CN113740950B - Coating composition, preparation method thereof, extinction film, lens module and terminal - Google Patents

Coating composition, preparation method thereof, extinction film, lens module and terminal Download PDF

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CN113740950B
CN113740950B CN202111301408.9A CN202111301408A CN113740950B CN 113740950 B CN113740950 B CN 113740950B CN 202111301408 A CN202111301408 A CN 202111301408A CN 113740950 B CN113740950 B CN 113740950B
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component
coating
film
black
coating composition
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CN113740950A (en
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徐川
陈牧
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Giant Glass Solid Energy Suzhou Film Material Co ltd
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Giant Glass Solid Energy Suzhou Film Material Co ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters

Abstract

The application relates to a coating composition, a preparation method thereof, a matt film, a lens module and a terminal, wherein the coating composition comprises a first component, the first component contains Ti element, Mg element and O element, and optional Fe element and/or Co element, and the molar ratio of the Ti element, the Mg element and the O element in the coating composition is 1 (0.2-1) to 0.8-1.5; when the first component contains the Fe element and/or the Co element, the weight of the Fe element and/or the Co element is 10% or less. The material has strong absorption effect in visible light and near infrared band, and the coating composition has a black extinction film with dual effects of transmission extinction and reflection extinction, thereby facilitating the design and optimization of a film system.

Description

Coating composition, preparation method thereof, extinction film, lens module and terminal
Technical Field
The application relates to a coating composition, a preparation method thereof, a matt film, a lens module and a terminal, and belongs to the field of coating materials.
Background
In recent years, as the volume of consumer optical products such as mobile phone cameras is smaller and smaller, the performance requirements are increased, and the demand for reflective and absorptive coating materials is more and more urgent. The current technology for such light-reflecting and light-absorbing materials is to use anodic black or organic coatings containing carbon particles. For example, in the process of manufacturing a camera, it is often necessary to perform a blackening process on the outer edge of the lens and the inner wall of the lens barrel. This process is typically made by a carbon-containing coating or an anodic blackening process with a low surface reflectivity. However, for process reasons and to improve the extinction of reflected light, such paint coatings are generally thicker and have a rougher surface, and are increasingly insufficient for small-sized lens applications such as mobile phone lenses with stringent requirements for volume and thickness. Although many attempts have been made to process the film by evaporation using a black film material, the reflection is too strong due to the main components of some common black film materials such as Cr — SiO and Ni — Cr being metals, and it is difficult to satisfy the situation where high extinction is required for both projection and reflection.
Along with the development of the mobile phone lens module towards high pixel, large aperture and ultra-thinness, the requirement of the consumer on the imaging quality of the camera module is higher and higher. However, when the lens is used in the sun, light is reflected by the edge area of the window of the optical filter, enters the image sensor for imaging after being diffusely reflected by the surface areas such as the inner wall of the lens and the image sensor, so that stray light is generated, ghost images and light spots appear on the lens, and the normal use of the lens is influenced.
Stray light is generally suppressed or eliminated as follows.
1. The inner wall of the lens is generally coated with a black coating to absorb the excessive light, and in the past, the lens is generally coated with a metal inner wall, so the coating is generally processed in a blackening way. With the increase of the use of polymer materials, the inner wall is blackened mainly by adopting a mode of adding black dye into a lens barrel material or coating black paint on the lens barrel material.
2. At present, the edge of the lens is mainly processed by coating black extinction coating. For eliminating irregular reflection light at the edge of the lens.
3. And black extinction diaphragms are added between the lenses to absorb stray light outside the light path. A black polymer ring is typically inserted between the lens and the holder to act as a gasket and diaphragm.
The current black matt coatings are mainly manufactured by adopting ink coating and screen printing methods. With the increasing demand for products, it is increasingly recognized that such black coating processes have the following disadvantages:
1. whether the ink coating or the screen printing is adopted, the appearance quality is difficult to reach the level of evaporation coating. Regardless of the pigment and the dispersant, the film prepared by the ink substances is thick and uneven. For example, when a display screen cover plate is prepared, the optical reflection characteristics of the display screen cover plate are far from those of the screen. Thus causing non-uniformity in the screen reflection. The cover plate can be seen with a black frame in a hidden way in appearance, and the effects of full screen black and no frame can not be achieved.
2. Because the ink or paint adopted by the coating process contains organic solvent, pollution and discharge are inevitable in the production of products. In most non-chemical industrial parks, such projects are difficult to pass the criticism, and even pass the criticality requires more environmental equipment and strict inspections.
3. As more and more lens materials no longer use metal but polymer, the original lens barrel anode blackening process is no longer suitable. For polymer lens barrels, other blackening processes need to be used.
4. The thickness of the color layer is generally no less than 10 microns regardless of the coating material used, while the thickness of the black matte film is no more than 0.5 microns using evaporation coating. This is of great importance for the design and production of many small or micro-optical devices.
Therefore, many attempts have been made to produce black matte films, as well as decorative black films, by vacuum evaporation coating. And use such films for black coatings (matting layers) on the inner walls of lenses, the outer edges of lenses, the periphery of screens or cover plates. This new process has great advantages over conventional coating methods.
However, the current black coating materials have some problems in preparing black films, which limits the application of the black films prepared by the vacuum evaporation coating process in the optical extinction direction. This is because the current black plating materials are often composed of one or more metal or semiconductor materials. This is due to the wide conduction band of the metal or semiconductor material. Can absorb light with a wide range of wavelengths to form extinction. However, since a metal material or a semiconductor has a large amount of free electrons, the free electrons cause a broad spectrum of uniform reflection on the surface of the material, which causes the surface to be strongly reflective, which is difficult to avoid. While such black films can absorb transmitted light by increasing the extinction coefficient, they tend to be largely ineffective at reflecting light. Particularly on smooth surfaces, the coated surface often exhibits a mirror-like effect.
The black film can be prepared by using a pure semiconductor material, but the common semiconductor material usually has weak light absorption capability, and because the full visible part cannot be covered by the rewinding width of the semiconductor, the color cast problem often exists, so that the film presents yellow or brown color tone and neutral extinction cannot be realized.
This is true of currently used Black coating materials such as Cr, Ni/Cr, Cr/SiO, Ni, etc., including those produced by some foreign factories such as Black A of Merck corporation, and the surface reflectivity of Black films prepared from these materials is much higher than that of the uncoated surfaces. Because the light reflection of the coating surface is far greater than the light reflection intensity of the ink surface, the coating cannot be used as a delustering coating to replace ink or a delustering paint coating at present.
Disclosure of Invention
The invention aims to provide a coating composition, a preparation method thereof, a matt film and a lens module/terminal, wherein the material has a strong absorption effect in visible light and near infrared bands, and the coating composition simultaneously has a black matt film with double effects of transmission extinction and reflection extinction, so that the design and optimization of a film system are facilitated.
In order to achieve the purpose, the application provides the following technical scheme: a coating composition comprises a first component, wherein the first component contains Ti element, Mg element and O element, and optional Fe element and/or Co element, and the molar ratio of the Ti element, the Mg element and the O element in the coating composition is 1 (0.2-1) to 0.8-1.5; when the first component contains the Fe element and/or the Co element, the weight of the Fe element and/or the Co element is 10% or less.
Further, in the first component, the Ti element is selected from Ti and TiO2、Ti2O3Or Ti3O5At least one of; and/or, the Mg element is selected from MgO; and/or the Fe element is selected from Fe2O3Or FeO; and/or the Co element is selected from Co2O3Or CoO.
Further, the coating composition further includes a second component selected from Nb2O5、NbO2、 Nb、Ta2O5、Ti3O5、Ti2O3、ZrO2Any one or more of ZrO or Zr.
Further, the coating composition further comprises a third component selected from SiO2、MgF2Or a silica alumina mix.
The application also provides a preparation method of the coating composition, which comprises the following steps:
s1, providing a first raw material as a first component, wherein the first raw material is selected from Ti and TiO2、Ti2O3Or Ti3O5And MgO; the first raw material further comprises Fe2O3Or FeO, and/or, Co2O3Or CoO; wherein the molar ratio of the Ti element, the Mg element and the O element is 1 (0.2-1) to 0.8-1.5, and the weight of the Fe element and/or the Co element is less than or equal to 10 percent;
s2, uniformly mixing the first raw materials and preparing the mixture into small particles;
s3, sintering the particles in the S2 to obtain a first component which is yellow to dark brown-yellow; the sintering treatment comprises the following steps: the temperature is increased to 600-950 ℃ at the speed of 7-13 ℃ per minute, then the material is heated to 1000-1600 ℃ at the speed of 2-4 ℃ per minute, the temperature is kept constant for at least 3 hours, the heating can be stopped after the reaction is finished, and the material is naturally cooled.
Further, in step S1, the method further includes providing a second material selected from Nb as a second component2O5、NbO2、Nb、Ta2O5、Ti3O5、Ti2O3、ZrO2Any one or more of ZrO, or Zr;
and a third raw material as a third component, the third raw material being selected from SiO2、MgF2Or a silica alumina mix.
The application also provides a matt film which comprises at least two black coating layers, a high-refraction layer and a low-refraction layer, wherein the low-refraction layer is arranged between the two black coating layers, or the high-refraction layer and the low-refraction layer are arranged between the two black coating layers; the black coating layer comprises a first component containing Ti, Mg and O, and Fe and/or Co, and the molar ratio of the Ti, Mg and O in the black coating layer is 1 (0.2-1) to 0.8-1.5; the weight of the Fe element and/or the Co element is less than or equal to 10%, and the Mg element is selected from MgO.
Further, the matting film further includes a high refractive layer containing a second component selected from Nb2O5、NbO2、Nb、Ta2O5、Ti3O5、Ti2O3、ZrO2Any one or more of ZrO or Zr.
Further, the extinction film also comprises a low-refraction layer, wherein the low-refraction layer contains a third component, and the third component is selected from SiO2、MgF2Or a silica alumina mix.
The application also provides a lens module, which comprises the extinction film.
The application also provides a terminal, which comprises the extinction film.
Compared with the prior art, the beneficial effect of this application lies in: the application provides a coating composition, a preparation method thereof, a matt film and a lens module or a terminal, wherein the material has a strong absorption effect in visible light and near infrared bands, and can be used for preparing a black matt film with dual effects of transmission extinction and reflection extinction. Meanwhile, the optical parameters such as the refractive index and the like are stable, so that the design and optimization of a film system are facilitated, and the optical film can be applied to the extinction film.
The reflectivity of the black coating layer prepared by the coating composition is less than 0.2% in a visible light range, the transmission light intensity is less than 0.01%, and the color of the coating layer can be prevented from color cast by the iron/cobalt compound component. Both transmitted and reflected light are significantly suppressed. The reflected light intensity is lower than that of black ink or matting paint, and the film thickness of the matting film can be controlled below 500nm and is far lower than the thickness of a common ink coating by hundreds of microns.
The material can be melted and evaporated into a film in vacuum by using an electron beam heating mode, the process is stable, the phenomena of splashing, decomposition and the like do not exist, and a uniform and firm film with good adhesive force is formed.
Meanwhile, compared with the process of coating by using ink dyes, the process has the advantages of simple process, short preparation time, high product yield and no emission of solvent gas. And the thickness of the film layer is below 500nm and far lower than the thickness of a plurality of hundreds of microns of a common ink coating. The optical module is very suitable for small optical modules such as mobile phone cameras, and the thickness and the weight of the system cannot be increased.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a graph showing the light transmittance and absorption of a matting film according to example III of the present application;
FIG. 2 is a graph showing the light transmittance and absorption of a matting film according to example four of the present application;
FIG. 3 is a graph showing the light transmittance and absorption of a matting film according to example five of the present application;
FIG. 4 is a graph showing the light transmission and absorption curves of a matting film according to example six of the present application;
FIG. 5 is a graph showing the light transmittance and absorption of a matting film according to example VII of the present application;
FIG. 6 is a graph showing the light transmittance and absorption of a matting film according to example VIII of the present application.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
It should be noted that: the terms "upper", "lower", "left", "right", "inner" and "outer" of the present invention are used for describing the present invention with reference to the drawings, and are not intended to be limiting terms.
In the description of the present application, it is noted that, unless explicitly stated or limited otherwise, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus. The specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art. Further, in the description of the present application, "a plurality" means two or more unless otherwise specified. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The terms "first," "second," "third," and the like in the description and claims of this application and in the above-described drawings are used for distinguishing between different objects and not for describing a particular order. Furthermore, the terms "include" and "have," as well as any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
The coating composition comprises a first component, wherein the first component contains Ti element, Mg element and O element, and optional Fe element and/or Co element, and the molar ratio of the Ti element, the Mg element and the O element in the coating composition is 1 (0.2-1) to 0.8-1.5; when the first component contains the Fe element and/or the Co element, the weight of the Fe element and/or the Co element is 10% or less.
Optionally, in the first component, the Ti element is selected from Ti and TiO2、Ti2O3Or Ti3O5At least one of (1). Further, Ti and TiO may be selected in consideration of cost2. And, optionally, Ti and TiO2The purity of (b) needs to be 2N5 or more.
Optionally, the Mg element is selected from MgO.
Optionally, the Fe element is selected from Fe2O3Or FeO.
Optionally, the Co element is selected from Co2O3Or CoO.
Optionally, the coating composition further comprises a second element having a high refractive index, the second element being selected from Nb2O5、NbO2、Nb、Ta2O5、Ti3O5、Ti2O3、ZrO2Any one or more of ZrO or Zr.
Optionally, the coating composition further comprises a third component with low refractive index, the third component being selected from SiO2、MgF2Or a silica alumina mix.
The application also provides a preparation method of the coating composition, which comprises the following steps:
s1, providing a first raw material as a first component, wherein the first raw material is selected from Ti and TiO2、Ti2O3Or Ti3O5And MgO;
s2, uniformly mixing the first raw materials and preparing the mixture into small particles;
s3, sintering the particles in the S2 to obtain a first component which is yellow to dark brown-yellow; alternatively, in S3, the sintering process of the particles requires sufficient time to remove impurities before the material reaches the sintering temperature, while ensuring uniform sintering of all materials. Specifically, the sintering treatment includes: the temperature is raised to 600-950 ℃ at a rate of 7-13 ℃ per minute. And heating the material to 1000-1600 ℃ at the speed of 2-4 ℃ per minute, keeping the temperature for at least 3 hours, and stopping heating after the reaction is finished to naturally cool the material.
Optionally, in step S1, the first raw material further includes Fe2O3Or FeO, and/or, Co2O3Or CoO; wherein the molar ratio of the Ti element, the Mg element and the O element is 1 (0.2-1) to 0.8-1.5, and the weight of the Fe element and/or the Co element is less than or equal to 10%.
Optionally, step S1 further includes providing a second material as the second component and a third material as the third component, wherein the second material is selected from Nb2O5、NbO2、Nb、Ta2O5、Ti3O5、Ti2O3、ZrO2Any one or more of ZrO, or Zr; the third raw material is selected from SiO2、MgF2Or a silica alumina mix.
The application also provides a matt film which comprises at least one Black coating layer (BB), wherein the Black coating layer comprises a first component containing Ti, Mg and O elements and optional Fe and/or Co elements, the molar ratio of the Ti, Mg and O elements in the Black coating layer is 1 (0.2-1) to (0.8-1.5), and the Mg element is selected from MgO; when the first component contains the Fe element and/or the Co element, the weight of the Fe element and/or the Co element is 10% or less. By adding the Fe element and/or the Co element, the color deviation can be adjusted according to the content of the Fe element and/or the Co element, so that the color of the extinction film is not subjected to color deviation.
Optionally, the matting film further comprises a high refractive layer containing a second component selected from Nb2O5、NbO2、Nb、Ta2O5、Ti3O5、Ti2O3、ZrO2Any one or more of ZrO or Zr.
Optionally, the matting film further comprises a low-refractive layer containing a third component selected from SiO2、MgF2Or a silica alumina mix.
Alternatively, the matting film may be a single layer or a multilayer structure.
Optionally, the extinction film may be a black extinction film for a lens module.
Optionally, the matting film may be prepared by a vacuum evaporation coating method, and indeed, may be prepared by other conventional methods.
Based on this, this application still provides a lens module, terminal that have adopted above-mentioned extinction film in an aspect, and optionally, be equipped with the lens cone in the lens module, the extinction film can set up the surface at the lens cone, for example: a top wall surface, a side wall surface, a low wall surface, or an outer wall surface and an inner wall surface.
The present application will be described in further detail with reference to specific examples.
EXAMPLE Material preparation of Black coating (BB-1)
1. According to Ti 17%, TiO2 50％，MgO 25％，Fe2O3The raw materials were weighed out at a ratio of 8% to give a total of 10 kg.
2. The raw materials are uniformly mixed using a ball mill or an intensive mixer.
3. The mixed raw materials are pressed into blocks by using an oil press, crushed into small particles and sieved.
4. The small particles were placed in a graphite crucible. And the crucible is placed in a vacuum sintering furnace.
5. The temperature was raised to 900 ℃ at a rate of 10 ℃ per minute. The material was then heated to about 1500 c at a rate of 3 c per minute. And keeping the temperature for more than 3 hours. After the reaction is finished, the heating can be stopped, and the material is naturally cooled.
6. The material is removed from the package and the material appears yellow to dark brownish yellow.
Measured and calculated, the BB-1 material had an n value of 2.3 and a k value of 3.0. The k value is high and stable. In the coating experiment process, the material can be melted into liquid state under the vacuum condition, has stable components and is not easy to decompose and deflate. It was also found that the material evaporated to a firm film, the film layer was black, and there was no color cast or interference.
EXAMPLE two Material preparation of Black coating (BB-2)
1. According to Ti 17%, TiO2 50％，MgO 25％，Fe2O3The raw materials were weighed in a proportion of 4% and CoO 4% to total 10 kg.
2. The raw materials are uniformly mixed using a ball mill or an intensive mixer.
3. The mixed raw materials are pressed into blocks by using an oil press, crushed into small particles and sieved.
4. The small particles were placed in a graphite crucible. And the crucible is placed in a vacuum sintering furnace.
5. The temperature was raised to 900 ℃ at a rate of 10 ℃ per minute. The material was then heated to about 1500 c at a rate of 3 c per minute. And keeping the temperature for more than 3 hours. After the reaction is finished, the heating can be stopped, and the material is naturally cooled.
6. The material is removed from the package and the material appears yellow to dark brownish yellow.
Measured and calculated, the BB-2 material has an n value of 2.3 and a k value of 3.0. The k value is high and stable. In the coating experiment process, the material can be melted into liquid state under the vacuum condition, has stable components and is not easy to decompose and deflate. It was also found that the material evaporated to a firm film, the film layer was black, and there was no color cast or interference.
EXAMPLE III preparation of external surface reflective Black matting film
1. The black coating layer BB-1 of the first example and Ti3O5、SiO2、MgF2The coating materials are respectively put into crucibles and put into 1300 model vacuum evaporation coating equipment.
2. And (3) loading the substrate or the part to be coated into the coating equipment, and closing the vacuum chamber door of the equipment. And vacuumizing to working vacuum.
3. And fully pre-melting the four materials used for coating to prepare for coating.
4. The coating process is set as follows:
initial degree of vacuum for evaporation 3X 10-3Pa, the temperature of the substrate is room temperature, the deposition rate is 5 angstroms/s, and the electron gun evaporation beam current is about 240 mA.
Adopting a Hall ion source, wherein the anode voltage of the ion source is 200V, the current is 1A, and the working medium: ar, gas flow rate of 10 sccm.
5. According to the thickness: 200nm/27.09nm/45.61nm/28.38nm/76.74 nm/air, and sequentially evaporating BB-1/SiO on the plastic substrate2/BB-1/Ti3O5/MgF2Preparing the black extinction film.
The transmittance and reflectance of the film are shown in fig. 1, and it can be seen from the graph that the black extinction film of the present embodiment has a reflectance of less than 0.2% in the visible light band with a wavelength of 340 to 720nm, and a transmittance of less than 0.2% in the visible light band in general. Therefore, the extinction film of the embodiment has a strong absorption effect and low reflectivity, and can be used for extinction inside a lens.
Example four preparation of Black matting film on the inner surface
1. The black coating materials BB-1 and Ti of the first example3O5、SiO2And respectively putting the coating materials into crucibles, and putting the crucibles into vacuum evaporation coating equipment.
2. And (3) loading the substrate or the part to be coated into the coating equipment, and closing the vacuum chamber door of the equipment. And vacuumizing to working vacuum.
3. And fully pre-melting the four materials used for coating to prepare for coating.
4. The coating process is set as follows:
initial degree of evaporation vacuum 4X 10-4Pa, the temperature of the substrate is room temperature, the deposition rate is 3 angstroms/S, and the electron gun evaporation beam current is about 300 mA.
By adopting a Hall ion source, the anode voltage of the ion source is 200V, the current is 2A, and the working medium: ar and O2The gas flow rate is 10sccm/2sccm, respectively.
5. According to the thickness: glass/13.46 nm/27.09nm/16.90nm/39.65nm/17.78nm/220 nm/air, Ti was evaporated on the glass in sequence3O5/SiO2/BB-1/SiO2/Ti3O5the/BB-1 was prepared as a black matte film.
As shown in FIG. 2, the transmittance and reflectance of the black matte film of the present embodiment are generally less than 0.1% in the visible light band with a wavelength of 400 to 670nm, and less than 0.05% in the visible light band. Therefore, the extinction film of the embodiment has strong absorption effect and low reflectivity, and can be used for coating a glass panel.
EXAMPLE five preparation of external surface reflective Black matting film
1. The black coating materials BB-1 and Ti of the first example3O5、SiO2、MgF2And respectively putting the coating materials into crucibles, and putting the crucibles into vacuum evaporation coating equipment.
2. And (3) loading the substrate or the part to be coated into the coating equipment, and closing the vacuum chamber door of the equipment. And vacuumizing to working vacuum.
3. And fully pre-melting the four materials used for coating to prepare for coating.
4. The coating process is set as follows:
initial degree of vacuum for evaporation 2X 10-3Pa, the temperature of the substrate is room temperature, the deposition rate is 5 angstroms/s, and the electron gun evaporation beam current is about 240 mA.
Adopting a Hall ion source, wherein the anode voltage of the ion source is 200V, the current is 1A, and the working medium: ar, gas flow rate of 10 sccm.
5. According to the thickness: glass/270 nm/32.11nm/29.08nm/16.87nm/14.48nm/19.58nm/82.38 nm/air, BB-1/SiO 2 was evaporated on the glass2/BB-1/SiO2/BB-1/Ti3O5/MgF2Preparing the black extinction film.
As shown in fig. 3, the black matte film of the present example generally had a reflectance of less than 0.1% in the visible light range and a light transmittance of less than 0.03% in the visible light range. Therefore, the extinction film of the embodiment has a strong absorption effect and low reflectivity, and can be used for extinction inside a lens.
EXAMPLE six preparation of Black matting film on the inner surface
1. The black coating materials BB-1 and Ti of the first example3O5、SiO2And respectively putting the coating materials into crucibles, and putting the crucibles into vacuum evaporation coating equipment.
2. And (3) loading the substrate or the part to be coated into the coating equipment, and closing the vacuum chamber door of the equipment. And vacuumizing to working vacuum.
3. And fully pre-melting the four materials used for coating to prepare for coating.
4. The coating process is set as follows:
initial degree of vacuum for evaporation 3X 10-3Pa, the temperature of the substrate is room temperature, the deposition rate is 5 angstroms/s, and the electron gun evaporation beam current is about 240 mA.
Adopting a Hall ion source, wherein the anode voltage of the ion source is 200V, the current is 1A, and the working medium: ar, gas flow rate of 10 sccm.
5. According to the thickness: glass/7.0 nm/37.47nm/40.28nm/31.18nm/14.55nm/1.02nm/220 nm/air, successively evaporating Ti on glass3O5/SiO2/Ti3O5/BB-1/Ti3O5/SiO2the/BB-1 was prepared as a black matte film.
As shown in fig. 4, the black matte film of the present example generally had a reflectance of less than 0.05% in the visible light band and a light transmittance of less than 0.1% in the visible light band.
EXAMPLE preparation of a seven outer surface reflective Black matting film
1. The black coating materials BB-2 and Ti of the second example3O5、SiO2And respectively putting the coating materials into crucibles, and putting the crucibles into vacuum evaporation coating equipment.
2. And (3) loading the substrate or the part to be coated into the coating equipment, and closing the vacuum chamber door of the equipment. And vacuumizing to working vacuum.
3. And fully pre-melting the four materials used for coating to prepare for coating.
4. The coating process is set as follows:
initial degree of vacuum for evaporation 3X 10-3Pa, the temperature of the substrate is room temperature, the deposition rate is 5 angstroms/s, and the electron gun evaporation beam current is about 240 mA.
Adopting a Hall ion source, wherein the anode voltage of the ion source is 200V, the current is 1A, and the working medium: ar, gas flow rate of 10 sccm.
5. According to the thickness: 220nm/9.4nm/148.9nm/113.4nm/14.5nm/61.1nm, and sequentially evaporating BB-2/Ti on the plastic substrate3O5/SiO2/BB-2/SiO2/Ti3O5Preparing the black extinction film.
As shown in fig. 5, the black matte film of the present example generally had a reflectance of less than 0.5% in the visible light band and a light transmittance of less than 0.25% in the visible light band. Therefore, the extinction film of the embodiment has a strong absorption effect and low reflectivity, and can be used for extinction inside a lens.
Example eight
1. The black coating materials BB-2 and Ti of the second example3O5、SiO2And respectively putting the coating materials into crucibles, and putting the crucibles into vacuum evaporation coating equipment.
2. And (3) loading the substrate or the part to be coated into the coating equipment, and closing the vacuum chamber door of the equipment. And vacuumizing to working vacuum.
3. And fully pre-melting the four materials used for coating to prepare for coating.
4. The coating process is set as follows:
initial degree of vacuum for evaporation 3X 10-3Pa, the temperature of the substrate is room temperature, the deposition rate is 5 angstroms/s, and the electron gun evaporation beam current is about 240 mA.
Adopting a Hall ion source, wherein the anode voltage of the ion source is 200V, the current is 1A, and the working medium: ar, gas flow rate of 10 sccm.
5. According to the thickness: glass/149 nm/26.4nm/126.7nm/98.95nm/36.82nm/230 nm/air, SiO was evaporated onto the glass in sequence2/Ti3O5/BB-2/SiO2/Ti3O5the/BB-2 is prepared into a black matt film.
As shown in fig. 6, the black matte film of the present example generally had a reflectance of less than 0.6% in the visible light band and a light transmittance of less than 0.08% in the visible light band.
In addition to the examples cited in the present application, in non-exemplified examples, it is also possible to carry out corresponding film system designs according to the formulations of the present application, and TiO can be used2、Ti、Ti2O3，TiO，Ti3O5And the like, as long as the final Ti/O ratio is achieved. Fe2O3And Co as a dopant molecular mosaic such as TiMgOxThe structure of (2) can be doped or undoped because of the effect of adjusting the color difference, but the total amount is less than 10% so as to avoid the color difference while ensuring the light absorption and reflection effects of the extinction film.
In summary, the following steps: the application provides a coating composition, a preparation method thereof, a matt film and a lens module/terminal, wherein the material has a strong absorption effect in visible light and near infrared bands, and can be used for preparing a black matt film with dual effects of transmission extinction and reflection extinction. Meanwhile, the optical parameters such as the refractive index and the like are stable, so that the design and optimization of a film system are facilitated, and the optical film can be applied to the extinction film.
The reflectivity of the black coating layer prepared by the coating composition is less than 0.2% in a visible light range, the transmission light intensity is less than 0.01%, and the color of the coating layer can be prevented from color cast by the iron/cobalt compound component. Both transmitted and reflected light are significantly suppressed. The reflected light intensity is lower than that of black ink or matting paint, and the film thickness of the matting film can be controlled below 500nm and is far lower than the thickness of a common ink coating by hundreds of microns.
The material can be melted and evaporated into a film in vacuum by using an electron beam heating mode, the process is stable, the phenomena of splashing, decomposition and the like do not exist, and a uniform and firm film with good adhesive force is formed.
Meanwhile, compared with the process of coating by using ink dyes, the process has the advantages of simple process, short preparation time, high product yield and no emission of solvent gas. And the thickness of the film layer is below 500nm and far lower than the thickness of a plurality of hundreds of microns of a common ink coating. The optical module is very suitable for small optical modules such as mobile phone cameras, and the thickness and the weight of the system cannot be increased.
Meanwhile, the process is simple, compared with the process of coating by using ink dyes, the preparation process of the matt film is short in time consumption and high in product yield, and solvent gas cannot be discharged.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. A method for preparing a coating composition, comprising:
s1, providing a first raw material as a first component, wherein the first raw material is selected from Ti and TiO2、Ti2O3Or Ti3O5Any one or more of these and MgO; the first raw material further comprises Fe2O3Or FeO, and/or, Co2O3Or CoO; wherein, in the first raw material, the molar ratio of Ti element, Mg element and O element is 1 (0.2-1) to 0.8-1.5, and the weight of Fe element and/or Co element is less than or equal to 10%;
s2, uniformly mixing the first raw materials and preparing the mixture into small particles;
s3, sintering the particles in the S2 to obtain a first component which is yellow to dark brown-yellow; the sintering treatment comprises the following steps: the temperature is increased to 600-950 ℃ at the speed of 7-13 ℃ per minute, then the material is heated to 1000-1600 ℃ at the speed of 2-4 ℃ per minute, the temperature is kept constant for at least 3 hours, the heating can be stopped after the reaction is finished, and the material is naturally cooled.
2. The method according to claim 1The method further includes providing a second material and a third material as a second component, wherein the second material is selected from Nb in step S12O5、NbO2、Nb、Ta2O5、Ti3O5、Ti2O3、ZrO2Any one or more of ZrO, or Zr; the third raw material is selected from SiO2、MgF2Or a silica alumina mix.
3. The coating composition prepared by the preparation method of claim 1 or 2, comprising a first component, wherein the first component contains Ti, Mg and O, and Fe and/or Co, the molar ratio of the Ti, Mg and O in the coating composition is 1 (0.2-1) to (0.8-1.5), and the Mg is selected from MgO; the weight of the Fe element and/or the Co element is less than or equal to 10%.
4. The plating composition according to claim 3, wherein in the first component, the Ti element is selected from Ti and TiO2、Ti2O3Or Ti3O5At least one of; the Fe element is selected from Fe2O3Or FeO; the Co element is selected from Co2O3Or CoO; the coating composition further comprises a second component and a third component, wherein the second component is Nb2O5、NbO2、Nb、Ta2O5、Ti3O5、Ti2O3、ZrO2Any one or more of ZrO, or Zr; the third component is selected from SiO2、MgF2Or a silica alumina mix.
5. The extinction film is characterized by comprising at least two black coating layers, a high-refraction layer and a low-refraction layer, wherein the low-refraction layer is arranged between the two black coating layers, or the high-refraction layer and the low-refraction layer are arranged between the two black coating layers; the black coating layer comprises the coating composition according to claim 3 or 4.
6. A matting film according to claim 5, wherein said high refractive layer contains a second component selected from Nb2O5、NbO2、Nb、Ta2O5、Ti3O5、Ti2O3、ZrO2Any one or more of ZrO or Zr.
7. A matting film according to claim 5, wherein said low-refractive layer contains a third component selected from SiO2、MgF2Or a silica alumina mix.
8. A lens module comprising the matting film according to any one of claims 5 to 7.
9. A terminal comprising the matting film according to any one of claims 5 to 7.
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