CN212864579U

CN212864579U - Neutral color double-layer antireflection coating and glass with same

Info

Publication number: CN212864579U
Application number: CN202021810741.3U
Authority: CN
Inventors: 王彪; 倪志龙; 张敏
Original assignee: Shanghai Xiyuan New Energy Technology Co ltd
Current assignee: Shanghai Xiyuan New Energy Technology Co ltd
Priority date: 2020-08-26
Filing date: 2020-08-26
Publication date: 2021-04-02
Anticipated expiration: 2030-08-26

Abstract

The utility model provides a neutral double-deck antireflection coating film and have glass of this coating film. Specifically, the utility model provides a neutral color double-layer antireflection coating, which comprises a bottom layer film layer and an antireflection film layer; the bottom film layer is positioned on the inner side of the neutral-color double-layer antireflection coating, and the antireflection film layer is positioned on the outer side of the neutral-color double-layer antireflection coating; and the outer side surface of the bottom film layer is an undulating surface. The utility model discloses a conventional antireflection coating reflection of light colour difference problem has been avoided to the coating film and the product percent of pass has been promoted greatly, and this double-deck antireflection coating preparation method is simple moreover.

Description

Neutral color double-layer antireflection coating and glass with same

Technical Field

The utility model relates to a nano-material and photovoltaic cell field. Specifically, the utility model relates to a neutral double-deck antireflection coating film and have glass of this coating film.

Background

In recent years, the worldwide energy shortage and environmental protection pressure greatly promote the research and development and application of solar cell photovoltaic modules. With the continuous optimization of solar cell photovoltaic modules, the conversion efficiency of crystalline silicon cells in the solar cell photovoltaic modules is continuously improved. Meanwhile, researches on the influence of the packaging material on the efficiency, appearance and the like of the assembly are increasingly carried out. At present, people generally adopt ultra-white photovoltaic glass with low iron content as packaging glass for a photovoltaic module of a solar cell, and the glass has high transmittance in a visible light wave band. But there is still about 4% reflection of the photovoltaic glass surface to visible light due to the refractive index difference between the photovoltaic glass and air. The transmittance of light can be effectively improved by coating a layer of antireflection film on the surface of the photovoltaic glass, so that the output power of the photovoltaic module of the solar cell is improved.

At present, the antireflection film for photovoltaic glass is subject to the requirement of cost, and a sol-gel method is mainly adopted to prepare the antireflection film made of a single-layer porous silicon oxide material. For example, patent publication No. CN1263354A discloses an acid-base two-step method for preparing an anti-reflective coating with high film-based bonding force by infiltrating an organic additive and a silane coupling agent into a silica nanoparticle crosslinked network or a particle network. Although the common single-layer antireflection film is easy to produce, the regulation and control means of the antireflection characteristic is single. Meanwhile, a common single-layer classical antireflection film generally presents an obvious blue or bluish-purple appearance, and when the photovoltaic module is actually applied, the single-layer antireflection film easily generates an obvious module appearance color difference phenomenon, so that the attractiveness and consistency of the module in actual application and the product yield are greatly influenced. So far, the preparation method and the application of the high-efficiency antireflection coated glass which is specially used for packaging the photovoltaic module and has the appearance problems of neutral color, difficult color difference generation and the like are quite rare.

Therefore, the research and development of a preparation method of the photovoltaic antireflection coated glass, which has the advantages of low process cost, simple technical route, suitability for industrial large-scale application, neutral color and difficulty in generating chromatic aberration, is urgently needed in the field.

SUMMERY OF THE UTILITY MODEL

The utility model aims at providing a neutral color antireflection coating or coating film which is easy to apply or prepare.

In a first aspect of the utility model, a neutral color double-layer antireflection coating is provided,

the neutral-color double-layer antireflection coating consists of a bottom layer film layer and an antireflection film layer;

wherein the content of the first and second substances,

the bottom film layer is positioned on the inner side (namely the side close to the surface to be coated) of the neutral double-layer antireflection coating; the antireflection film layer is positioned on the outer side of the neutral double-layer antireflection coating;

and the outer side surface of the bottom film layer is an undulating surface.

In another preferred example, the surface of the undulating surface is distributed with plateau-like convex portions and valley-like concave portions surrounding the plateau-like convex portions.

In another preferred embodiment, the surface of the undulating surface is distributed with 1 × 10 per square meter⁵～1×10⁷And a plurality of said elevated convex portions.

In another preferred embodiment, the length dimension of the raised plateau-like projection is 0.1-2 mm.

In another preferred example, the distances from the highest point of the high-land-shaped convex part to the surface to be coated are the same or different.

In another preferred embodiment, the thinnest part of the bottom film layer has a thickness D_minThe thickness of the thickest part of the bottom film layer is D_max(ii) a And D_min＝0.3～0.625D_max(ii) a Preferably, D_min＝0.375～0.5D_max。

In another preferred example, the thickness of the thinnest part of the bottom film layer is 30-50 nm; and/or the thickness of the thickest part of the bottom film layer is 80-100 nm.

In another preferred embodiment, the thickness of the anti-reflective layer is 100-120 nm.

In another preferred embodiment, the outer side surface of the antireflection film layer substantially fluctuates with the fluctuation of the fluctuation surface of the outer surface of the bottom film layer.

In another preferred example, the thickness of the neutral color double-layer antireflection coating is 130-220 nm.

In another preferred embodiment, the thickest part of the bottom film layer refers to the highest part of the raised land-like part.

In another preferred example, the refractive index of the antireflection film layer is 1.26 to 1.30.

In another preferred example, the undulating surface is generated by a benard spin phenomenon (or a benard vortex).

In another preferred example, the plateau-like convex portion and the valley-like concave portion surrounding the plateau-like convex portion are generated by a benard swirl phenomenon (or benard vortex).

In another preferred example, the bottom layer film layer is formed by bottom layer sol;

and the bottom layer sol is prepared by the following method:

providing a pre-mixture comprising a catalyst, a silicon source, water and a mixed alcohol solvent, and carrying out hydrolytic polymerization reaction on an organic silicide in the pre-mixture to obtain a bottom layer sol;

wherein, the mixed alcohol solvent consists of methanol, ethanol and isopropanol.

In another preferred embodiment, the alcohol solution mixture comprises: 5 to 50 parts by mole (preferably, 5 to 40 parts by mole, more preferably, 5 to 30 parts by mole, still more preferably, 10 to 30 parts by mole, most preferably, 20 to 30 parts by mole) of methanol.

In another preferred embodiment, the alcohol solution mixture comprises: 5 to 40 parts by mole (preferably, 5 to 30 parts by mole, more preferably, 5 to 20 parts by mole, most preferably, 10 to 20 parts by mole) of ethanol.

In another preferred embodiment, the alcohol solution mixture comprises: 10 to 90 parts by mole (preferably 30 to 90 parts by mole, more preferably 50 to 90 parts by mole, still more preferably 50 to 80 parts by mole, most preferably 50 to 70 parts by mole) of isopropyl alcohol.

In another preferred embodiment, the alcohol solution mixture comprises: 5-50 parts by mole of methanol; 5-40 parts by mole of ethanol; and 10-90 molar parts of isopropanol.

In another preferred embodiment, the alcohol solution mixture comprises: 5-30 molar parts of methanol; 5-20 parts by mole of ethanol; and 50-90 molar parts of isopropanol.

In another preferred embodiment, the alcohol solution mixture comprises: 20-30 molar parts of methanol; 10-20 molar parts of ethanol; and 50-70 molar parts of isopropanol.

In another preferred example, the mixed alcohol solvent consists of 5-50 mol% of methanol, 5-40 mol% of ethanol and the balance of isopropanol.

In another preferred example, the mixed alcohol solvent consists of 5-30 mol% of methanol, 5-20 mol% of ethanol and the balance of isopropanol.

In another preferred example, the mixed alcohol solvent consists of 20-30 mol% of methanol, 10-20 mol% of ethanol and the balance of isopropanol.

In another preferred example, in the pre-mixture, the molar ratio of the silicon source to the mixed alcohol solvent is (0.01-1): 10; preferably, the ratio is (0.05-0.4): 10; more preferably, it is (0.1 + -0.03): 10; most preferably (0.1. + -. 0.01): 10.

In another preferred embodiment, in the pre-mixture, the molar ratio of the silicon source to the catalyst is 1 (0.2-5); preferably, the ratio is 1 (0.5-2); more preferably, 1 is (1. + -. 0.3); most preferably, it is 1 (1. + -. 0.1).

In another preferred example, in the pre-mixture, the molar ratio of the silicon source to the water is 1 (1-25); preferably, the ratio is 1 (2.5-10); more preferably, 1 is (5. + -. 1.5); most preferably, it is 1 (5. + -. 0.5).

In another preferred embodiment, the premix comprises: 80-120 parts by mol of a mixed alcohol solvent; 0.8-1.2 molar parts of silicon source; 0.8-1.2 molar parts of a catalyst; 1-20 parts by mole of water.

In another preferred embodiment, the pre-mixture comprises 90-110 molar parts of mixed alcohol solvent.

In another preferred embodiment, the pre-mixture comprises 0.9 to 1.1 molar parts of silicon source.

In another preferred embodiment, the pre-mixture comprises 0.9-1.1 molar parts of the catalyst.

In another preferred embodiment, the pre-mixture comprises 3 to 10 molar parts of water.

In another preferred embodiment, the pre-mixture comprises 4-6 molar parts of water; more preferably, it comprises 4.5 to 5.5 molar parts of water.

In another preferred embodiment, in step (1), the catalyst is an acid catalyst.

In another preferred embodiment, in step (1), the catalyst is selected from the group consisting of: nitric acid, hydrochloric acid, or a combination thereof.

In another preferred example, in step (1), the silicon source is an organic silicide.

In another preferred embodiment, in step (1), the silicon source is selected from the group consisting of: tetraethyl orthosilicate, tetramethyl orthosilicate, or a combination thereof.

In another preferred example, the neutral-color double-layer antireflection coating is a film formed by the production method according to the second aspect.

In a second aspect of the present invention, there is provided a method of forming a neutral color double-layer antireflection coating on a desired surface, the method comprising the steps of:

(1) preparing a primer sol for applying the primer film,

the method comprises the following steps: providing a pre-mixture comprising a catalyst, a silicon source, water and a mixed alcohol solvent, and carrying out hydrolytic polymerization reaction on an organic silicide in the pre-mixture to obtain a bottom layer sol;

wherein the mixed alcohol solvent consists of methanol, ethanol and isopropanol;

(2) applying the bottom layer sol obtained in the step (1) to a required surface, and drying the bottom layer sol on the surface to form a bottom layer dry film on the surface;

(3) curing the bottom layer dry film to form a bottom layer film;

(4) an antireflection film is applied on the outer side surface of the underlayer film, thereby forming a neutral-color double-layer antireflection coating film as described in the first aspect on the surface.

In another preferred example, the surface to be coated refers to the surface of a glass substrate, or the surface of the glass substrate after other functional film layers are applied.

In another preferred embodiment, the surface is a smooth or substantially smooth surface.

In another preferred example, in the step (2), the primer layer sol obtained in the step (1) is applied to the surface of the glass substrate needing coating through a roller coating, spraying and/or dipping pulling method.

In another preferred embodiment, in the step (2), the drying is performed under 0.5 to 1.5 (preferably, 0.8 to 1.2; more preferably, 1. + -. 0.1) atmospheres.

In another preferred example, in the step (2), the drying is performed under normal pressure.

In another preferred example, in the step (2), the drying is performed at 10-40 ℃, preferably 15-30 ℃; more preferably at 20-25 ℃.

In another preferred example, in the step (2), the drying is performed in air.

In another preferred example, the step (2) includes the steps of:

(2.1) applying the primer sol obtained in step (1) to the surface, thereby forming a primer wet film on the surface; and

(2.2) allowing the bottom layer wet film to gradually evaporate and dry in the air, thereby forming a bottom layer dry film.

In another preferred example, in the step (3), the curing treatment is a heat treatment.

In another preferred example, in the step (3), the heat treatment is to heat the gel bottom layer to the first heat treatment temperature, and then cool it.

In another preferred example, in the step (3), the first heat treatment temperature is more than or equal to 80 ℃; preferably, the temperature is 80 to 200 ℃; more preferably, it is 80 to 150 ℃; most preferably, it is 80 to 120 ℃.

In another preferred embodiment, in the step (3), the heating time for the heat treatment is 0.5 to 30 minutes, more preferably 0.5 to 10 minutes, and still more preferably 0.5 to 2 minutes.

In another preferred example, in the step (3), the cooling is natural cooling.

In another preferred example, in the step (3), the cooling is to be performed to 10 to 40 ℃; preferably, 15 to 30 ℃; more preferably to 20-25 ℃.

In another preferred example, in the step (3), the cooling is to room temperature.

In another preferred example, in the step (4), an antireflection film is formed on the surface of the underlying film layer by a sol-gel method.

In another preferred example, the step (4) includes the steps of:

(4.1) applying an anti-reflective film coating liquid to the outer side surface of the underlying film, thereby forming a dry anti-reflective film on the outer side surface of the underlying film; and

(4.2) curing the antireflection dry film so as to plate the neutral-color double-layer antireflection coating on the surface to be coated.

In another preferred example, in the step (4), the coating solution for antireflection film may be prepared by itself or may be commercially available.

In another preferable example, in the step (4), the antireflection film coating solution is an antireflection film coating solution for forming an antireflection film by a sol-gel method.

In another preferred embodiment, in step (4.2), the treatment is a heat treatment.

In another preferred example, in the step (4.2), the heat treatment is such that the antireflective dried film is heated to the second heat treatment temperature, and thereafter, is cooled.

In another preferred example, the second heat treatment temperature depends on the antireflection film coating solution used.

In another preferred example, in the step (4.2), the second heat treatment temperature is 100 to 1500 ℃; preferably, the temperature is 500 to 1000 ℃; more preferably, 600 to 800 ℃; most preferably, it is 650 to 750 ℃.

In another preferred embodiment, in the step (4.2), the heating time of the heat treatment is 0.5 to 30 minutes, more preferably 0.5 to 10 minutes, and still more preferably 1 to 5 minutes; most preferably, 2 to 3 minutes.

In another preferred example, in the step (4.2), the cooling is program cooling or natural cooling; preferably, natural cooling is used.

In another preferred example, in the step (4.2), the cooling is to be carried out to 10-40 ℃; preferably, 15 to 30 ℃; more preferably to 20-25 ℃.

In another preferred example, in the step (4.2), the cooling is to room temperature.

In another preferred embodiment, the alcohol solution mixture comprises:

5-50 parts by mole of methanol;

5-40 parts by mole of ethanol; and

10-90 molar parts of isopropanol.

In another preferred embodiment, the alcohol solution mixture comprises:

5-30 molar parts of methanol;

5-20 parts by mole of ethanol; and

50-90 molar parts of isopropanol.

In another preferred embodiment, the alcohol solution mixture comprises:

20-30 molar parts of methanol;

10-20 parts by mole of ethanol; and

50-70 parts by mole of isopropanol.

In another preferred embodiment, the premix comprises:

80-120 parts by mol of a mixed alcohol solvent;

0.8-1.2 molar parts of a silicon source;

0.8-1.2 molar parts of a catalyst;

1-20 parts by mole of water;

In another preferred embodiment, in step (1), the catalyst is an acid catalyst.

In a third aspect of the present invention, there is provided a neutral color double-layer antireflection coating formed by the manufacturing method according to the second aspect.

In a fourth aspect of the present invention, there is provided a coated glass, comprising:

a glass substrate; and

a neutral-color double-layer antireflection coating provided on at least one surface of the glass substrate, wherein the neutral-color double-layer antireflection coating is as described in the first aspect or the third aspect.

In another preferred embodiment, the glass substrate is a flat glass substrate.

In another preferred embodiment, the glass substrate is an ultra-white embossed glass substrate.

In another preferred embodiment, the thickness of the glass substrate is 2 to 5 mm.

In another preferred example, the glass substrate is a glass substrate which is not plated or applied with a functional film, or a glass substrate which is plated or provided with one or more other functional films on one surface, or a glass substrate which is plated or provided with one or more other functional films on two surfaces.

In another preferred example, the coated glass is a flat plate-shaped coated glass;

and the single surface of the coated glass is provided with the coated glass with the neutral color double-layer antireflection coating, or the coated glass is coated glass with the two surfaces both provided with the neutral color double-layer antireflection coating.

In another preferred example, the coated glass is coated glass with the neutral-color double-layer antireflection coating arranged on one surface;

and the coated glass comprises:

a glass substrate (1) having a first surface;

a first base film layer (21) disposed on the first surface; and

a first anti-reflection film layer (31) arranged on the outer side surface of the first bottom film layer; and is

The first underlayer film is defined as the underlayer film, and the first anti-reflective film is defined as the anti-reflective film.

In another preferred example, the coated glass is coated glass with the neutral color double-layer antireflection coating arranged on both surfaces;

and the coated glass comprises:

a glass substrate (1) having a first surface and a second surface;

a first base film layer (21) disposed on the first surface;

a first anti-reflection film layer (31) arranged on the outer side surface of the first bottom film layer;

a second base film layer (22) disposed on the second surface; and

a second anti-reflection film layer (32) disposed on an outer side of the second bottom film layer;

the first bottom film layer and the second bottom film layer are defined as the bottom film layers, and the first anti-reflection film layer and the second anti-reflection film layer are defined as the anti-reflection film layers.

In another preferred example, the first underlayer film layer (21) and the first antireflection film layer (31) together form a neutral color double-layer antireflection film as described in the first aspect.

In another preferred example, the second underlying film layer (22) and the second anti-reflective film layer (32) together form a neutral color dual layer anti-reflective film as described in the first aspect.

In another preferred example, the coated glass presents a neutral color when reflecting natural light.

In another preferred example, the coated glass basically does not show blue, purple and blue-purple when reflecting natural light.

In another preferred example, the neutral-color double-layer antireflection coated glass presents neutral-color reflection under natural light.

In another preferred example, the neutral double-layer antireflection coated glass basically does not reflect blue, purple and blue-purple light under natural light.

In another preferred example, the neutral-color double-layer antireflection coating is applied by the method according to the second aspect.

In a fifth aspect of the present invention, there is provided a method for manufacturing coated glass, the method comprising the steps of:

(a) providing a glass substrate; and

(b) applying a neutral-color double-layer antireflection coating on at least one surface of the glass substrate by the method according to the second aspect, thereby obtaining the coated glass.

In another preferred example, the step (b) is to apply the neutral-color double-layer antireflection coating simultaneously on 2 surfaces of the glass substrate by the method according to the second aspect, thereby obtaining the coated glass.

In another preferred example, the step (b) is to apply the neutral-color double-layer antireflection coating on only 1 surface of the glass substrate by the method according to the second aspect, thereby obtaining the coated glass.

In a sixth aspect of the present invention, there is provided a coated glass produced by the production method according to the fifth aspect.

It is understood that within the scope of the present invention, the above-mentioned technical features of the present invention and those specifically described below (e.g. in the examples) can be combined with each other to constitute new or preferred technical solutions. Not to be reiterated herein, but to the extent of space.

Drawings

FIG. 1 shows a schematic cross-sectional view of a coated glass of the present application coated with a single double layer coating.

FIG. 2 is a schematic cross-sectional view of a coated glass of the present application having a double-coated surface.

Fig. 3 shows the undulating surface of the outer side of the bottom film layer.

Fig. 4 shows a schematic cross-sectional view of glass coated with the double-layer antireflection film of the present invention.

Wherein, each mark is as follows:

1 is a substrate (such as a glass substrate), 21 and 22 are respectively a first bottom film layer and a second bottom film layer, 31 and 32 are respectively a first antireflection film layer and a second antireflection film layer; 41 is a raised part; 42 is a valley-shaped concave portion surrounding the plateau-shaped convex portion.

Fig. 5 shows a scanning electron microscope image of a cross section of the glass sample plated with the double-layer photovoltaic antireflection coating obtained in example 1.

Fig. 6 shows transmittance spectra of the glass samples coated with the double-layer photovoltaic antireflection coating on one side and the uncoated photovoltaic glass samples as reference obtained in example 1.

Fig. 7 shows the reflection of the appearance of the double-layer photovoltaic antireflection coated glass prepared in the examples and comparative examples of the present application under natural light, where the left-hand one shows the bright bluish purple reflection of the single-layer coated glass under natural light (comparative example 1), the left-hand two shows the bluish neutral reflection of the coated glass under natural light (example 3), the right-hand one shows the bluish reflection of the coated glass under natural light (comparative example 2), and the right-hand two shows the neutral reflection of the coated glass under natural light (example 1).

Detailed Description

The inventors have conducted extensive and intensive studies. It has been unexpectedly found that by preparing a bottom layer film having a specific structure on a glass substrate surface using a mixed alcohol solvent of a specific composition as a solvent for a coating solution or sol used in a sol-gel process, and then applying an antireflection film on the bottom layer film, the blue or bluish-violet appearance of a conventional antireflection film can be avoided while maintaining the original performance (e.g., antireflection ability) of the antireflection film. Based on this, the utility model discloses the people has accomplished the utility model discloses.

Term(s) for

In this context, "inner" and "outer" are relative relationships, which are for purposes of illustration only and are not limiting. Generally, in this context, "inner side" means the side close to the substrate (glass) surface or the surface to be coated or the side to be coated, and correspondingly "outer layer" means the side remote from the substrate.

As used herein, the term "dip draw" or "dip draw" refers to a conventional film forming or coating method in which a substrate or a substrate is immersed in a coating sol and then smoothly drawn out from the sol at a uniform speed to form a uniform liquid film on the surface of the substrate due to viscosity and gravity. This technique is also referred to herein as "lift-coating".

As used herein, the term "roll coating" refers to a process in which a carrier for a coating sol is applied by a roll to form a wet film of a certain thickness on the surface of the roll, and then the wet film is applied to the surface to be coated by the coating sol by contacting the roll with the object to be coated during rotation.

As used herein, the term "benard vortex" or "benard phenomenon" refers to Rayleigh-benard convection (Rayleigh-benard convection), which broadly refers to a type of natural convection that often occurs on a layer of fluid surface heated from the bottom. The convection cells with regular shapes formed on the surface by the fluid subjected to convection are called as Benard cells.

Herein, the terms "neutral color double-layer antireflection coating", "double-layer antireflection coating", and "double-layer coating" may be used interchangeably to refer to a neutral color double-layer antireflection coating as described in the first aspect.

As used herein, the term "neutral color," also known as the achromatic color system, refers to a gray series of varying shades of black, white, and blended from black and white, and the neutral color does not belong to the cool tone nor to the warm tone.

As used herein, the term "length dimension", or periodic dimension referred to as the length or width of the raised plateau portion, refers to the maximum distance between any 2 points on the edge line or perimeter line of the raised plateau portion when the outer side of the underlying film layer is viewed in a direction perpendicular to the surface to be coated.

Double-layer antireflection coating and coated glass with same

As shown in fig. 3 and 4, the utility model provides a neutral color double-layer antireflection coating (or simply referred to as double-layer coating),

the neutral-color double-layer antireflection coating consists of a bottom layer film layer (21) and an antireflection film layer (31);

wherein the content of the first and second substances,

the bottom film layer is positioned on the inner side of the neutral double-layer antireflection coating (namely one side of the surface needing coating), and the antireflection film layer is positioned on the outer side of the neutral double-layer antireflection coating; and the outer side surface of the bottom film layer is an undulating surface. Preferably, the surface of the undulating surface is distributed with raised land portions (41) and valley recessed portions (42) surrounding the raised land portions.

Preferably, the distribution be inhomogeneous distribution or anomalous distribution, the utility model discloses in make through this unique undulation surface the utility model provides a double-deck antireflection coating film can be when effectively reducing the glass reflection and increasing the transmissivity, unexpected and promote double-deck antireflection coating film reflection of light condition remarkably, make it only demonstrate neutral color or basic neutral color, the reflection of light colour difference greatly leads to the serious flaw of product when having avoided using on a large scale the material that has antireflection coating film like glass, produces a large amount of products of scrapping, pleasing to the eye scheduling problem.

Preferably, the underlayer film layer is as previously defined and the antireflective film layer is as previously defined.

Preferably, the antireflection film layer is as defined above.

Preferably, the antireflection film layer is obtained by applying a coating solution for applying an antireflection film, which is prepared by itself or is commercially available, to the underlying film layer by a conventional method, or a method recommended by a manufacturer, or a method herein.

The utility model also provides coated glass with double-deck antireflection coating, coated glass include:

a glass substrate (1); and

a double anti-reflective coating (as described above) disposed on at least one surface of the glass substrate.

In one embodiment, the present invention provides a coated glass having the double-layered coating film disposed on one side or both sides as shown in fig. 1; the coated glass comprises:

a glass substrate (1) having a first surface;

a first base film layer (21) disposed on the first surface; and

a first anti-reflective film layer (31) disposed on the first base film layer; and is

In another embodiment, the present invention provides a coated glass having the double-layered coating film on both surfaces as shown in fig. 2; the coated glass comprises:

a glass substrate (1) having a first surface and a second surface;

a first base film layer (21) disposed on the first surface;

a first anti-reflective film layer (31) disposed on the first base film layer;

a second base film layer (22) disposed on the second surface; and

a second anti-reflective film layer (32) disposed on the second bottom film layer;

It should be understood that fig. 1 and 2 are merely intended to provide a dual-layer antireflection film layer in opposing relation to a substrate (e.g., glass) and therefore do not show the relief surface therein.

Neutral-color photovoltaic double-layer antireflection coated glass and preparation method and application thereof

The utility model aims at providing a high-transmittance photovoltaic double-layer antireflection coated glass with neutral color and difficult chromatic aberration generation and a preparation method thereof.

In another embodiment, the present invention provides a method for preparing a composition comprising the steps of:

1. preparing a bottom layer sol A by taking organic silicon compounds such as tetraethyl orthosilicate, tetramethyl orthosilicate and the like as silicon sources in a mixed alcohol solvent of isopropanol-ethanol-methanol and taking nitric acid, hydrochloric acid and the like as catalysts through hydrolytic polymerization reaction; preferably, the specific steps are: adding a certain amount of methanol and ethanol into isopropanol, mixing and stirring to obtain a mixed alcohol solvent, sequentially adding a silicon source such as tetraethyl orthosilicate, tetramethyl orthosilicate and the like, a catalyst such as nitric acid, hydrochloric acid and the like and water into the mixed alcohol solvent, and stirring at room temperature for 1-3 hours to obtain a bottom layer sol A. (ii) a

Preferably, in the mixed alcohol solvent, the proportion of methanol is 5-30%, the proportion of ethanol is 5-20%, and the balance is isopropanol.

Preferably, the alcohol solvent is mixed: silicon source: catalyst: the molar ratio of water is 20: 0.2: 0.2: 1.

2. coating the bottom layer sol A on the surface of the super-white embossed photovoltaic glass substrate at room temperature of 20-25 ℃ by means of roller coating, spraying, pulling, coating and other technical means, then gradually volatilizing and drying the bottom layer sol A in the air to form a gel bottom layer, wherein the thickness of the gel bottom layer is in a non-uniform distribution state (preferably, the thickness of the gel bottom layer is controlled to be about 30-50nm in a thin area, and about 80-100nm in a thicker area, and the cycle length size of the non-uniform distribution of the film layer is usually about 0.1-2 mm). The reason for the uneven distribution of the film layer is to effectively utilize the natural phenomenon of the Benard vortex generated by the liquid convection when the bottom layer sol A volatilizes on the glass substrate.

And 3, heating the glass substrate coated with the bottom layer of the unevenly distributed gel to be more than 80 ℃ (such as heating by a heating furnace and the like), and then cooling to room temperature.

4. Plating the antireflection coating solution on the surface of the gel bottom layer of the glass substrate obtained in the step (3) at room temperature of 20-25 ℃ by means of roller coating, spraying, lifting coating and other technical means, thereby obtaining a double-layer gel coating on the ultra-white embossed photovoltaic glass.

The antireflection coating solution used in this step can be commercially available antireflection coating solution (for example, KhepriCoat T2 coating solution from imperial corporation, shanghai, seiki, new energy technology limited, E1 coating solution from shanghai, seikagaku, ltd, 760# -coating solution from wuxinkang high new material limited), after the glass is normally tempered and heated, the refractive index of the coating layer is required to be 1.26-1.30, and the thickness of the coating layer is required to be 100-.

5. And heating the super glass sample coated with the double-layer gel coating to 650-750 ℃ (such as by a heating furnace and other equipment), heating for 2-3 minutes, and then cooling to room temperature to obtain the double-layer photovoltaic antireflection coated glass.

The utility model discloses a main advantage includes:

(a) the appearance of the double-layer coated glass shows neutral color under natural light on the basis of keeping the high-efficiency anti-reflection performance.

(b) The utility model discloses a preparation technology of double-deck coated glass is simple and convenient, low, the technical route of process cost is simple, is fit for the large-scale application of industrialization. And the prepared double-layer coated glass has stable quality and small color difference among batches. When the glass packaging assembly is used, the problem of appearance flaws caused by chromatic aberration of glass coating can be obviously reduced, and the convenience of the application of the coated glass on the assembly is improved.

(c) The coated glass is observed under natural light, and the appearance reflection of light is neutral. In the aspect of optical gain index, the average transmittance of the glass sample coated with the double-layer antireflection coating is increased to 2.5% (single-sided coating) or 5.0% (double-sided coating) in the range of 1100nm in wavelength 400 compared with the uncoated glass sample, and the gain index is consistent with that of the glass sample coated with the antireflection coating only.

The present invention will be further described with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are mole percentages and mole parts.

Example 1

1mol of methanol, 0.5mol of ethanol and 3.5mol of isopropanol are mixed and stirred, 0.05mol of tetraethyl orthosilicate, 0.05mol of concentrated hydrochloric acid and 0.25mol of water are sequentially added, and the mixture is stirred for 2 hours at room temperature to form bottom layer sol A.

The bottom layer sol A is coated to the surface of a super white embossed photovoltaic glass substrate with the thickness of 3.2mm at room temperature of 20 ℃ by a roller coating mode, and then the bottom layer sol A is volatilized and dried to become a gel bottom layer in the air (until the weight and the thickness of the gel layer are kept stable and unchanged). The thickness of the gel bottom layer was observed to be around 40nm in the thin region and around 90nm in the thicker region. The length of the period of the film layer which is not uniformly distributed is about 0.1-1 mm.

Setting the temperature of an oven to be 150 ℃, heating the ultra-white embossed photovoltaic glass sample wafer coated with the non-uniformly distributed gel bottom layer for about 1 minute until the surface temperature of the sample reaches about 80 ℃, taking out the sample, and cooling to room temperature.

Plating an E1 type coating solution of Shanghai West Source New energy technology Limited onto the surface of the gel bottom layer of the ultra-white embossed photovoltaic glass sample at room temperature of 20 ℃ by a roller coating method to obtain the ultra-white embossed photovoltaic glass sample sheet with a single-side coated with a double-layer gel coating.

Heating the super-white embossed photovoltaic glass sample wafer coated with the double-layer gel coating to 700 ℃ by a heating furnace for 2.5 minutes, and then cooling to room temperature. After heating, the refractive index of the single-layer antireflection coating layer on the surface of the sample is about 1.28, and the thickness of the coating layer is about 110 nm.

The obtained double-layer photovoltaic antireflection coated glass is observed under natural light, and the reflected light in the appearance is neutral (the light reflection effect is shown in figure 7). Meanwhile, the average transmittance of the glass sample with the single-side coated with the double-layer photovoltaic antireflection coating is increased by about 2.5 percent (see figure 6) in the range of the wavelength of 400-1100nm compared with that of the glass sample without the coating.

The sectional electron micrograph of the double-layer photovoltaic antireflection coated glass is shown in figure 5.

Example 2

1.5mol of methanol, 1mol of ethanol and 2.5mol of isopropanol are mixed and stirred, 0.05mol of tetramethyl orthosilicate, 0.05mol of concentrated nitric acid and 0.25mol of water are sequentially added, and the mixture is stirred for 1 hour at room temperature to form bottom layer sol A.

Coating the bottom layer sol A on the surface of the super-white embossed photovoltaic glass substrate with the thickness of 2.5mm at room temperature of 25 ℃ by a lifting coating mode, and then volatilizing and drying the bottom layer sol A in the air to form a gel bottom layer. The thickness of the gel bottom layer was observed to be around 30nm in the thin region and around 100nm in the thicker region. The cycle length size of the film layer which is not uniformly distributed is about 0.1-2 mm.

Setting the temperature of an oven to be 150 ℃, heating the ultra-white embossed photovoltaic glass sample wafer coated with the non-uniformly distributed gel bottom layer for about 1 minute until the surface temperature of the sample reaches about 100 ℃, taking out the sample, and cooling to room temperature.

And coating a Khepri coat T2 type coating solution of Dusmann, Netherlands on the surface of the gel bottom layer of the ultra-white embossed photovoltaic glass sample at room temperature of 25 ℃ by a lifting coating method to obtain the ultra-white embossed photovoltaic glass sample piece with double-layer gel coating plated on two sides.

Heating the ultra-white embossed photovoltaic glass sample wafer with the double-layer gel coating plated on the two sides to 650 ℃ through a heating furnace for 3 minutes, and then cooling to room temperature. After heating, the refractive index of the single-layer antireflection coating layer on the surface of the sample is about 1.26, and the thickness of the coating layer is about 120 nm.

The obtained double-layer photovoltaic antireflection coated glass is observed under natural light, and the reflected light of the appearance is neutral (the light reflecting effect is basically the same as that of the example 1). Meanwhile, the average transmittance of the glass sample with the double-sided photovoltaic antireflection coating is increased by about 4.8 percent compared with that of the glass sample without the coating in the wavelength range of 400-1100 nm.

Example 3

0.25mol of methanol, 0.25mol of ethanol and 4.5mol of isopropanol are mixed and stirred, 0.05mol of tetraethyl orthosilicate, 0.05mol of concentrated hydrochloric acid and 0.25mol of water are sequentially added, and the mixture is stirred for 3 hours at room temperature to form bottom layer sol A.

Coating the bottom layer sol A to the surface of a super-white embossed photovoltaic glass substrate with the thickness of 3.2mm at room temperature of 20 ℃ by a roller coating mode, and then volatilizing and drying the bottom layer sol A in the air to form a gel bottom. The thickness of the gel bottom layer was observed to be around 50nm in the thin region and around 80nm in the thicker region. The length of the period of the film layer which is not uniformly distributed is about 0.1-1 mm.

Heating the super-white embossed photovoltaic glass sample wafer coated with the double-layer gel coating to 750 ℃ by a heating furnace for 2 minutes, and then cooling to room temperature. After heating, the refractive index of the single-layer antireflection coating layer on the surface of the sample is about 1.3, and the thickness of the coating layer is about 100 nm.

The obtained double-layer photovoltaic antireflection coated glass is observed under natural light, and the reflected light in the appearance is slightly bluish neutral color (the light reflection effect is shown in fig. 7). Meanwhile, the average transmittance of the glass sample with the single-side plated with the double-layer photovoltaic antireflection coating is increased by about 2.5 percent compared with that of the glass sample without the coating in the wavelength range of 400-1100 nm.

Comparative example 1

The method comprises the steps of plating a KhaprCoat T2 type coating solution of Dusmann, Netherlands on the surface of the ultra-white embossed photovoltaic glass at room temperature of 20 ℃ by a roller coating method to obtain an ultra-white embossed photovoltaic glass sample sheet with a single-layer gel coating on one side.

Heating the ultrawhite embossed photovoltaic glass sample coated with the common single-layer gel coating to 700 ℃ by a heating furnace for 2.5 minutes, and then cooling to room temperature to obtain the ultrawhite embossed photovoltaic glass sample coated with the common single-layer antireflection coating on one side. After heating, the refractive index of the single-layer antireflection coating layer on the surface of the sample is about 1.28, and the thickness of the coating layer is about 110 nm.

The obtained ultra-white embossed photovoltaic glass with a single-sided plated common single-layer antireflection coating is observed under natural light, reflected light in appearance is bright blue-purple, and the whole sample surface is accompanied with a certain roller painting color difference phenomenon (the reflection effect is shown in fig. 7). Meanwhile, the average transmittance of the glass sample with a single-sided common single-layer antireflection coating is increased by about 2.5 percent compared with that of the glass sample without the coating in the wavelength range of 400-1100 nm.

Comparative example 2

0.05mol of tetramethyl orthosilicate, 0.05mol of concentrated nitric acid and 0.25mol of water are sequentially added into 5mol of isopropanol, and the mixture is stirred for 1 hour at room temperature to form bottom layer sol A.

Coating the bottom layer sol A on the surface of the super-white embossed photovoltaic glass substrate with the thickness of 2.5mm at room temperature of 25 ℃ by a lifting coating mode, and then volatilizing and drying the bottom layer sol A in the air to form a gel bottom layer. The thickness of the gel bottom layer was observed to be about 60-70 nm. The thickness distribution of the film layer is more uniform.

Setting the temperature of an oven to be 150 ℃, heating the ultra-white embossed photovoltaic glass sample wafer plated with the uniformly distributed gel bottom layer for about 1 minute until the surface temperature of the sample reaches about 100 ℃, taking out the sample, and cooling to room temperature.

And plating an E1 type coating solution of Shanghai West Source New energy technology Limited onto the surface of the gel bottom layer of the ultra-white embossed photovoltaic glass sample at room temperature of 25 ℃ by a lifting coating method to obtain the ultra-white embossed photovoltaic glass sample wafer with double-layer gel coatings on two sides.

Heating the ultra-white embossed photovoltaic glass sample wafer with the double-layer gel coating plated on the two sides to 650 ℃ through a heating furnace for 3 minutes, and then cooling to room temperature. After heating, the refractive index of the single-layer antireflection coating layer on the surface of the sample is about 1.27, and the thickness of the film layer is about 120 nm.

The obtained double-layer photovoltaic antireflection coated glass is observed under natural light, and the appearance reflection is obviously dark blue (the reflection effect is shown in figure 7). Meanwhile, the average transmittance of the glass sample with the double-sided photovoltaic antireflection coating is increased by about 4.8 percent compared with that of the glass sample without the coating in the wavelength range of 400-1100 nm.

Compared with single-layer antireflection coated glass, a uniform gel bottom layer with the thickness of about 60-70nm changes the film surface reflection color observed by the double-layer photovoltaic antireflection coated glass under natural light, but the coated glass with the appearance reflection presenting neutral color cannot be obtained.

All documents mentioned in this application are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the appended claims.

Claims

1. A neutral color double-layer antireflection coating,

wherein the content of the first and second substances,

the bottom film layer is positioned on the inner side of the neutral double-layer antireflection coating, and the antireflection film layer is positioned on the outer side of the neutral double-layer antireflection coating;

and the outer side surface of the bottom film layer is an undulating surface.

2. The neutral-color double-layer antireflection coating of claim 1, wherein the undulating surface is a surface on which raised portions in the form of hills and recessed portions in the form of valleys around the raised portions in the form of hills are distributed.

3. The neutral-color double-layer antireflection coating of claim 2, wherein 1 x 10 is distributed per square meter of the surface of the undulating surface⁵～1×10⁷And a raised portion of said plateau.

4. The neutral-color double-layer antireflection coating of claim 2, wherein the raised portions have a length dimension of 0.1 to 2 mm.

5. The neutral-color double-layer antireflection coating of claim 1, wherein the thinnest portion of the underlying film layer has a thickness D_minThe thickness of the thickest part of the bottom film layer is D_max(ii) a And D_min＝0.3～0.625D_max。

6. The neutral-color double-layer antireflection coating of claim 1,

the thickness of the thinnest part of the bottom film layer is 30-50 nm; and/or

The thickness of the thickest part of the bottom film layer is 80-100 nm; and/or

The thickness of the antireflection film layer is 100-120 nm.

7. The neutral-color double-layered antireflection coating of claim 1, wherein the antireflection film layer is an antireflection film layer having a refractive index of 1.26 to 1.30.

8. A coated glass, comprising:

a glass substrate; and

the neutral-color double-layer antireflection coating of claim 1 provided on at least one surface of the glass substrate.

9. The coated glass according to claim 8, wherein the coated glass is a coated glass provided with the neutral-color double antireflection coating on one side;

and the coated glass comprises:

a glass substrate (1) having a first surface;

a first base film layer (21) disposed on the first surface; and

and, the first underlayer film layer is defined as the underlayer film layer described in claim 1, and the first antireflection film layer is defined as the antireflection film layer described in claim 1.

10. The coated glass according to claim 8, wherein the coated glass is a coated glass having both surfaces provided with the neutral-color double-layer antireflection coating;

and the coated glass comprises:

a glass substrate (1) having a first surface and a second surface;

a first base film layer (21) disposed on the first surface;

a second base film layer (22) disposed on the second surface; and

also, the first and second underlying film layers are defined as the underlying film layer described in claim 1, and the first and second antireflection film layers are defined as the antireflection film layer described in claim 1.