-infrared composition, which can include a copper compound, a phosphonic acid, and a phosphorus-containing compound.

[0037] The copper compound is mainly used as a source of copper ions, and is a known divalent copper ion (Cu 2+ Copper compounds, such as copper salts, capable of providing the above-mentioned copper salts can be used. Examples include copper acetate or copper acetate hydrate, as well as anhydrous or hydrated copper chloride, copper formate, copper stearate, copper benzoate, copper pyrophosphate, copper naphthenate, and copper citrate. In one embodiment, the copper compound is copper acetate.

[0038] The phosphonic acid is represented by the following formula 1: TIFF0007802865000002.tif2659In the formula, R is a substituted or unsubstituted C1 to C 12 Alkyl or substituted or unsubstituted C6-C 12 It is aryl.

[0039] The alkyl includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, etc., and substituted alkyl includes, but is not limited to, haloalkyl, hydroxyalkyl, nitroalkyl, alkoxyalkyl, etc. The aryl includes, but is not limited to, phenyl, naphthyl, etc., and substituted aryl includes, but is not limited to, haloaryl (e.g., chlorophenyl), nitroaryl, hydroxyaryl, alkoxyaryl, alkylaryl, haloalkylaryl, nitroalkylaryl, and hydroxyalkylaryl. In one embodiment, the phosphonic acid is butylphosphonic acid.

[0040] The phosphorus-containing compound is represented by the following formulas 2 to 4: TIFF0007802865000003.tif6552In the formula, R, R1, R2, and R3 each independently represent a substituted or unsubstituted C1 to C 12 Alkyl or C6-C 12 and aryl, and the definitions thereof are the same as those of R in Formula 1.

[0041] The phosphorus-containing compound may have a dispersing function, uniformly dispersing the components (formed copper complexes) in the composition without agglomerating them. One effect of this function is that the crystallite size in the composition is 100 nm or less, or even between 5 nm and 80 nm, or between 20 nm and 60 nm, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, or 100 nm. When the crystallite size is 5 nm or more, sufficient near-infrared absorbing properties are exhibited, while when the crystallite size is 100 nm or less, the average particle number of aggregated particles is small, and the haze of products manufactured using the near-infrared absorbing composition is low. In the present disclosure, at least one phosphorus-containing compound represented by Formulas 2 to 4 is used to prepare the near-infrared absorbing composition.

[0042] The ratio of the copper compound, the phosphonic acid, and the phosphorus-containing compound in the near-infrared absorbing composition can be adjusted as needed. For example, in the near-infrared absorbing composition, the amount of the copper compound may be 150 parts by mass, and examples thereof include 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or 150 parts by mass, and the amount of the phosphonic acid may be 100 parts by mass, and Examples of the total amount of phosphorus-containing compounds include 1 to 90 parts by mass, examples of which include 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 parts by mass.

[0043] In one embodiment, the near-infrared absorbing composition of the present disclosure contains all of the phosphorus-containing compounds represented by Formulas 2 to 4, and the ratio thereof can be adjusted as necessary. For example, in the near-infrared absorbing composition, the amount of the phosphorus-containing compound represented by Formula 2 may be 1 to 90 parts by mass, the amount of the phosphorus-containing compound represented by Formula 3 may be 1 to 90 parts by mass, and the amount of the phosphorus-containing compound represented by Formula 4 may be 1 to 90 parts by mass, and among them, the amount of each of the phosphorus-containing compounds represented by Formulas 2 to 4 may be 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 parts by mass. In another embodiment, the ratio of the phosphorus-containing compound represented by Formula 2:the phosphorus-containing compound represented by Formula 3:the phosphorus-containing compound represented by Formula 4 is 20:20:50.

[0044] In one embodiment, the near infrared absorbing composition of the present disclosure may be in the form of a dispersion, i.e., further contains a solvent in addition to the copper compound, phosphonic acid, and phosphorus-containing compound. During preparation, the copper compound, phosphonic acid, and phosphorus-containing compound can be added to and mixed in a solvent, and the ratio of these components to the solvent is 1:5 to 1:1, for example, but is not limited to, 1:3.

[0045] The solvent may be selected from known solvents, including, but not limited to, water, alcohols, ketones, ethers, esters, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, etc. Specific examples of the alcohols include methanol, ethanol, and propanol. Examples of the esters include alkyl formates, alkyl acetates, alkyl propionates, alkyl butyrates, alkyl lactates, alkyl alkoxyacetates, 3-alkoxyalkyl propionates, 2-alkoxyalkyl propionates, alkyl 2-alkoxy-2-methylpropionates, alkyl pyruvates, alkyl acetoacetates, and alkyl 2-oxobutyrates. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene and xylene.

[0046] The mixing may be performed by thoroughly stirring at room temperature (for example, 25° C.), for example, but is not limited to, 4 hours or more, 6 hours or more, or 8 hours or more.

[0047] The components in the near infrared absorbing composition interact and react to form a copper complex, which has the chemical formula Cu 2+ X, where Cu 2+ is provided by a copper compound and X is provided by a phosphonic acid and / or phosphorus-containing compound.

[0048] In one embodiment, the near-infrared absorbing composition may be in the form of a coating liquid. Specifically, the near-infrared absorbing composition in the form of a dispersion may be mixed with an optical resin to form a coating liquid, and the ratio of the dispersion to the optical resin may be 5:1 to 1:1 or 3:1 to 1:1, for example, but is not limited to, 0.65:0.35. When the near-infrared absorbing composition in the form of a coating liquid is used, it is applied on a substrate and dried and cured to form a near-infrared absorbing layer.

[0049] The optical resin may be a thermoplastic resin and / or a photocurable resin. In one embodiment, the optical resin is selected from polycarbonates, polyesters, polycycloolefin polymers, polyacrylic acids, siloxane resins, and polyimides. In one embodiment, the optical resin is a siloxane resin.

[0050] In addition, in order to carry out the curing process, a curing agent, for example, a photocuring agent, may be further added, so that the composition can be cured by light irradiation to form a film.

[0051] In an embodiment, the haze of the near infrared absorbing layer of the present disclosure is 0.4% or less, 0.3% or less, or 0.2% or less, for example, 0.4%, 0.35%, 0.3%, 0.25%, 0.2%, 0.19%, 0.18%, 0.17%, 0.16%, 0.15%, 0.14%, 0.13%, 0.12%, 0.11%, or 0.1%.

[0052] The thickness of the near-infrared absorbing layer also affects the near-infrared absorbing properties. Generally, as the thickness of the near-infrared absorbing layer increases, the near-infrared blocking ability also increases, but this does not satisfy the requirement for thinning. On the other hand, as the thickness of the near-infrared absorbing layer decreases, the near-infrared blocking ability also decreases. In an embodiment, the near-infrared absorbing layer of the present disclosure can achieve excellent near-infrared blocking ability even when it has a small thickness. Specifically, the thickness of the near-infrared absorbing layer is between 25 μm and 150 μm, between 50 μm and 150 μm, or between 100 μm and 150 μm, for example, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 146 μm, 147 μm, or 150 μm.

[0053] In one embodiment, the X-ray photoelectron spectrum of the near-infrared absorbing layer of the present disclosure has at least one main peak when the binding energy is 930 eV to 940 eV. In one embodiment, the counts per second of the at least one main peak are 4500 or more, 4600 or more, 4700 or more, 4800 or more, 4900 or more, or 5000 or more.

[0054] In one embodiment, the near-infrared absorbing layer of the present disclosure has a maximum transmittance for incident light in a wavelength range of 930 nm to 950 nm (including 940 nm incident light) of 0.1% or less, less than 0.1%, 0.05% or less, less than 0.05%, 0.01% or less, less than 0.01%, 0.0005% or less, or less than 0.005%, for example, 0.1%, 0.09%, 0.08%, 0.07%, 0.06%, 0.05%, 0.04%, 0.03%, 0.02%, 0.01%, 0.009%, 0.008%, 0.007%, 0.006%, 0.005%, 0.004%, 0.003%, 0.002%, or 0.001%. On the other hand, the OD value for incident light wavelengths of 930 nm to 950 nm (including incident light of 940 nm) is 3 or more, more than 3, 3.5 or more, more than 3.5, 4 or more, more than 4, 4.5 or more, or more than 4.5, for example, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9. In one embodiment, the minimum transmittance of the near-infrared absorbing layer of the present disclosure for incident light wavelengths in the range of 460 nm to 560 nm is 80% or more or 85% or more, for example, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%.

[0055] In one embodiment, the near-infrared absorbing layer of the present disclosure has a pass band overlapping with a wavelength range of 350 nm to 850 nm, 350 nm to 800 nm, or 350 nm to 750 nm, and the center wavelength of the pass band is within a wavelength range of 350 nm to 850 nm, 350 nm to 800 nm, 350 nm to 750 nm, 400 nm to 700 nm, 450 nm to 650 nm, 500 nm to 600 nm, or 500 nm to 550 nm. In this specification, the term "pass band" refers to a domain in which the transmittance of incident light within a wavelength range is 50% or more, and the term "center wavelength of the pass band" refers to the average value of two wavelengths of incident light when the transmittance of the incident light is 50%.

[0056] In one embodiment, the substrate layer can be used to support the near-infrared absorbing layer and to assist the filtering effect of the near-infrared absorbing layer, further improving the optical performance of the filter, for example, further improving the near-infrared and ultraviolet blocking effect. The substrate layer can be glass, for example, clear glass (e.g., AF32 glass) or blue glass. When blue glass is selected, the substrate layer can exhibit a near-infrared blocking effect. The blue glass, for example, phosphate glass, is blue glass formed from materials such as metaphosphate compounds, carbonate compounds, metal oxides, and metal fluorides. Here, the metaphosphate compounds include, but are not limited to, aluminum metaphosphate, magnesium metaphosphate, lithium metaphosphate, zinc metaphosphate, and calcium metaphosphate. The carbonate compounds include, but are not limited to, calcium carbonate, barium carbonate, and strontium carbonate. The metal oxides include, but are not limited to, copper oxide, aluminum oxide, zinc oxide, and magnesium oxide. The metal fluoride includes, but is not limited to, aluminum fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, and zinc fluoride. A homogenized glass can be obtained by uniformly mixing glass raw materials and placing them in a crucible, which is then placed in a furnace in an air atmosphere or a reducing atmosphere and heated to a temperature of 700°C to 1000°C.

[0057] In one embodiment, the substrate layer is blue glass, in which the molar ratio of phosphorus / (aluminum + lanthanum + niobium + yttrium) may be 1.5 to 16, and the molar ratio of fluorine / (fluorine + oxygen) may be 0.01 to 0.2. In one embodiment, the blue glass contains 35 to 55 mol% phosphorus, 3.5 to 15 mol% aluminum, 15 to 25 mol% alkali metal, 10 to 35 mol% alkaline earth metal and divalent metal, 10 to 21 mol% copper, and 0 to 7 mol% total of lanthanum, niobium, and yttrium, and the molar ratio of copper / phosphorus is 0.25 to 0.7, and the molar ratio of fluorine / (fluorine + oxygen) is 0.01 to 0.2.

[0058] In one embodiment, the thickness of the substrate layer is between 200 μm and 500 μm, between 200 μm and 400 μm, or between 200 μm and 300 μm, for example, 200 μm, 225 μm, 250 μm, 275 μm, 300 μm, 325 μm, 350 μm, 375 μm, 400 μm, 425 μm, 450 μm, 475 μm, or 500 μm.

[0059] The arrangement order of the layers in the filter of the present disclosure is not limited. For example, as shown in FIG. 1A , filter 1 includes a near-infrared absorbing layer 10 and a substrate layer 20, and near-infrared absorbing layer 10 is located on substrate layer 20.

[0060] In one embodiment, the filter of the present disclosure further includes a filter layer. In one embodiment, the location of the filter layer in the filter is not limited. For example, as shown in FIG. 1A , the filter layer 30 is located on the opposite side of the substrate layer 20 from the near-infrared absorbing layer 10, i.e., the near-infrared absorbing layer 10 and the filter layer 30 are located on both sides of the substrate layer 20. In another embodiment, as shown in FIG. 3 , the filter layer 30 in filter 1″ may be located between the near-infrared absorbing layer 10 and the substrate layer 20. Also, as shown in FIG. 4 , the near-infrared absorbing layer 10 in filter 1′′ may be located between the filter layer 30 and the substrate layer 20.

[0061] The filter layer is used to ensure that the near-infrared absorbing layer exhibits excellent optical performance, for example, further improving the near-infrared and ultraviolet blocking effects. In one embodiment, the filter layer can include a first absorbing dye layer and a second absorbing dye layer, each containing a near-infrared absorbing dye and an ultraviolet absorbing dye. As shown in Figures 1B and 1C, the filter layer 30 in the filter 1 specifically has a double-layer structure consisting of a first absorbing dye layer 31 and a second absorbing dye layer 32. The only difference between Figures 1B and 1C is the arrangement order of the first absorbing dye layer 31 and the second absorbing dye layer 32.

[0062] The filter layer may comprise a transparent resin material, which may include, but is not limited to, an epoxy resin, a polyurethane, a polyacrylate, a polyolefin, a polycarbonate, a polycyclic olefin, and a polyvinyl butyral, and the resin material may be the base of a filter layer coating solution.

[0063] The near-infrared absorbing dyes, such as azo compounds, diimine compounds, dithiophene metal complexes, squaraine compounds, cyanine compounds, and phthalocyanine compounds, can have a maximum absorption wavelength adjusted to 650 to 1100 nm, or more specifically, 650 to 750 nm. The ultraviolet absorbing dyes include, for example, azomethine compounds, indole compounds, ketone compounds, benzimidazole compounds, and triazine compounds.

[0064] In one embodiment, the thickness of the filter layer is 0.5 μm to 10 μm, for example, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm. When the filter layer has a multi-layer structure, for example, a double-layer structure of a first absorbing dye layer and a second absorbing dye layer, the thickness of each layer is 0.5 μm to 10 μm, for example, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm.

[0065] In one embodiment, the filter of the present disclosure further comprises at least one anti-reflective layer on the outermost side of the filter. As shown in Figure 2, anti-reflective layer 40 is on the outermost side of both sides of filter 1'.

[0066] In one embodiment, the anti-reflection layer is a coating formed from at least one material selected from TiO2, SiO2, Y2O3, MgF2, Al2O3, Nb2O5, AlF3, Bi2O3, Gd2O3, LaF3, PbTe, Sb2O3, SiO, SiN, Ta2Os, ZnS, ZnSe, ZrO2, and Na3AlF6. In one embodiment, the anti-reflection layer is formed by alternately stacking TiO2 layers and SiO2 layers.

[0067] In one embodiment, the thickness of the antireflective layer is 0.5 μm to 10 μm, for example, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm.

[0068] In one embodiment, the filter of the present disclosure further includes a protective layer, and the material of the protective layer is an optical resin. For the optical resin here, see the optical resin used in the near-infrared absorbing composition in the form of a coating liquid.

[0069] In one embodiment, the thickness of the protective layer is 10 μm to 30 μm, for example, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm. In one embodiment, the protective layer is on the near-infrared absorbing layer or between the near-infrared absorbing layer and a layer covering it. As shown in FIG. 2, the protective layer 12 is located between the near-infrared absorbing layer 10 and the anti-reflection layer 40. The protective layer is used to protect the near-infrared absorbing layer because the material of the near-infrared absorbing layer is soft, and directly performing post-processing on it can easily scratch the surface of the near-infrared absorbing layer, which may ultimately cause peeling of the near-infrared absorbing layer. Therefore, forming a protective layer on the near-infrared absorbing layer in advance can prevent damage.

[0070] In one embodiment, the filter of the present disclosure further includes an adhesive layer between the near-infrared absorbing film and the substrate layer. As shown in FIG. 2, adhesive layer 11 is located between near-infrared absorbing layer 10 and substrate layer 20. The adhesive layer may be made of a material known in the art for adhering two adjacent layers, such as hexamethyldisilazane (HMDS). The adhesive layer is used to prevent the near-infrared absorbing layer from peeling off from the substrate layer under certain conditions, thereby improving the stability of the filter.

[0071] In one embodiment, the filter of the present disclosure includes a substrate layer, a near-infrared absorbing layer, a filter layer, an adhesive layer, a protective layer, and an anti-reflection layer. As shown in Figure 2, the filter 1' of the present disclosure includes a substrate layer 20, a near-infrared absorbing layer 10 on one side of the substrate layer 20, an adhesive layer 11 between the substrate layer 20 and the near-infrared absorbing layer, a filter layer 30 on the other side of the substrate layer 20, a protective layer 12 on the near-infrared absorbing layer 10, and anti-reflection layers 40 on the outermost sides of both sides of the filter.

[0072] In one embodiment, the total thickness of the filter of the present disclosure is about 225 μm to about 800 μm, about 250 μm to about 500 μm, or about 300 μm to about 500 μm, for example, about 225 μm, about 250 μm, about 275 μm, about 300 μm, about 325 μm, about 350 μm, about 375 μm, about 400 μm, about 425 μm, about 450 μm, about 475 μm, about 500 μm, about 550 μm, about 600 μm, about 650 μm, about 700 μm, about 750 μm, or about 800 μm.

[0073] In one embodiment, the haze of a filter of the present disclosure is 0.5% or less, 0.4% or 0.3% or less, for example, 0.5%, 0.45%, 0.4%, 0.35%, 0.3%, 0.25%, 0.2%, 0.19%, 0.18%, 0.17%, 0.16%, 0.15%, 0.14%, 0.13%, 0.12%, 0.11%, or 0.1%.

[0074] In one embodiment, the maximum transmittance of the filter of the present disclosure for incident light in the wavelength range of 930 nm to 950 nm (including incident light of 940 nm) is 0.01% or less, less than 0.01%, 0.005% or less, or less than 0.005%, for example, 0.01%, 0.009%, 0.008%, 0.007%, 0.006%, 0.005%, 0.004%, 0.00 3%, 0.002%, 0.001%, while the OD value for the incident light wavelength range of 930 nm to 950 nm (including incident light at 940 nm) is 4 or greater, greater than 4, 4.5 or greater, greater than 4.5, 4.8 or greater, or greater than 4.8, for example, 4, 4.01, 4.1, 4.2, 4.3, 4.4, 4.5, 4.51, 4.6, 4.7, 4.8, 4.81, 4.9. In one embodiment, the minimum transmittance of the filter of the present disclosure for the incident light wavelength range of 460 nm to 560 nm is 80% or greater, or 85% or greater, for example, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%.

[0075] In one embodiment, a filter of the present disclosure has a passband that overlaps with a wavelength range of 350 nm to 850 nm, 350 nm to 800 nm, or 350 nm to 750 nm, and the center wavelength of the passband is within a wavelength range of 350 nm to 850 nm, 350 nm to 800 nm, 350 nm to 750 nm, 400 nm to 700 nm, 450 nm to 650 nm, 500 nm to 600 nm, or 500 nm to 550 nm.

[0076] In one embodiment, when incident light is incident on a filter of the present disclosure at angles of incidence of 0 degrees and 30 degrees, respectively, the center wavelength of the passband shifts by 1.4 nm or less, e.g., 1.4 nm, 1.3 nm, 1.2 nm, or 1.1 nm. In one embodiment, when incident light is incident on a filter of the present disclosure at angles of incidence of 0 degrees and 35 degrees, respectively, the center wavelength of the passband shifts by 1.9 nm or less, e.g., 1.9 nm, 1.8 nm, or 1.7 nm.

[0077] The present disclosure will be further described in detail with reference to the following specific examples, which are not intended to limit the scope of the present disclosure.

[0078] Manufacturing Example 1 Near-infrared absorbing layer 150 parts by weight of copper acetate and 15,000 parts by weight of ethanol were mixed and stirred at room temperature for 1.5 hours to form a first mixture. Separately, 20 parts by weight of a phosphorus-containing compound represented by Formula 2 (Plysurf A242G, purchased from Nippon Daiichi Kogyo Seiyaku Co., Ltd.), 20 parts by weight of a phosphorus-containing compound represented by Formula 3 (Plysurf W542C, purchased from Nippon Daiichi Kogyo Seiyaku Co., Ltd.), and 50 parts by weight of a compound represented by Formula 4 (Plysurf A285C, purchased from Nippon Daiichi Kogyo Seiyaku Co., Ltd.) were mixed with 1,500 parts by weight of ethanol to form a second mixture. The first mixture and the second mixture were mixed and stirred at room temperature for 1 hour. Subsequently, 100 parts by weight of butylphosphonic acid was added and the mixture was stirred at room temperature for 3 hours to allow the mixture to react. The mixture was then placed in an oven at 85°C and left for 12 hours to obtain a powder. The powder and xylene were mixed in a mass ratio of 1:3 to form a dispersion, and the dispersion and an optical resin were mixed in a mass ratio of 0.65:0.35 to form a coating solution, which was then applied to a substrate and baked at 70°C for 30 minutes to obtain a near-infrared absorbing layer. The transmittance graph of the near-infrared absorbing layer is shown in Figure 7.

[0079] The near-infrared absorbing layer described above was analyzed by X-ray photoelectron spectroscopy (ESCA / XPS). The X-ray photoelectron spectrum is shown in Figure 5. When the binding energy is between 930 eV and 940 eV, a characteristic peak associated with a copper complex (Cu(PO x ) y , CuO, Cu2O, Cu(OH)2) have been observed. Note that the peak that appears when the binding energy is 940 eV or higher is a satellite peak.

[0080] Filter layer 0.02 g of a squaraine compound and a cyanine compound were added to 5 g of epoxy resin as infrared absorbing dyes, and the resulting mixture was coated on a substrate and baked at 70°C for 30 minutes to obtain a first absorbing dye layer. 0.02 g of a triazine compound was added to 5 g of epoxy resin as an ultraviolet absorbing dye, and the resulting mixture was coated on a substrate and baked at 70°C for 30 minutes to obtain a second absorbing dye layer.

[0081] The transmittance graph of the first absorbing dye layer and the second absorbing dye layer described above is shown in FIG.

[0082] In addition, a filter layer having a double layer structure was formed by forming a first absorbing dye layer on the aforementioned substrate, and then further forming a second absorbing dye layer on the first absorbing dye layer, the transmittance graph of which is shown in Figure 7.

[0083] Manufacturing Example 2 Based on the description herein, blue glass was used as the substrate layer. Next, a filter layer was formed on one side of the blue glass substrate layer using the method described in Preparation Example 1. Next, a near-infrared absorbing layer was formed on the other side of the blue glass substrate layer using the same method described in Preparation Example 1. Transmittance graphs for the aforementioned substrate layer, a double-layer structure of substrate layer + filter layer, and a triple-layer structure of substrate layer + near-infrared absorbing layer + filter layer are shown in Figure 8. The results indicated that a filter with a double-layer structure of substrate layer + filter layer alone lacks sufficient blocking effect against incident near-infrared light. In contrast, a filter with a triple-layer structure of substrate layer + near-infrared absorbing layer + filter layer exhibits excellent blocking effect against incident near-infrared light, particularly incident light of 850 nm or above. Thus, the near-infrared absorbing layer significantly improves the near-infrared blocking effect of the substrate layer + near-infrared absorbing layer of the present disclosure while maintaining high transmittance in the visible light range.

[0084] Example 1 The structural arrangement of each layer in the filter of Example 1 is as shown in Figure 2. The substrate layer is blue glass with a thickness of 200 μm, the adhesive layer is hexamethyldisilazane with a thickness of 60 μm, the near-infrared absorbing layer is prepared according to the method described in Preparation Example 1 and has a thickness of 145.44 μm, the protective layer is optical resin with a thickness of 20 μm, the filter layer is prepared according to the method described in Preparation Example 1 and has a thickness of 5 μm, and the anti-reflection layer is composed of alternating TiO2 layers and SiO2 layers, with a total thickness of 1 μm.

[0085] Examples 2 to 4 and Comparative Example 1 Filters were prepared according to the method of Example 1, but the thickness of the near-infrared absorbing layer was changed to 146.22 μm, 147.44 μm, and 146.63 μm, resulting in Examples 2 to 4. In addition, a filter was prepared according to the method of Example 1, but the thickness of the near-infrared absorbing layer was changed to 165.11 μm, resulting in Comparative Example 1.

[0086] The transmittance graphs of the above-mentioned Examples 1 to 4 and Comparative Example 1 are shown in FIGS. 9 to 12, and the transmittance data are shown in Table 1 below.

[0087] [Table 1]

[0088] Based on these results, the filters of the present disclosure have extremely high blocking power for incident light wavelengths of 930 nm to 950 nm, reaching OD values ​​of 4.5 or more. To further illustrate the OD values ​​of the filters of the present disclosure for incident light wavelengths of 930 nm to 950 nm, Figure 13 was created based on the transmittance graph and its data, and this graph represents the OD value graph for wavelengths of 930 nm to 950 nm for the filters of Examples 1 to 4. Meanwhile, the filters of the present disclosure have excellent transmittance for visible light, have a passband that overlaps with the wavelength range of 350 nm to 850 nm, and the center wavelength of the passband is within the wavelength range of 350 nm to 850 nm.

[0089] FIG. 14 shows the transmittance spectra of the filter of Example 1 when incident light is incident at different angles of 0 degrees, 30 degrees, and 35 degrees, from which the shift amount can be observed. Similarly, FIG. 15 shows the transmittance spectra of the filter of Example 3 when incident light is incident at different angles of 0 degrees, 30 degrees, and 35 degrees. The results show that the transmittance graphs obtained by incident light on the filter at different angles of incidence are very similar. Taking the transmittance data of Examples 1 and 3 as an example (as shown in Table 2 below), when incident light is incident at 0 degrees and 30 degrees, respectively, the shift amounts of the center wavelength of the passband are 1.1 nm and 1.4 nm, respectively, and when incident light is incident at 0 degrees and 35 degrees, respectively, the shift amounts of the center wavelength of the passband are 1.7 nm and 1.9 nm, respectively. In contrast, the filter of Comparative Example 2, which was prepared according to the method of Example 1 but did not have a near-infrared absorbing layer, exhibited a very large shift in the center wavelength of the passband of 9.6 nm when incident at 0 degrees and 30 degrees, and an even larger shift of 10.1 nm when incident at 0 degrees and 30 degrees. It is known that such a large shift can cause glare and ghosting. On the other hand, the filter of the present disclosure exhibited a small shift, significantly reducing glare and ghosting and improving image quality.

[0090] [Table 2]

[0091] The above-described embodiments and specific examples do not limit the present disclosure, and the described technical features and approaches can be combined with each other. The present disclosure can also be implemented or applied in other different embodiments. Various changes and modifications can be made to the details described in this specification according to different viewpoints and applications without departing from the present disclosure. [Explanation of symbols]

[0092] 1, 1', 1", 1"': Filter 10: Near-infrared absorbing layer 11: Adhesive layer 12:Protective layer 20: Base material layer 30: Filter layer 31: First absorbing dye layer 32: Second absorbing dye layer 40: Anti-reflection layer

Claims

1. A filter comprising a substrate layer and a near-infrared absorbing layer overlying the substrate layer, The near-infrared absorbing layer includes a copper complex, and the copper complex is formed from a copper compound used to supply copper ions, a phosphonic acid represented by the following formula 1, and a phosphorus-containing compound represented by any one of formulas 2 to 4: (In the formula, R, R １ , R ２ , R ３ are each independently a substituted or unsubstituted C １ ~C １２ Alkyl or substituted or unsubstituted C ６ ~C １２ It is aryl. A filter having an OD value of greater than 4 for incident light wavelengths of 930 nm to 950 nm.

2. The substituted or unsubstituted C １ ~C １２ The alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl, and the substituted or unsubstituted C ６ ~C １２ 2. The filter of claim 1, wherein aryl is selected from the group consisting of phenyl, naphthyl, and chlorophenyl.

3. 2. The filter according to claim 1, wherein the near-infrared absorbing layer has a haze of 0.4% or less.

4. 2. The filter of claim 1, wherein the X-ray photoelectron spectrum of the near-infrared absorbing layer has at least one main peak when the binding energy is between 930 electron volts (eV) and 940 eV.

5. 5. The filter of claim 4, wherein the value of the counts per second of the at least one main peak is 4500 or more.

6. 10. The filter of claim 1, wherein the OD value for an incident light wavelength of 940 nm is greater than 4.

5.

7. 2. The filter according to claim 1, wherein the near-infrared absorbing layer has a thickness of 25 μm to 150 μm.

8. 2. The filter according to claim 1, wherein the material of the substrate layer is glass, and the thickness of the substrate layer is 200 μm to 500 μm.

9. The filter of claim 1 , further comprising a filter layer on the opposite side of the substrate layer from the near-infrared absorbing layer.

10. 10. The filter of claim 9, wherein the filter layer further comprises a first absorbing dye layer and / or a second absorbing dye layer, the first absorbing dye layer comprising a near-infrared absorbing dye and the second absorbing dye layer comprising an ultraviolet absorbing dye.

11. 11. The filter according to claim 10, wherein the near-infrared absorbing dye is at least one selected from the group consisting of an azo compound, a diimine compound, a dithiophene metal complex, a squaraine compound, a cyanine compound, and a phthalocyanine compound.

12. 11. The filter according to claim 10, wherein the ultraviolet absorbing dye is at least one selected from the group consisting of azomethine compounds, indole compounds, ketone compounds, benzimidazole compounds, and triazine compounds.

13. 11. The filter of claim 10, wherein the thickness of the first absorbing dye layer and the second absorbing dye layer is 0.5 μm to 10 μm, respectively, and the total thickness of the filter layer is 0.5 μm to 10 μm.

14. 10. The filter of claim 1, further comprising at least one anti-reflective layer on an outermost side of the filter.

15. The material of the at least one anti-reflection layer is TiO ２ , SiO ２ , Y ２ O ３ , MgF ２ , A1 ２ O ３ , Nb ２ O ５ , AlF ３ , Bi ２ O ３ , Gd ２ O ３ , LaF ３ , PbTe, Sb ２ O ３ , SiO, SiN, Ta ２ Os, ZnS, ZnSe, ZrO ２ and Na ３ AlF ６ The filter according to claim 14, which is at least one selected from the group consisting of: and has a thickness of 0.5 μm to 10 μm.

16. 15. The filter of claim 14, further comprising a protective layer made of an optical resin.

17. 17. The filter of claim 16, wherein the protective layer has a thickness of 10 μm to 30 μm, and the protective layer is located between the near-infrared absorbing layer and the anti-reflection layer.

18. 2. The filter of claim 1, wherein the total thickness is from 225 μm to 800 μm.

19. 2. The filter of claim 1, wherein the haze is 0.5% or less.

20. 2. The filter according to claim 1, wherein the maximum transmittance for incident light in the wavelength range of 930 nm to 950 nm is 0.01% or less.

21. 21. The filter of claim 20, wherein the maximum transmittance for incident light in the wavelength range of 930 nm to 950 nm is 0.005% or less.

22. 2. The filter according to claim 1, wherein the minimum transmittance for incident light in the wavelength range of 460 nm to 560 nm is 80% or more.

23. 2. The filter according to claim 1, wherein the minimum transmittance for incident light in the wavelength range of 460 nm to 560 nm is 85% or more.

24. 10. The filter of claim 1, having a passband that overlaps the wavelength range of 350 nm to 850 nm, the center wavelength of the passband being within the wavelength range of 350 nm to 850 nm.

25. 25. The filter of claim 24, wherein the center wavelength of the passband shifts by 1.4 nm or less when incident light is incident on the filter at angles of incidence of 0 degrees and 30 degrees, respectively.

26. 26. The filter of claim 25, wherein the center wavelength of the passband shifts by 1.9 nm or less when incident light is incident on the filter at angles of incidence of 0 degrees and 35 degrees, respectively.

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