阅读说明：本技术 一种灰色基调的光阀及其应用 (Light valve with gray tone and application thereof ) 是由 赵世勇 李亚男 张达玮 肖淑勇 张昱喆 梁斌 于 2021-02-24 设计创作，主要内容包括：本发明提供了一种灰色基调的光阀,所述光阀暗态为灰色基调,亮态为透明。所述灰色基调为：在CIELab颜色坐标里,20＜L＜45,-0.5＜a＜1.5,-2.5＜b＜2.5。本发明提供了一种具有特定的灰色基调的光阀,其暗态为灰色,亮态为透明,是一种具有中间色调--灰色基调的光阀。本发明提高了对光阀的选择性,进一步拓宽了光阀应用的深度和宽度。(The invention provides a light valve with gray basic tone, wherein the dark state of the light valve is gray basic tone, and the bright state of the light valve is transparent. The grey tone is: in CIELab color coordinates, L is more than 20 and less than 45, a is more than 0.5 and less than 1.5, and b is more than 2.5 and less than 2.5. The present invention provides a light valve with specific gray tone, its dark state is gray, its bright state is transparent, and it is a light valve with intermediate tone-gray tone. The invention improves the selectivity of the light valve and further widens the depth and width of the light valve application.)

1. A light valve with gray tone is characterized in that the dark state of the light valve is gray tone, and the bright state of the light valve is transparent;

the grey tone is:

in CIELab color coordinates, L is more than 20 and less than 45, a is more than 0.5 and less than 1.5, and b is more than 2.5 and less than 2.5.

2. A light valve as claimed in claim 1, characterized in that the grey basic tones are in particular:

in CIELab color coordinates, L is more than 25 and less than 40, a is more than 0.2 and less than 1, and b is more than 1.5 and less than 1.5.

3. The light valve of claim 1, wherein the light valve is an electro-switchable light film that is energized to adjust dark and light states;

the manner of energizing includes alternating current.

4. A light valve of grey tone, comprising two transparent electrodes and a polymer matrix layer sandwiched between the electrodes;

a liquid suspension medium is dispersed in the polymer matrix layer;

the liquid suspension medium has dispersed therein solid particles.

5. A light valve as claimed in claim 4, wherein the solid particles comprise an inorganic-organic complex;

the solid particles comprise nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester, iodine, metal halide and modified cellulose according to raw materials;

the mass ratio of the iodine to the metal halide is (0.3-3): 1;

the mass ratio of the nitrogen-containing heterocyclic carboxylic acid or the nitrogen-containing heterocyclic carboxylic ester to the metal halide is (0.1-1): 1;

the mass ratio of the modified cellulose to the metal halide is (0.2-3): 1.

6. the light valve of claim 5, wherein the metal halide comprises lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, scandium chloride, titanium chloride, vanadium chloride, chromium chloride, manganese chloride, iron chloride, cobalt chloride, nickel chloride, ruthenium chloride, rhodium chloride, palladium chloride, osmium chloride, iridium chloride, platinum chloride, copper chloride, zinc chloride, cadmium chloride, aluminum chloride, gallium chloride, indium chloride, tin chloride, lead chloride, antimony chloride, bismuth chloride, rare earth chlorides; one or more of lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, strontium iodide, barium iodide, ferrous iodide, cobalt iodide, nickel iodide, copper iodide, zinc iodide, cadmium iodide, indium iodide, tin iodide, and lead iodide;

the modified cellulose comprises one or more of nitrocellulose, ethylcellulose, cellulose acetate and cellulose butyrate.

7. The light valve of claim 5, wherein the nitrogen-containing heterocyclic carboxylic acid or the nitrogen-containing heterocyclic carboxylic acid ester comprises one or more compounds represented by formulas (1) to (11);

wherein X is (COOH)_nOr (COOR)_nN is an integer of 1 to 3;

wherein X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

wherein X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

wherein X is (COOH)_nOr (COOR)_nN is an integer of 1 to 6;

r is C1-C6 alkyl;

8. the light valve of claim 4, wherein the solid particles have a particle length of 50 to 800 nm;

the aspect ratio between the particle length and the particle width of the solid particles is (2-30): 1;

the polymer matrix layer is formed by UV curing of organic silicone oil with unsaturated bonds;

the liquid suspension medium comprises a non-conductive liquid;

the liquid suspension medium comprises one or more of a mineral insulating material, a synthetic insulating material and a vegetable oil;

the transparent electrode comprises at least one of ITO conductive glass, an ITO/PET conductive film, a nano Ag wire/PET conductive film, a graphene conductive film and a nano Cu wire/PET conductive film.

9. A light valve as claimed in claim 8, wherein the synthetic insulating material comprises one or more of silicone oil, fluorocarbon organic compound, plasticizer, dodecylbenzene and polybutyleneoil;

the plasticizer comprises one or more of dioctyl phthalate, dibutyl phthalate, diisooctyl phthalate and triisodecyl trimellitate;

the liquid suspension medium is dispersed in the polymer matrix layer in the form of droplets;

the liquid suspension medium has a droplet size diameter of 1-10 μm;

the particle length of the solid particles is 200-500 nm;

the aspect ratio between the particle length and the particle width of the solid particles is (3-15): 1;

the thickness of the polymer matrix layer is 30-200 mu m;

the thickness of the transparent electrode is 100-300 μm.

10. Use of a light valve according to any of claims 1 to 3 or a light valve according to any of claims 4 to 9 in the field of smart windows, automotive mirrors, glasses or displays.

Technical Field

The invention belongs to the technical field of light valves, and relates to a light valve with gray tone and application thereof.

Background

A light valve is a device that can adjust the transmittance of light passing through itself, and is also called a light adjusting film, which is a smart film. Traditional membrane of adjusting luminance is direct with the film laminating on glass, makes the film of adjusting luminance present to pierce through and vaporific through voltage again, has realized that people pierce through and the dual requirement of protection privacy to glass, even when opaque, daylighting still fine, this is that all curtains can't realize at present to the heat energy of focusing has insulating reflection effect, makes indoor warm in winter and cool in summer, environmental protection and energy saving. The product utilizes the optical characteristics of liquid crystal to realize the photoelectric function of the film, and is widely applied in Europe, America and other countries at present.

Nowadays, light valves are more particularly devices capable of controlling the light transmittance by adjusting the voltage applied thereto, such devices also being referred to as electrochromic devices. Specifically, a light valve (hereinafter, abbreviated as LV) refers to a device that can control the transmittance of light passing through a medium by adjusting the level of Alternating Current (AC) voltage applied to the medium. The light valve has the advantages of active regulation of light transmittance and energy conservation, and can be used as intelligent windows of spacecrafts, high-speed rails, automobiles, buildings and the like, as well as rearview mirrors, sunglasses, displays and the like.

Although light valve devices containing nanoparticles were further invented over eighty years ago, and although suspended particle light modulating films have been developed for many years, the dark state of such films has been blue. In practical applications, some people do not like the cool tone, but prefer other intermediate tones, but in the prior art, the dark state of the suspended particle light valve is basically blue, which causes obstacles to further development, which not only limits the selection motivation of customers, but also limits the application of the light valve device containing nanoparticles in more technical fields.

Therefore, how to find another light valve with a primary color of dark state of the light valve, solve the above-mentioned problems of the current light valve application, and widen the depth and width of the application has become one of the focuses of the extensive attentions of many researchers with prospective ideas in this field.

Disclosure of Invention

In view of the above, the present invention provides a light valve with gray tone and its application. The light valve provided by the invention has the dark state of gray and the bright state of transparent, and is a light valve with a medium tone, namely a gray tone. The invention improves the selectivity of the light valve and further widens the depth and width of the light valve application.

The invention provides a light valve with gray basic tone, wherein the dark state of the light valve is the gray basic tone, and the bright state of the light valve is transparent;

the grey tone is:

in CIELab color coordinates, L is more than 20 and less than 45, a is more than 0.5 and less than 1.5, and b is more than 2.5 and less than 2.5.

Preferably, the grey tones are specifically:

in CIELab color coordinates, L is more than 25 and less than 40, a is more than 0.2 and less than 1, and b is more than 1.5 and less than 1.5.

Preferably, the light valve is an electro-dimming film which can adjust dark state and bright state when being electrified;

the manner of energizing includes alternating current.

The invention provides a light valve with gray tone, which comprises two transparent electrodes and a polymer matrix layer clamped between the electrodes;

a liquid suspension medium is dispersed in the polymer matrix layer;

the liquid suspension medium has dispersed therein solid particles.

Preferably, the solid particles comprise an inorganic-organic complex;

the solid particles comprise nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester, iodine, metal halide and modified cellulose according to raw materials;

the mass ratio of the iodine to the metal halide is (0.3-3): 1;

the mass ratio of the nitrogen-containing heterocyclic carboxylic acid or the nitrogen-containing heterocyclic carboxylic ester to the metal halide is (0.1-1): 1;

the mass ratio of the modified cellulose to the metal halide is (0.2-3): 1.

preferably, the metal halide includes lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, scandium chloride, titanium chloride, vanadium chloride, chromium chloride, manganese chloride, ferric chloride, cobalt chloride, nickel chloride, ruthenium chloride, rhodium chloride, palladium chloride, osmium chloride, iridium chloride, platinum chloride, copper chloride, zinc chloride, cadmium chloride, aluminum chloride, gallium chloride, indium chloride, tin chloride, lead chloride, antimony chloride, bismuth chloride, rare earth chloride; one or more of lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, strontium iodide, barium iodide, ferrous iodide, cobalt iodide, nickel iodide, copper iodide, zinc iodide, cadmium iodide, indium iodide, tin iodide, and lead iodide;

the modified cellulose comprises one or more of nitrocellulose, ethylcellulose, cellulose acetate and cellulose butyrate.

Preferably, the nitrogen-containing heterocyclic carboxylic acid or the nitrogen-containing heterocyclic carboxylic ester includes one or more compounds represented by formulas (1) to (11);

wherein X is (COOH)_nOr (COOR)_nN is an integer of 1 to 3;

wherein X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

wherein X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

wherein X is (COOH)_nOr (COOR)_nN is an integer of 1 to 6;

r is C1-C6 alkyl;

preferably, the particle length of the solid particles is 50-800 nm;

the aspect ratio between the particle length and the particle width of the solid particles is (2-30): 1;

the polymer matrix layer is formed by UV curing of organic silicone oil with unsaturated bonds;

the liquid suspension medium comprises a non-conductive liquid;

the liquid suspension medium comprises one or more of a mineral insulating material, a synthetic insulating material and a vegetable oil;

the transparent electrode comprises at least one of ITO conductive glass, an ITO/PET conductive film, a nano Ag wire/PET conductive film, a graphene conductive film and a nano Cu wire/PET conductive film.

Preferably, the synthetic insulating material comprises one or more of silicone oil, fluorocarbon organic compound, plasticizer, dodecylbenzene and polybutylece oil;

the plasticizer comprises one or more of dioctyl phthalate, dibutyl phthalate, diisooctyl phthalate and triisodecyl trimellitate;

the liquid suspension medium is dispersed in the polymer matrix layer in the form of droplets;

the liquid suspension medium has a droplet size diameter of 1-10 μm;

the particle length of the solid particles is 200-500 nm;

the aspect ratio between the particle length and the particle width of the solid particles is (3-15): 1;

the thickness of the polymer matrix layer is 30-200 mu m;

the thickness of the transparent electrode is 100-300 μm.

The invention also provides an application of the light valve in any one of the technical schemes or the light valve in any one of the technical schemes in the fields of intelligent windows, car mirrors, glasses or displays.

The invention provides a light valve with gray basic tone, wherein the dark state of the light valve is gray basic tone, and the bright state of the light valve is transparent. The grey tone is: in CIELab color coordinates, L is more than 20 and less than 45, a is more than 0.5 and less than 1.5, and b is more than 2.5 and less than 2.5. Compared with the prior art, the light valve device provided by the invention aims at the problem that the dark state of the existing light valve device containing nano suspended particles is blue. The present invention provides a light valve with specific gray tone, its dark state is gray, its bright state is transparent, and it is a light valve with intermediate tone-gray tone. The invention improves the selectivity of the light valve and further widens the depth and width of the light valve application.

The experimental result shows that the light valve manufactured by adopting the gray solid particles has the total light transmittance of 72.1 percent and the dark state of gray tone, wherein L is 32.88, a is 0.53 and b is-0.72, thereby overcoming the defect that the light valve in the prior art has the dark state of blue tone, obtaining better technical effect and having good application prospect.

Drawings

FIG. 1 is a schematic diagram of a light valve made in accordance with the present invention prior to power-on;

FIG. 2 is a schematic diagram of a light valve prepared according to the present invention after being energized;

FIG. 3 is an SEM image of gray solid particles made according to the present invention;

fig. 4 is a comparison of dark/bright transmission spectra for gray-based light valves made in accordance with the present invention.

Detailed Description

For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.

All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.

All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts electronic purity or purity requirements conventional in the light valve technical field.

The invention provides a light valve with gray basic tone, wherein the dark state of the light valve is gray basic tone, and the bright state of the light valve is transparent.

The grey tone is:

in CIELab color coordinates, L is more than 20 and less than 45, a is more than 0.5 and less than 1.5, and b is more than 2.5 and less than 2.5.

The definition and concept of the light valve are not particularly limited, and those skilled in the art can select and adjust the light valve according to the practical application, composite situation and product performance, and the light valve of the present invention preferably refers to an electrochromic device containing suspended nanoparticles, a light valve having a dark state and a bright state, and being capable of being adjusted by power-on. In particular, the light valve is preferably an electro-switchable film that is switched on to adjust the dark and light states.

The invention is not particularly limited in principle to the energizing manner, and a person skilled in the art can select and adjust the energizing manner according to the actual application condition, the quality requirement and the product performance.

The alternating current voltage is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, quality requirements and product performance, the light valve dark gray tone is better guaranteed, the light transmittance of the light valve bright state is improved, subsequent application is better facilitated, and the alternating current voltage is preferably 5-500V, more preferably 100-400V, and more preferably 200-300V. In the present invention, the voltage value of the alternating current preferably means a voltage effective value.

In the present invention, the light valve is gray-based in the dark state and transparent in the bright state.

The invention has no special limitation on the full light transmittance of the light valve in the bright state in principle, and a person skilled in the art can select and adjust the full light transmittance according to the actual application condition, the quality requirement and the product performance, in order to better ensure the gray tone of the light valve in the dark state, improve the light transmittance of the light valve in the bright state and better facilitate the subsequent application, the full light transmittance of the light valve in the bright state is preferably more than or equal to 50%.

The invention has no special limitation on the total light transmittance of the light valve in the dark state in principle, and a person skilled in the art can select and adjust the light valve according to the actual application condition, the quality requirement and the product performance, in order to better ensure the gray tone of the light valve in the dark state, improve the light transmittance of the light valve in the bright state and better facilitate the subsequent application, the total light transmittance of the light valve in the dark state is preferably less than or equal to 1%.

In the present invention, the light valve dark state is a gray primary tone.

The specific range of the gray tone is not particularly limited in principle, and a person skilled in the art can select and adjust the gray tone according to the actual application condition, the quality requirement and the product performance, so that the gray tone of the dark state of the light valve is better ensured, the light transmittance of the bright state of the light valve is improved, and the subsequent application is better facilitated, wherein the gray tone is as follows:

in CIELab color coordinates, L is more than 20 and less than 45, a is more than 0.5 and less than 1.5, and b is more than 2.5 and less than 2.5.

Preferably, 25 < L < 40, more preferably, 30 < L < 35. Specifically, L is more than 25 and less than 40.

Preferably, -0.3 < a < 1.3, more preferably, -0.1 < a < 1, more preferably, 0.2 < a < 0.7. Specifically, a is more than-0.2 and less than 1.

Preferably, -2 < b < 2, more preferably, -1.5 < b < 1.5, more preferably, -1 < b < 1. Specifically, b is more than-1.5 and less than 1.5.

The invention provides a light valve with gray tone, which comprises two transparent electrodes and a polymer matrix layer clamped between the electrodes;

a liquid suspension medium is dispersed in the polymer matrix layer;

the liquid suspension medium has dispersed therein solid particles.

In the present invention, the light valve includes two transparent electrodes.

The transparent electrode preferably comprises at least one of ITO conductive glass, an ITO/PET conductive film, a nano Ag wire/PET conductive film, a graphene conductive film and a nano Cu wire/PET conductive film, and more preferably comprises ITO conductive glass, an ITO/PET conductive film, a nano Ag wire/PET conductive film, a graphene conductive film and a nano Cu wire/PET conductive film.

The thickness of the transparent electrodes is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, quality requirements and product performance, the thickness of the transparent electrodes, namely the thicknesses of the two transparent electrodes, can be preferably 100-300 micrometers, more preferably 140-260 micrometers and more preferably 180-220 micrometers respectively, so that the gray tone of the dark state of the light valve can be better ensured, the light transmittance of the bright state of the light valve can be improved, and the subsequent application can be better facilitated.

In the present invention, the light valve includes a polymer matrix layer sandwiched between electrodes.

The thickness of the polymer matrix layer is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application condition, the quality requirement and the product performance, in order to better ensure the gray tone of the dark state of the light valve, improve the light transmittance of the light valve in the bright state and better facilitate the subsequent application, the thickness of the polymer matrix layer is preferably 30-200 μm, more preferably 70-160 μm, and more preferably 110-120 μm.

The invention has no special limitation on the selection of the polymer matrix layer in principle, and a person skilled in the art can select and adjust the polymer matrix layer according to the actual application condition, the quality requirement and the product performance.

In the present invention, a liquid suspension medium is dispersed in the polymer matrix layer of the light valve.

The invention has no special limitation on the shape of the liquid suspension medium in principle, and a person skilled in the art can select and adjust the shape according to the actual application condition, the quality requirement and the product performance. Specifically, the diameter of the liquid suspension medium is 1-10 μm, more preferably 3-8 μm, and still more preferably 5-6 μm.

The selection of the liquid suspension medium is not particularly limited in principle, and a person skilled in the art can select and adjust the liquid suspension medium according to the actual application condition, the quality requirement and the product performance. Specifically, one or more of a mineral insulating material, a synthetic insulating material, and a vegetable oil is more preferably included, and a mineral insulating material, a synthetic insulating material, or a vegetable oil is more preferably included.

The selection of the synthetic insulating material is not particularly limited in principle, and a person skilled in the art can select and adjust the synthetic insulating material according to the actual application condition, the quality requirement and the product performance, in order to better ensure the gray tone of the dark state of the light valve, improve the light transmittance of the light valve in the bright state and better facilitate the subsequent application, the synthetic insulating material preferably comprises one or more of organic silicon oil, fluorocarbon organic compounds, plasticizers, dodecylbenzene and polybutyleneoil, and more preferably comprises organic silicon oil, fluorocarbon organic compounds, plasticizers, dodecylbenzene or polybutyleneoil.

The selection of the plasticizer is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application condition, quality requirements and product performance, and the plasticizer preferably comprises one or more of dioctyl phthalate, dibutyl phthalate, diisooctyl phthalate and triisodecyl trimellitate, more preferably dioctyl phthalate, dibutyl phthalate, diisooctyl phthalate or triisodecyl trimellitate, so as to better ensure the gray tone of the dark state of the light valve, improve the light transmittance of the bright state of the light valve and better facilitate subsequent application.

In the present invention, the light valve includes a polymer matrix layer sandwiched between electrodes, and a liquid suspension medium dispersed in the polymer matrix layer, and solid particles dispersed in the liquid suspension medium.

The composition of the solid particles is not particularly limited in principle, and a person skilled in the art can select and adjust the solid particles according to the actual application condition, the quality requirement and the product performance.

More specifically, the solid particles preferably include nitrogen-containing heterocyclic carboxylic acid or ester, iodine, metal halide and modified cellulose in terms of raw materials.

In the invention, the mass ratio of the iodine to the metal halide is not particularly limited in principle, and a person skilled in the art can select and adjust the iodine to the metal halide according to the actual application condition, the quality requirement and the product performance, in order to better ensure the gray tone of the dark state of the light valve, improve the light transmittance of the bright state of the light valve and better facilitate the subsequent application, the mass ratio of the iodine to the metal halide is preferably (0.3-3): 1, more preferably (0.8 to 2.5): 1, more preferably (1.3 to 2.0): 1.

in the invention, the mass ratio of the nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester to the metal halide is not particularly limited in principle, and a person skilled in the art can select and adjust the nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester according to the actual application condition, the quality requirement and the product performance, in order to better ensure the gray tone of the dark state of the light valve, improve the light transmittance of the bright state of the light valve and better facilitate the subsequent application, the mass ratio of the nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester to the metal halide is preferably (0.1-1): 1, more preferably (0.3 to 0.8): 1, more preferably (0.5 to 0.6): 1.

the invention has no particular limitation on the specific selection of the nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester in principle, and a person skilled in the art can select and adjust the nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester according to the actual application condition, the quality requirement and the product performance, in order to better ensure the gray tone of the dark state of the light valve, improve the light transmittance of the bright state of the light valve and better facilitate the subsequent application, the nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester preferably comprises one or more compounds shown in formulas (1) to (11);

wherein X is (COOH)_nOr (COOR)_nN is preferably an integer of 1 to 3, and specifically may be 1, 2 or 3.

Wherein X is (COOH)_nOr (COOR)_nN is preferably an integer of 1 to 4, and specifically may be 1, 2, 3 or 4.

Wherein X is (COOH)_nOr (COOR)_nN is preferably an integer of 1 to 4, and specifically may be 1, 2, 3 or 4.

Wherein X is (COOH)_nOr (COOR)_nN is preferably an integer of 1 to 6, and may be 1, 2, 3, 4, 5 or 6.

In the present invention, in the formulae (1) to (4), R is preferably an alkyl group, more preferably an alkyl group having from C1 to C6, and may be an alkyl group having from C2 to C5 or an alkyl group having from C3 to C4.

The specific selection of the metal halide is not particularly limited in principle, and those skilled in the art can select and adjust the metal halide according to the actual application condition, quality requirements and product performance, and the metal halide preferably includes lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, scandium chloride, titanium chloride, vanadium chloride, chromium chloride, manganese chloride, ferric chloride, cobalt chloride, nickel chloride, ruthenium chloride, rhodium chloride, palladium chloride, osmium chloride, iridium chloride, platinum chloride, copper chloride, zinc chloride, cadmium chloride, aluminum chloride, gallium chloride, indium chloride, tin chloride, lead chloride, antimony chloride, bismuth chloride and rare earth chloride, so as to better ensure the gray tone of the dark state of the light valve, improve the light transmittance of the bright state of the light valve and better facilitate subsequent application; lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, strontium iodide, barium iodide, ferrous iodide, cobalt iodide, nickel iodide, copper iodide, zinc iodide, cadmium iodide, indium iodide, tin iodide, and lead iodide, more preferably one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, scandium chloride, titanium chloride, vanadium chloride, chromium chloride, manganese chloride, iron chloride, cobalt chloride, nickel chloride, ruthenium chloride, rhodium chloride, palladium chloride, osmium chloride, iridium chloride, platinum chloride, copper chloride, zinc chloride, cadmium chloride, aluminum chloride, gallium chloride, indium chloride, tin chloride, lead chloride, antimony chloride, bismuth chloride, rare earth chlorides; lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, strontium iodide, barium iodide, ferrous iodide, cobalt iodide, nickel iodide, copper iodide, zinc iodide, cadmium iodide, indium iodide, tin iodide, or lead iodide. Specifically, magnesium chloride, strontium chloride, barium chloride, scandium chloride, titanium chloride, vanadium chloride, chromium chloride, manganese chloride, ferric chloride, cobalt chloride, nickel chloride, ruthenium chloride, rhodium chloride, palladium chloride, osmium chloride, iridium chloride, platinum chloride, copper chloride, zinc chloride, cadmium chloride, aluminum chloride, gallium chloride, indium chloride, tin chloride, lead chloride, antimony chloride, and rare earth chloride; one or more of magnesium bromide, strontium bromide, barium bromide, magnesium iodide, strontium iodide, barium iodide, ferrous iodide, cobalt iodide, nickel iodide, copper iodide, zinc iodide, cadmium iodide, indium iodide, tin iodide, and lead iodide.

The selection of the modified cellulose is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application condition, quality requirements and product performance, and in order to better ensure the gray tone of the dark state of the light valve, improve the light transmittance of the light valve in the bright state and better facilitate subsequent application, the modified cellulose preferably comprises one or more of nitrocellulose, ethyl cellulose, cellulose acetate and cellulose butyrate, and more preferably nitrocellulose, ethyl cellulose, cellulose acetate or cellulose butyrate.

The length of the solid particles is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, quality requirements and product performance, the light valve light state gray tone is better guaranteed, the light transmittance of the light valve light state is improved, subsequent application is better facilitated, and the particle length of the solid particles is preferably 50-800 nm, more preferably 150-700 nm, more preferably 250-600 nm, more preferably 350-500 nm, and particularly can be 200-500 nm.

The invention has no special limitation on the width of the solid particles in principle, and a person skilled in the art can select and adjust the width according to the actual application condition, the quality requirement and the product performance, in order to better ensure the gray tone of the dark state of the light valve, improve the light transmittance of the bright state of the light valve and better facilitate the subsequent application, the aspect ratio between the particle length and the particle width of the solid particles is preferably (2-30): 1, more preferably (7-25): 1, more preferably (12-20): 1, specifically can be (3-15): 1.

the invention is a complete and detailed integral technical scheme, better ensures the gray tone of the dark state of the light valve, improves the light transmittance of the light valve in the bright state, and is better convenient for subsequent application, and also provides a method for synthesizing gray solid particles, which comprises the following steps:

wherein the component A is iodine, the component B is metal halide, the component C is nitrogen heterocyclic carboxylic acid or nitrogen heterocyclic carboxylic ester, the component D is modified cellulose, and the mass ratio of the components is A: b: c: d is 0.3-3: 1: 0.1-1: 0.2 to 3.

The method comprises the following steps of taking isoprene acetate as a solvent, taking low-carbon alcohol with the carbon atom number less than 8 and distilled water as a charge balancing agent, and feeding the components in a mass ratio of A: and B component: and C, component C: the component D is 0.3-3: 1: 0.1-1: 0.2-3, and the preparation method comprises the following specific steps:

a. adding D component modified cellulose, A component iodine, isoamyl acetate and B component metal halide in a corresponding mass component ratio into a glass flask, heating to 5-150 ℃, adding low-carbon alcohol, distilled water and C component nitrogen-containing heterocyclic carboxylic acid or nitrogen-containing heterocyclic carboxylic ester after iodine is dissolved, continuously heating and keeping the temperature, stirring for reaction for 0.1-20 hours, and then naturally cooling.

b. Centrifuging the reaction solution for 0.2-2 hours under the condition of not higher than 5000G to remove large-particle products, centrifuging the supernatant for 0.5-20 hours under the condition of not lower than 10000G, and discarding the supernatant to obtain light-operated particles, thereby obtaining gray solid particles.

The gray solid particles designed by the invention mainly comprise inorganic-organic complexes. Wherein the metal atom in the metal halide (component B) forms a chemical bond with the nitrogen atom in the nitrogen-containing heterocyclic carboxylic acid or ester (component C). Iodine (a component) also forms polyiodide complexes with the metal atoms in the metal halide (B component). The selected modified cellulose can inhibit the agglomeration of formed nano particles, control the production speed of different crystal faces and promote a certain crystal face to grow rapidly in priority to other crystal faces, so that a rodlike appearance is generated. The water and the low-carbon alcohol added in the preparation method balance the inorganic-organic complex in a hydrogen bond or coordination bond mode, play a role in balancing charges and the like, and enable the structure of the inorganic-organic complex to be more stable.

When an electric field is not applied (in an off state), the gray solid particles in the suspension are randomly dispersed due to brownian motion, and light beams entering the light valve are absorbed and/or scattered, so that the light valve has poor light transmittance and is relatively dark. When an electric field is applied (on state), the solid particles are polarized by the electric field, and the state of the solid particles is changed, so that the absorption/scattering and transmission of light are influenced, most of light can pass through the light valve, and the light valve has effectively enhanced light transmission and is relatively transparent.

Referring to fig. 1, fig. 1 is a schematic structural diagram of a light valve prepared according to the present invention before power is applied. Wherein 100 is a transparent electrode, 200 is a polymer matrix layer, 300 is a liquid suspension medium, and 400 is a solid particle.

Referring to fig. 2, fig. 2 is a schematic structural diagram of a light valve prepared according to the present invention after being powered on. Wherein 100 is a transparent electrode, 200 is a polymer matrix layer, 300 is a liquid suspension medium, and 400 is a solid particle.

When no electric field is applied (in an off state), the particles 400 in the liquid suspension medium 300 are randomly dispersed due to brownian motion, and light beams entering the light valve are absorbed and/or scattered, so that the light valve has poor light transmittance and is relatively dark. The structure is shown in fig. 1. When an electric field is applied (on state), the particles 400 are polarized by the electric field and are thus aligned in a direction in which the electric field is parallel to each other, so that most of the light can pass through the light valve, which has an effectively enhanced light transmittance and is relatively transparent, as shown in fig. 2.

The invention also provides an application of the light valve in any one of the technical schemes or the light valve in any one of the technical schemes in the fields of intelligent windows, car mirrors, glasses or displays.

The above steps of the present invention provide a light valve with a gray tone, which is a light valve with a specific gray tone, wherein the dark state is gray, the bright state is transparent, and the light valve has a middle tone-gray tone. The invention improves the selectivity of the light valve and further widens the depth and width of the light valve application.

The experimental result shows that the light valve manufactured by adopting the gray solid particles has the total light transmittance of 72.1 percent and the dark state of gray tone, wherein L is 32.88, a is 0.53 and b is-0.72, thereby overcoming the defect that the light valve in the prior art has the dark state of blue tone, obtaining better technical effect and having good application prospect.

For further illustration of the present invention, the gray tone light valve and its application will be described in detail with reference to the following embodiments, but it should be understood that these embodiments are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following embodiments.

[ example 1 ]

Preparation of Gray solid particles

Iodine (component A), metal halide (component B), nitrogen-containing heterocyclic carboxylic acid or ester (component C) and modified cellulose (component D);

the feeding mass ratio of each component is component A: and B component: and C, component C: the component D is 1.5: 1.0: 1.0: 1.6.

into a 250 ml three neck round bottom glass flask was added 30 g of isoamyl acetate solution containing 21.2 wt% nitrocellulose (1/4sec SS), 6 g of I₂70 g of isoamyl acetate, 3.9 g of anhydrous PbI₂And heated to 42 ℃. Etc. I₂After dissolution, 6 grams of n-propanol, 0.8 grams of distilled water and 4 grams of 2, 5-pyrazinedicarboxylic acid dihydrate were added to a three-necked round bottom glass flask. The reaction was stirred with heating at 42 ℃ for 4 hours and then allowed to cool naturally.

The reaction solution was centrifuged at 1350G for 0.5 hours to remove large particle product. Centrifuging the supernatant at 18000G for 5 hours, discarding the supernatant to obtain light-operated particles, namely gray solid particles, and fully dispersing the gray solid particles by using 250 ml of isoamyl acetate.

The grey solid particles prepared in example 1 of the invention were characterized.

Referring to fig. 3, fig. 3 is an SEM image of gray solid particles prepared according to the present invention.

SEM characterization results showed that the gray solid particles had a particle length of 338nm, a particle width of 62nm, and a particle aspect ratio of 5.5.

40 g of TDTM (tridecyl trimellitate) were placed in a 250 ml round-bottomed glass flask and the dispersion of isoamyl acetate of the gray solid particles prepared above was added in portions, the isoamyl acetate was removed by means of a rotary evaporator and finally the treatment was continued at 80 ℃ for 3 hours using a rotary evaporator. The resulting suspension of grey solid particles was designated LCP-1.

[ example 2 ]

Preparation of black solid particles

Following the procedure as in [ example 1 ] except that 5.0 g of the anhydrous CdI₂Instead of 3.9 g of anhydrous PbI₂The mixture is heated and stirred for reaction for 2 hours at 46 ℃, and the feeding mass ratio of the components is 1.5: 1.25: 1.0: 1.57.

SEM characterization results show that the black solid particles have a particle length of 365nm, a particle width of 68nm and a particle aspect ratio of 5.4. The resulting suspension of black solid particles is referred to as LCP-2.

[ example 3 ]

Preparation of Gray solid particles

According to the method of [ example 1 ], 6 g of isopropanol is used instead of 6 g of n-propanol, and the mixture is heated and stirred at 50 ℃ for reaction for 3 hours, wherein the feeding mass ratio of the components is that of the component A: and B component: and C, component C: the component D is 1.5: 0.975: 1.0: 1.57.

SEM characterization results showed that the gray solid particles had a particle length of 303nm, a particle width of 52nm, and a particle aspect ratio of 5.8. The resulting suspension of grey solid particles (called LCP-3).

[ example 4 ]

Preparation of Gray solid particles

Following the procedure as in [ example 1 ] except that 4.6 g of anhydrous SrI₂Instead of 3.9 g of anhydrous PbI₂Heating and stirring at 42 ℃ for reaction for 1 hour, wherein the feeding mass ratio of the components is component A: and B component: and C, component C: the component D is 1.5: 1.15: 1.0: 1.57.

SEM characterization results showed that the gray solid particles had a particle length of 289nm, a particle width of 40nm, and a particle aspect ratio of 7.2. The resulting suspension of grey solid particles (called LCP-4).

[ example 5 ]

Preparation of Gray solid particles

The procedure was followed as in example 1 except that 3, 6-dimethyl-2, 5-pyrazinedicarboxylic acid dihydrate was used in place of 2, 5-pyrazinedicarboxylic acid dihydrate.

SEM characterization results showed that the grey solid particles had a particle length of 448nm, a particle width of 71nm and a particle aspect ratio of 6.3. A suspension of grey solid particles (called LCP-5) was obtained.

[ example 6 ]

Preparation of dark grey solid particles

Following the procedure of [ example 1 ] except that 4.2 g of anhydrous CoI₂Instead of 3.9 g of anhydrous PbI₂。

SEM characterization results showed that the dark gray solid particles had a particle length of 431nm, a particle width of 75nm, and a particle aspect ratio of 5.7. A suspension of dark grey solid particles (designated LCP-6) was obtained.

[ example 7 ]

Preparation of blue-gray solid particles

Following the procedure as in [ example 1 ] except that 4 g of anhydrous BaBr₂Instead of 3.9 g of anhydrous PbI₂。

SEM characterization results showed that the blue-gray solid particles had a particle length of 388nm, a particle width of 66nm, and a particle aspect ratio of 5.9. The resulting suspension of blue-grey solid particles (designated LCP-7).

[ example 8 ]

Preparation of solid particles of grey black

Following the procedure as in [ example 1 ] except that 2.4 g of anhydrous PdCl were added₂Instead of 3.9 g of anhydrous PbI₂。

SEM characterization results showed that the gray black solid particles had a particle length of 439nm, a particle width of 68nm, and a particle aspect ratio of 6.5. The resulting suspension of grey-black solid particles (called LCP-8).

[ example 9 ]

Fabrication of LV-1 light valves from LCP-1

0.03 g of a photoinitiator 819, 3.0 g of solid particle suspension LCP-1 and 7.0 g of silicone oil having an unsaturated bond were uniformly mixed to obtain a matrix emulsion for a light control layer.

The above-prepared optical control layer substrate emulsion was coated on a PET/ITO transparent electrode with a thickness of 60 μm using a doctor blade type automatic film coater (MSK-AFA-III, MTI Corporation), and another PET/ITO transparent electrode was coated on the optical control layer wet film to obtain a wet film containing an optical control layer. Curing the mixture for 1 minute in an X200-150 UV curing machine manufactured by Aventk company with a UV power of 700W/m under a nitrogen atmosphere²Thus obtaining the LV-1 light valve.

Referring to fig. 4, fig. 4 is a comparison of dark/bright transmission spectra for gray-based light valves made in accordance with the present invention.

As can be seen from fig. 4, when no voltage is applied (off state), LV-1 shows a gray tone and the total light transmittance is 0.9%, there is no significant absorption peak, and the light valve is gray-toned. When 50 Hz 110V AC was applied (on state), LV-1 became clear and the total light transmission was 65.8%.

Specific results are shown in table 1.

[ example 10 ]

Fabrication of LV-2 light valves from LCP-2

Manufactured and tested as per [ example 9 ] except that LCP-2 was used instead of LCP-1, designated as LV-2, with specific results as shown in table 1.

[ example 11 ]

Fabrication of LV-3 light valves from LCP-3

Manufactured and tested as per [ example 9 ] except that LCP-3 was used instead of LCP-1, designated as LV-3, with specific results as shown in table 1.

[ example 12 ]

Fabrication of LV-4 light valves from LCP-4

Manufactured and tested as per [ example 9 ] except that LCP-4 was used instead of LCP-1, designated as LV-4, with specific results as shown in table 1.

[ example 13 ]

Fabrication of LV-5 light valves from LCP-5

Manufactured and tested as per [ example 9 ] except that LCP-5 was used instead of LCP-1, designated as LV-5, with specific results as shown in table 1.

[ example 14 ]

Fabrication of LV-6 light valves from LCP-6

Manufactured and tested as per [ example 9 ] except that LCP-6 was used instead of LCP-1, designated as LV-6, with specific results as shown in table 1.

[ example 15 ]

Fabrication of LV-7 light valves from LCP-7

Manufactured and tested as per [ example 9 ] except that LCP-7 was used instead of LCP-1, designated as LV-7, with specific results as shown in table 1.

[ example 16 ]

Fabrication of LV-8 light valves from LCP-8

Manufactured and tested as per [ example 9 ] except that LCP-8 was used instead of LCP-1, designated as LV-8, with specific results as shown in table 1.

Table 1 shows performance data of the light valves prepared in the examples of the present invention.

TABLE 1

From example 9 to example 16, it can be seen that the grey solid particle light valve has good light control properties.

The test shows that the total light transmittance of the gray light valve of the invention reaches 72.1%, in the CIELab color coordinate, L is 32.88, a is 0.53, and b is-0.72, thus effectively overcoming the defect that the light valve in the prior art has a dark state of blue tone.

In conclusion, the gray solid particles are obtained by using different metal halides or different reaction conditions, the total light transmittance of the light valve manufactured by the gray solid particles reaches 72.1 percent, the defect that the dark state of the light valve is blue tone in the prior art is overcome, a better technical effect is obtained, and the light valve has a good application prospect and has important significance.

The gray tone light valve and its applications provided by the present invention are described in detail above, and the principles and embodiments of the present invention are described herein using specific examples, which are provided only to help understand the method and its core ideas of the present invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combined methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.