阅读说明：本技术 光阀装置、光控粒子及其制备方法 (Light valve device, light-controlled particles and preparation method thereof ) 是由 赵世勇 李亚男 张达玮 肖淑勇 张昱喆 梁斌 于 2021-09-08 设计创作，主要内容包括：本发明提供了一种光阀装置,与现有技术相比,本发明提供的光阀装置采用的固体控光粒子的主体为无机-有机配合物,其为非蓝色固体颗粒,在没有施加电场(关闭状态)时,悬浮介质液滴内的固体控光粒子由于布朗运动而呈现随机分散,此时进入光阀的光束被吸收和/或散射,光阀透光性差,相对较暗,且暗态为非蓝色基调；当施加电场时(开启状态),固体控光粒子被电场极化,其形貌和状态发生改变,从而影响光阀对光的吸收/散射和透过,使大部分光可以穿过光阀,光阀透光性增强,相对明亮,实现了光阀装置暗态基色的调制。(The invention has provided a light valve device, compared with prior art, the body of the solid light-controlling particle that the light valve device that the invention provides uses is inorganic-organic complex, it is non-blue solid particle, when not exerting the electric field (closed state), the solid light-controlling particle in the suspension medium liquid drop presents the random dispersion because of brownian's movement, the light beam entering the light valve at this moment is absorbed and/or scattered, the light valve light transmissivity is bad, relatively darker, and the dark state is non-blue basic tone; when an electric field is applied (in an opening state), the solid light-controlling particles are polarized by the electric field, and the shapes and the states of the solid light-controlling particles are changed, so that the absorption/scattering and transmission of the light valve to light are influenced, most of the light can pass through the light valve, the light transmittance of the light valve is enhanced, the light valve is relatively bright, and the modulation of the dark primary color of the light valve device is realized.)

1. A light valve device, comprising:

a first transparent substrate having a first refractive index,

a first transparent electrode formed on the first transparent substrate,

a second transparent substrate, which is transparent to light,

a second transparent electrode formed on a second transparent substrate, the first transparent electrode and the second transparent electrode being disposed opposite to each other, an

A light control layer disposed between the first transparent electrode and the second transparent electrode; the light management layer includes a polymer matrix;

wherein the polymer matrix is dispersed with suspension medium droplets, and solid light-controlling particles are distributed in the suspension medium droplets;

the solid light-controlling particles are formed from raw materials comprising: iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrogen-containing organic ligand and nitrocellulose;

the light valve device is in a dark state with non-blue basic tone, and in a bright state with transparency;

the non-blue key is as follows: in CIELab color coordinates, L is more than 10 and less than 40, a is more than-5 and less than 5, and b is more than-1.5 and less than 5.

2. A light valve device according to claim 1, wherein the mass ratio of iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrogen-containing organic ligand and nitrocellulose is 1: (0.2-1): (0.05-1): (0.2-2): (0.01-3).

3. A light valve device as claimed in claim 1, characterized in that the main group metal iodide is selected from one or more of lithium iodide, sodium iodide, potassium iodide, rubidium iodide, caesium iodide, ammonium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, indium iodide, tin iodide and lead iodide;

the transition metal organic complex and/or rare earth metal organic complex is selected from titanium (III) acetylacetonate, titanium (IV) acetylacetonate, vanadium acetylacetonate, chromium (III) acetylacetonate, manganese (II) acetylacetonate, iron (III) acetylacetonate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, nickel (II) acetylacetonate, copper (II) acetylacetonate, zirconium (III) acetylacetonate, molybdenum (Mo) acetylacetonate, ruthenium (II) acetylacetonate, rhodium (II) acetylacetonate, palladium (II) acetylacetonate, iridium (III) acetylacetonate, yttrium (Y) acetylacetonate, lanthanum (Ce) acetylacetonate, europium (I) acetylacetonate, dysprosium (Dy) acetylacetonate, ferrocene, cobaltocene, nickelocene, manganese (cyclopentadienyl), titanocene, chromium (cyclopentadienyl), copper (cyclopentadienyl), ruthenium (cyclopentadienyl), vanadium (cyclopentadienyl), zirconium (cyclopentadienyl), lanthanum (cyclopentadienyl), copper (phthalocyanine), nickel (phthalocyanine), zinc (phthalocyanine), cobalt (phthalocyanine), iron (phthalocyanine), vanadium (phthalocyanine), manganese (B) (B) and B) (B) and B) (B) and (B) and B) (B) and (B) C (B) and (B) and, One or more of manganese phthalocyanine, chromium phthalocyanine, ruthenium phthalocyanine, zirconium phthalocyanine, lanthanum phthalocyanine, copper porphyrin, cobalt porphyrin, nickel porphyrin, iron porphyrin, vanadium porphyrin, ruthenium porphyrin, zirconium porphyrin and lanthanum porphyrin;

the nitrogen-containing organic ligand is selected from a nitrogen-containing heterocyclic carboxylic acid ligand and/or a nitrogen-containing heterocyclic carboxylic ester ligand.

4. The light valve device according to claim 1, wherein the nitrogen-containing organic ligand is selected from one or more compounds represented by formula (1) to formula (16):

in the formula (1), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

in the formula (2), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 3;

in the formula (3), X is (COOH)_nOr (COOR)_nN is an integer of 1-2;

in the formula (4), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 5;

in the formula (5), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

in the formula (6), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

in the formula (9), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 7;

in the formula (10), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 7;

in the formula (11), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 6;

wherein R in the formulae (1) to (6) and (9) to (11) is independently selected from C1-C6 alkyl.

5. The light valve device according to claim 1, wherein the solid light-controlling particles have a particle length of 50 to 800 nm; the particle aspect ratio of the solid light-controlling particles is 2-30.

6. A light valve device according to claim 1, wherein said polymer matrix is cross-linked and cured from a silicone oil polymer matrix precursor having unsaturated bonds;

the suspension medium liquid drop is non-conductive liquid and comprises at least one of fluorocarbon organic compounds, phthalic acid esters, trimellitic acid esters, dodecyl benzene, polybutylece oil, polyacrylate, polymethacrylate, epoxidized soybean oil and epoxidized linseed oil.

7. The light valve device of claim 1, wherein the first and second transparent substrates comprise glass plates; or

The first and second transparent substrates comprise transparent plastic sheets;

the first transparent electrode comprises at least one of ITO, FZO, IZO, GZO, AZO, nano Ag wires, conductive graphene, a PEDOT conductive layer and nano Cu wires; the second transparent electrode comprises at least one of ITO, FZO, IZO, GZO, AZO, nano Ag wires, conductive graphene, a PEDOT conductive layer and nano Cu wires.

8. A light valve device according to claim 1, wherein an insulating layer is provided on the first transparent electrode and/or the second transparent electrode.

9. A method of making a light valve device as claimed in claim 1, comprising

Providing solid light-controlling particles;

providing a suspension medium;

mixing the solid light-controlling particles with the suspension medium to form a mixture of suspension medium containing solid light-controlling particles;

providing a polymer matrix precursor;

mixing an initiator for initiating crosslinking and curing of the polymer matrix precursor, the mixture of the suspension medium containing the solid light-controlling particles and the polymer matrix precursor to obtain a light-controlling layer matrix emulsion;

coating the matrix emulsion of the light control layer on a first transparent electrode of a first transparent substrate to form a wet film of the light control layer;

covering a second transparent electrode on a second transparent substrate on the wet film of the light control layer; and

and crosslinking and curing the wet film of the light control layer to obtain the light valve device.

10. A solid light-controlling particle formed from a feedstock comprising: iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrogen-containing organic ligand and nitrocellulose.

11. A method for preparing solid light-controlling particles, comprising:

s1) mixing iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrocellulose and an organic solvent, then adding low carbon alcohol, distilled water and a nitrogen-containing organic ligand, and stirring for reaction to obtain a reaction solution;

s2) centrifuging the reaction solution under the condition that the concentration is not higher than 5000g to obtain a supernatant;

s3) centrifuging the supernatant under the condition that the weight of the supernatant is not less than 10000g to obtain the solid light-controlling particles.

12. The method of claim 11, wherein the organic solvent is selected from isoamyl acetate;

the number of carbon atoms of the lower alcohol is less than 8;

the mixing temperature is 5-150 ℃;

the temperature of the stirring reaction is 5-150 ℃; the stirring reaction time is 0.1-20 h;

the centrifugation time in the step S2) is 0.2-2 h;

the centrifugation time in the step S3) is 0.5-20 h.

13. A privacy glass assembly comprising a first glass plate and a second glass plate, the light valve device of claim 1 disposed between the first glass plate and the second glass plate; the first transparent substrate and the second transparent substrate are transparent plastic sheets;

a first adhesive layer is arranged between the first glass plate and the light valve device, and/or

And a second adhesive layer is arranged between the second glass plate and the light valve device.

Technical Field

The invention belongs to the technical field of light valves, and particularly relates to a non-blue basic tone light valve device, light-operated particles and a preparation method thereof.

Background

The light valve is a device that can adjust the transmittance of light passing through itself, and particularly, in the present invention, the light valve refers to a device that can control the transmittance of light by adjusting a voltage applied thereto, which is also called an electrochromic device. 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 the device can be used as an intelligent window, a vehicle rearview mirror, a sunglass, a display and the like of a spacecraft, a high-speed rail, an automobile, a building and the like.

Light valves include those with plastic sheets, such as PET, as the substrate, herein we refer to the light modulating film, and those with glass as the substrate, herein we refer to the light modulating glass, depending on the substrate of the light valve. The light adjusting film is laminated and is called a light adjusting glass assembly.

Eighty-seven years ago, light valve devices containing nanoparticles were invented. Although suspended particle light modulating films have been developed for many years, the dark state of such light modulating films is blue. In practice, people do not like this cool tone much, but rather prefer non-blue colors such as the intermediate tone gray.

It can be seen that in the prior art, the suspended particle light valve is blue in dark state, and the monotonous cold tone cannot meet the requirements of people for various colors. Therefore, there is a need to invent a technique for better modulating the primary color of the dark state of a light valve.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a light valve device with non-blue color tone, light control particles and a method for preparing the same.

The present invention provides a light valve device comprising:

a first transparent substrate having a first refractive index,

a first transparent electrode formed on the first transparent substrate,

a second transparent substrate, which is transparent to light,

a second transparent electrode formed on a second transparent substrate, the first transparent electrode and the second transparent electrode being disposed opposite to each other, an

A light control layer disposed between the first transparent electrode and the second transparent electrode; the light management layer includes a polymer matrix;

wherein the polymer matrix is dispersed with suspension medium droplets, and solid light-controlling particles are distributed in the suspension medium droplets;

the solid light-controlling particles are formed from raw materials comprising: iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrogen-containing organic ligand and nitrocellulose;

the light valve device is in a dark state with non-blue basic tone, and in a bright state with transparency;

the non-blue key is as follows: in CIELab color coordinates, L is more than 10 and less than 40, a is more than-5 and less than 5, and b is more than-1.5 and less than 5.

Preferably, the mass ratio of the iodine, the main group metal iodide, the transition metal organic complex and/or the rare earth metal organic complex, the nitrogen-containing organic ligand and the nitrocellulose is 1: (0.2-1): (0.05-1): (0.2-2): (0.01-3).

Preferably, the main group metal iodide is selected from one or more of lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, ammonium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, indium iodide, tin iodide and lead iodide;

the transition metal organic complex and/or rare earth metal organic complex is selected from titanium (III) acetylacetonate, titanium (IV) acetylacetonate, vanadium acetylacetonate, chromium (III) acetylacetonate, manganese (II) acetylacetonate, iron (III) acetylacetonate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, nickel (II) acetylacetonate, copper (II) acetylacetonate, zirconium (III) acetylacetonate, molybdenum (Mo) acetylacetonate, ruthenium (II) acetylacetonate, rhodium (II) acetylacetonate, palladium (II) acetylacetonate, iridium (III) acetylacetonate, yttrium (Y) acetylacetonate, lanthanum (Ce) acetylacetonate, europium (I) acetylacetonate, dysprosium (Dy) acetylacetonate, ferrocene, cobaltocene, nickelocene, manganese (cyclopentadienyl), titanocene, chromium (cyclopentadienyl), copper (cyclopentadienyl), ruthenium (cyclopentadienyl), vanadium (cyclopentadienyl), zirconium (cyclopentadienyl), lanthanum (cyclopentadienyl), copper (phthalocyanine), nickel (phthalocyanine), zinc (phthalocyanine), cobalt (phthalocyanine), iron (phthalocyanine), vanadium (phthalocyanine), manganese (B) (B) and B) (B) and B) (B) and (B) and B) (B) and (B) C (B) and (B) and, One or more of manganese phthalocyanine, chromium phthalocyanine, ruthenium phthalocyanine, zirconium phthalocyanine, lanthanum phthalocyanine, copper porphyrin, cobalt porphyrin, nickel porphyrin, iron porphyrin, vanadium porphyrin, ruthenium porphyrin, zirconium porphyrin and lanthanum porphyrin;

the nitrogen-containing organic ligand is selected from a nitrogen-containing heterocyclic carboxylic acid ligand and/or a nitrogen-containing heterocyclic carboxylic ester ligand.

Preferably, the nitrogen-containing organic ligand is selected from one or more compounds represented by formula (1) to formula (16):

in the formula (1), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

in the formula (2), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 3;

in the formula (3), X is (COOH)_nOr (COOR)_nN is an integer of 1-2;

in the formula (4), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 5;

in the formula (5), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

in the formula (6), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

in the formula (9), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 7;

in the formula (10), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 7;

in the formula (11), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 6;

wherein R in the formulae (1) to (6) and (9) to (11) is independently selected from C1-C6 alkyl.

Preferably, the particle length of the solid light-controlling particles is 50-800 nm; the particle aspect ratio of the solid light-controlling particles is 2-30.

Preferably, the polymer matrix is formed by crosslinking and curing a silicone oil polymer matrix precursor with an unsaturated bond;

the suspension medium liquid drop is non-conductive liquid and comprises at least one of fluorocarbon organic compounds, phthalic acid esters, trimellitic acid esters, dodecyl benzene, polybutylece oil, polyacrylate, polymethacrylate, epoxidized soybean oil and epoxidized linseed oil.

Preferably, the first and second transparent substrates comprise glass plates; or

The first and second transparent substrates comprise transparent plastic sheets.

Preferably, the first transparent electrode includes at least one of ITO, FZO, IZO, GZO, AZO, nano Ag wire, conductive graphene, and nano Cu wire; the second transparent electrode comprises at least one of ITO, FZO, IZO, GZO, AZO, nano Ag wires, conductive graphene, a PEDOT conductive layer and nano Cu wires.

Preferably, an insulating layer is disposed on the first transparent electrode and/or the second transparent electrode.

The invention also provides a preparation method of the light valve device, which comprises the steps of

Providing solid light-controlling particles;

providing a suspension medium;

mixing the solid light-controlling particles with the suspension medium to form a mixture of suspension medium containing solid light-controlling particles;

providing a polymer matrix precursor;

mixing an initiator for initiating crosslinking and curing of the polymer matrix precursor, the mixture of the suspension medium containing the solid light-controlling particles and the polymer matrix precursor to obtain a light-controlling layer matrix emulsion;

coating the matrix emulsion of the light control layer on a first transparent electrode of a first transparent substrate to form a wet film of the light control layer;

covering a second transparent electrode on a second transparent substrate on the wet film of the light control layer;

and crosslinking and curing the wet film of the light control layer to obtain the light valve device.

The present invention also provides a solid light-controlling particle formed from raw materials comprising: iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrogen-containing organic ligand and nitrocellulose.

The invention also provides a preparation method of the solid light-controlling particle, which comprises the following steps:

s1) mixing iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrocellulose and an organic solvent, then adding low carbon alcohol, distilled water and a nitrogen-containing organic ligand, and stirring for reaction to obtain a reaction solution;

s2) centrifuging the reaction solution under the condition that the concentration is not higher than 5000g to obtain a supernatant;

s3) centrifuging the supernatant under the condition that the weight of the supernatant is not less than 10000g to obtain the solid light-controlling particles.

Preferably, the organic solvent is selected from isoamyl acetate;

the number of carbon atoms of the lower alcohol is less than 8;

the mixing temperature is 5-150 ℃;

the temperature of the stirring reaction is 5-150 ℃; the stirring reaction time is 0.1-20 h;

the centrifugation time in the step S2) is 0.2-2 h;

the centrifugation time in the step S3) is 0.5-20 h.

The invention also provides a light modulation glass component, which comprises a first glass plate, a second glass plate and the light valve device, wherein the light valve device is arranged between the first glass plate and the second glass plate; the first transparent substrate and the second transparent substrate are transparent plastic sheets;

a first adhesive layer is arranged between the first glass plate and the light valve device, and/or

And a second adhesive layer is arranged between the second glass plate and the light valve device.

The invention provides a light valve device, which comprises a first transparent substrate, a first transparent electrode formed on the first transparent substrate, a second transparent electrode formed on the second transparent substrate, a light control layer arranged between the first transparent electrode and the second transparent electrode, and a first electrode layer and a second electrode layer which are arranged on the first transparent substrate; the light management layer includes a polymer matrix; wherein the polymer matrix is dispersed with suspension medium droplets, and solid light-controlling particles are distributed in the suspension medium droplets; the solid light-controlling particles are formed from raw materials comprising: iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrogen-containing organic ligand and nitrocellulose. Compared with the prior art, the main body of the solid light-controlling particles adopted by the light valve device provided by the invention is an inorganic-organic complex which is non-blue solid particles, when an electric field is not applied (in an off state), the solid light-controlling particles in the suspension medium liquid drop are randomly dispersed due to Brownian motion, at the moment, light beams entering the light valve are absorbed and/or scattered, the light valve has poor light transmission and is relatively darker, and the dark state is non-blue tone; when an electric field is applied (in an opening state), the solid light-controlling particles are polarized by the electric field, and the shapes and the states of the solid light-controlling particles are changed, so that the absorption/scattering and transmission of the light valve to light are influenced, most of the light can pass through the light valve, the light transmittance of the light valve is enhanced, the light valve is relatively bright, and the modulation of the dark primary color of the light valve device is realized.

Tests show that the light valve device made of the solid light-controlling particles has the total light transmittance of 69.1 percent, the dark state is a non-blue basic tone, L is 33.72, a is 0.15, and b is-0.81, so that the single defect that the light valve is blue basic tone in the dark state in the prior art is overcome, a better technical effect is obtained, and the light valve device has a good application prospect.

Drawings

FIG. 1a is a schematic structural diagram of a light valve device according to the present invention before power is applied;

FIG. 1b is a schematic diagram of a light valve device according to the present invention after power is applied;

FIG. 2 is a scanning electron micrograph of gray solid particles obtained in example 2 of the present invention;

FIG. 3 is a graph of the contrast of the dark state transmission spectra of the light valves obtained in comparative example 3, example 7 and example 8 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a solid light-controlling particle, which is formed by raw materials comprising the following components: iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrogen-containing organic ligand and nitrocellulose.

Wherein the mass ratio of the iodine, the main group metal iodide, the transition metal organic complex and/or the rare earth metal organic complex, the nitrogen-containing organic ligand and the nitrocellulose is preferably 1: (0.2-1): (0.05-1): (0.2-2): (0.01 to 3), more preferably 1: (0.2-1): (0.1-1): (0.2-1.5): (0.05-3), and preferably 1: (0.5-1): (0.1-1): (0.2-1): (0.2-3).

The main group metal iodide is preferably one or more of lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, ammonium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, indium iodide, tin iodide and lead iodide.

The organic complex of transition metal and/or organic complex of rare earth metal is preferably one or more of organic complexes of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, iridium, yttrium, lanthanum, cerium, europium and dysprosium, more preferably titanium (III) acetylacetonate, titanium (IV) acetylacetonate, vanadium acetylacetonate, chromium acetylacetonate, manganese (II) acetylacetonate, manganese (III) acetylacetonate, iron (II) acetylacetonate, iron (III) acetylacetonate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, nickel acetylacetonate, copper acetylacetonate, zirconium acetylacetonate, molybdenum acetylacetonate, ruthenium acetylacetonate, rhodium acetylacetonate, palladium acetylacetonate, iridium acetylacetonate, yttrium acetylacetonate, cerium acetylacetonate, europium acetylacetonate, dysprosium acetylacetonate, ferrocene, cobaltocene, nickelocene, Manganese diocene, titanium diocene, chromium diocene, copper diocene, ruthenium diocene, vanadium diocene, zirconium diocene, lanthanum diocene, copper phthalocyanine, nickel phthalocyanine, zinc phthalocyanine, cobalt phthalocyanine, iron phthalocyanine, vanadium phthalocyanine, manganese phthalocyanine, chromium phthalocyanine, ruthenium phthalocyanine, zirconium phthalocyanine, lanthanum phthalocyanine, copper porphyrin, cobalt porphyrin, nickel porphyrin, iron porphyrin, vanadium porphyrin, ruthenium porphyrin, zirconium porphyrin and lanthanum porphyrin.

The nitrogen-containing organic ligand is preferably a nitrogen-containing heterocyclic carboxylic acid ligand and/or a nitrogen-containing heterocyclic carboxylic ester ligand; wherein the nitrogen-containing heterocyclic ring can be a five-membered heterocyclic ring, a six-membered heterocyclic ring or a condensed ring heterocyclic ring, and in the invention, the nitrogen-containing organic ligand is preferably one or more of compounds represented by formula (1) to formula (16):

in the formula (1), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

in the formula (2), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 3;

in the formula (3), X is (COOH)_nOr (COOR)_nN is an integer of 1-2;

in the formula (4), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 5;

in the formula (5), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

in the formula (6), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 4;

in the formula (9), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 7;

in the formula (10), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 7;

in the formula (11), X is (COOH)_nOr (COOR)_nN is an integer of 1 to 6;

among them, each R in the formulae (1) to (6) and (9) to (11) is independently preferably an alkyl group having C1 to C6, more preferably an alkyl group having C1 to C4, and still more preferably an alkyl group having C1 to C3. In the above structure, n is the number of substituents on the nitrogen-containing heterocycle in the nitrogen-containing organic ligand, unless otherwise specified.

The nitrocellulose is known to those skilled in the art, and SS1/4S is used in the present invention.

The solid light-controlling particles provided by the invention are non-blue solid particles, and the main body of the solid light-controlling particles is an inorganic-organic complex. Wherein the metal iodide and the metal atom in the metal-organic complex form a chemical bond with the nitrogen atom in the nitrogen-containing organic ligand; iodine also forms polyiodide complexes with metal iodides and metal atoms in metalorganic complexes; the selected nitrocellulose can inhibit the agglomeration of formed nano particles, control the growth speed of different crystal faces and promote a certain crystal face to grow rapidly in preference to other crystal faces, so that a rodlike appearance is generated.

The particle length of the solid light-controlling particle provided by the invention is preferably 50-800 nm, more preferably 100-600 nm, further preferably 200-500 nm, further preferably 240-480 nm, further preferably 260-450 nm, and most preferably 260-435 nm; in the embodiments provided herein, the solid light-controlling particles have a particle length of 310nm, 328nm, 298nm, 265nm, 411nm, or 432 nm; the solid light-controlling particles are in a rod-like shape, so that the solid light-controlling particles have a certain aspect ratio, and in the invention, the particle aspect ratio of the solid light-controlling particles is preferably 2-30, more preferably 2-20, still more preferably 4-10, and most preferably 4.5-5.5; in embodiments provided herein, the solid light-controlling particles have an aspect ratio of specifically 4.5, 4.8, 5, or 5.5.

The invention also provides a preparation method of the solid light-controlling particle, which comprises the following steps: s1) mixing iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrocellulose and an organic solvent, then adding low carbon alcohol, distilled water and a nitrogen-containing organic ligand, and stirring for reaction to obtain a reaction solution; s2) centrifuging the reaction solution under the condition that the concentration is not higher than 5000g to obtain a supernatant; s3) centrifuging the supernatant under the condition that the weight of the supernatant is not less than 10000g to obtain the solid light-controlling particles.

Wherein, the sources of all raw materials are not specially limited and can be sold in the market; the types and proportions of the iodine, the main group metal iodide, the transition metal organic complex and/or the rare earth metal organic complex, the nitrocellulose and the nitrogen-containing organic ligand are the same as those described above, and are not described herein again.

Mixing iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrocellulose and an organic solvent, then adding low carbon alcohol, distilled water and a nitrogen-containing organic ligand, and stirring for reaction to obtain a reaction solution; wherein the organic solvent is preferably an organic solvent capable of dissolving nitrocellulose, and is more preferably isoamyl acetate; the mixing temperature is preferably 5-150 ℃, more preferably 20-120 ℃, further preferably 30-100 ℃, and most preferably 40-80 ℃; mixing until iodine is dissolved, adding low carbon alcohol, distilled water and nitrogen-containing organic ligand, and stirring for reaction; the temperature of the stirring reaction is preferably 5-150 ℃, more preferably 20-120 ℃, further preferably 30-100 ℃, and most preferably 40-80 ℃; the stirring reaction time is preferably 0.1-20 h, more preferably 0.5-15 h, still more preferably 2-12 h, and most preferably 4-6 h. Water and 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.

Centrifuging the reaction solution at a temperature of not more than 5000g to remove large-particle products and obtain a supernatant; the centrifugation condition is preferably 500-4000 g, more preferably 1000-3000 g, further preferably 1000-2000 g, and most preferably 1350 g; the time for centrifugation is preferably 0.2-2 h, and more preferably 0.5-1 h.

Centrifuging the supernatant under the condition of not less than 10000 g; the centrifugation condition is preferably 10000-40000 g, more preferably 10000-30000 g, still more preferably 15000-20000 g, and most preferably 18000 g; the centrifugation time is preferably 0.5-20 h, more preferably 2-15 h, still more preferably 4-10 h, and most preferably 5-8 h. Centrifuging and discarding the supernatant to obtain the solid light-controlling particles.

The invention also provides a light valve device which comprises the solid light-controlling particles.

The invention also provides a light valve device, which comprises a first transparent substrate, a first transparent electrode formed on the first transparent substrate, a second transparent electrode formed on the second transparent substrate, a light control layer arranged between the first transparent electrode and the second transparent electrode, and a first electrode layer and a second electrode layer which are arranged on the first transparent substrate; the light management layer includes a polymer matrix; wherein the polymer matrix is dispersed with suspension medium droplets, and solid light-controlling particles are distributed in the suspension medium droplets; the solid light-controlling particles are formed from raw materials comprising: iodine, main group metal iodide, transition metal organic complex and/or rare earth metal organic complex, nitrogen-containing organic ligand and nitrocellulose.

The light valve device provided by the invention is non-blue in a dark state and transparent in a bright state; the non-blue key is as follows: in CIELab color coordinates, L is more than 10 and less than 40, a is more than-5 and less than 5, and b is more than-1.5 and less than 5; preferably, the non-blue basic tones are specifically: in CIELab color coordinates, L is more than 10 and less than 40, a is more than-2 and less than 5, and b is more than-1.5 and less than 2.

The light valve device provided by the invention is preferably an electro-dimming film which can adjust dark state and bright state when being electrified; the electrifying mode is preferably alternating current; the alternating current effective value is preferably 5-500V alternating current.

The light valve device comprises a first transparent substrate and a second transparent substrate; the first transparent substrate and the second transparent substrate are transparent substrates known to those skilled in the art, and are not particularly limited, and in the present invention, the first transparent substrate and the second transparent substrate are preferably glass plates and/or plastic sheets.

A first transparent electrode is arranged on the first transparent substrate; a second transparent electrode is arranged on the second transparent substrate; the transparent electrode is a transparent electrode well known to those skilled in the art, and is not particularly limited, and in the present invention, the first transparent electrode includes at least one of ITO, FZO, IZO, GZO, AZO, nano Ag wire, conductive graphene, PEDOT conductive layer, and nano Cu wire; the second transparent electrode comprises at least one of ITO, FZO, IZO, GZO, AZO, nano Ag wires, conductive graphene, a PEDOT conductive layer and nano Cu wires.

The first transparent substrate and a first transparent electrode formed on the first transparent substrate form a first conductive substrate; the second transparent substrate and a second transparent electrode formed on the second transparent substrate form a second conductive substrate; the first conductive substrate and the second conductive substrate are preferably at least one of ITO conductive glass, FTO conductive glass, FZO conductive glass, izo (indium zinc oxide) conductive glass, GZO (ga.zno) conductive glass, AZO (Al-doped ZnO) conductive glass, ITO/PET conductive film, nano Ag wire/PET conductive film, graphene conductive film, nano Cu wire/PET conductive film, PEDOT conductive layer/PET, and the conductive substrate having an insulating layer covering on a transparent electrode.

A light control layer is arranged between the two transparent electrodes; the thickness of the light control layer is preferably 10-200 μm, more preferably 20-180 μm, still more preferably 30-150 μm, and most preferably 40-100 μm; in the embodiments provided herein, the thickness of the light control layer is specifically 80 μm; the light management layer includes a polymer matrix; the polymer matrix is preferably cross-linked and cured from a silicone oil polymer matrix precursor having an unsaturated bond, and more preferably cross-linked and UV cured from a silicone oil polymer matrix precursor having an unsaturated bond.

The polymer matrix is dispersed with a suspension medium; in the present invention, the suspension medium is preferably dispersed in the form of droplets in the polymer matrix; the suspending medium is preferably a non-conductive liquid, and more preferably comprises at least one of a fluorocarbon organic compound, a phthalate, a trimellitate, a dodecylbenzene, a polybutyleneoil, a polyacrylate, a polymethacrylate, an epoxidized soybean oil, and an epoxidized linseed oil.

The suspension medium liquid drop is dispersed with solid light control particles; the solid light-controlling particles are the same as those described above, and are not described herein again.

The mass ratio of the total mass of the suspension medium droplets and the solid light-controlling particles to the polymer matrix in the light valve device provided by the invention is preferably 1: (1-5), more preferably 1: (1.5-4), and preferably 1: (2 to 3.5), most preferably 1: (2.2-3).

The mass ratio of the suspension medium liquid drops to the solid light control particles is preferably (5-25): 1, more preferably (10 to 20): 1, most preferably (12-18): 1.

the main body of the solid light-controlling particles adopted by the light valve device provided by the invention is an inorganic-organic complex which is non-blue solid particles, when an electric field is not applied (in a closed state), the solid light-controlling particles in the suspension liquid are randomly dispersed due to Brownian motion, at the moment, light beams entering the light valve are absorbed and/or scattered, the light valve has poor light transmission and is relatively darker, and the dark state is a non-blue primary tone; when an electric field is applied (in an opening state), the solid light-controlling particles are polarized by the electric field, and the shapes and the states of the solid light-controlling particles are changed, so that the absorption/scattering and transmission of the light valve to light are influenced, most of the light can pass through the light valve, the light transmittance of the light valve is effectively enhanced, the light valve is relatively bright, and the modulation of the dark primary color of the light valve device is realized.

Referring to fig. 1, when no electric field is applied (in an off state), the solid light-controlling particles G40 in the suspension medium droplets G30 are randomly dispersed due to brownian motion, and at this time, the light beam entering the light valve is absorbed and/or scattered, and the light valve has poor light transmittance and is relatively dark, and has a structure as shown in fig. 1 a; when an electric field is applied (on state), the solid light-controlling particles G40 are polarized by the electric field and aligned in a direction parallel to each other by the electric field, so that most of the light can pass through the light valve, which has a structure as shown in fig. 1b, and the light valve has effectively enhanced light transmittance and relatively bright transparency.

The invention also provides a preparation method of the light valve device, which comprises the following steps:

providing solid light-controlling particles;

providing a suspension medium;

mixing the solid light-controlling particles with the suspension medium to form a mixture of suspension medium containing solid light-controlling particles;

providing a polymer matrix precursor;

mixing an initiator for initiating crosslinking and curing of the polymer matrix precursor, the mixture of the suspension medium containing the solid light-controlling particles and the polymer matrix precursor to obtain a light-controlling layer matrix emulsion;

coating the matrix emulsion of the light control layer on a first transparent electrode of a first transparent substrate to form a wet film of the light control layer;

covering a second transparent electrode on a second transparent substrate on the wet film of the light control layer;

and crosslinking and curing the wet film of the light control layer to obtain the light valve device.

The solid light-controlling particles, the suspension medium, the first transparent substrate, the first transparent electrode, the second transparent electrode and the second transparent substrate are the same as described above, and are not repeated herein.

Mixing the solid light-controlling particles with the suspension medium to form a mixture of suspension medium containing solid light-controlling particles; the mass ratio of the suspension medium to the solid light-controlling particles is preferably (5-25): 1, more preferably (10 to 20): 1, most preferably (12-18): 1.

providing a polymer matrix precursor; the polymer matrix precursor is preferably a silicone oil having an unsaturated bond.

Mixing an initiator for initiating crosslinking and curing of the polymer matrix precursor, the mixture of the suspension medium containing the solid light-controlling particles and the polymer matrix precursor to obtain a light-controlling layer matrix emulsion; the initiator is preferably a photoinitiator; the type of the photoinitiator can be selected according to actual needs, and is not particularly limited, and the photoinitiator 819 is specifically adopted in the embodiment of the invention; the mass of the photoinitiator is preferably 0.05% to 1%, more preferably 0.1% to 0.6%, and still more preferably 0.2% to 0.5% of the mass of the polymer matrix precursor.

Coating the matrix emulsion of the light control layer on a first transparent electrode of a first transparent substrate to form a wet film of the light control layer; covering a second transparent electrode on a second transparent substrate on the wet film of the light control layer; and crosslinking and curing the wet film of the light control layer to obtain the light valve device. The crosslinking curing is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen; the crosslinking curing is preferably ultraviolet curing; the preferable power of the ultraviolet curing is 500-1000W/m²(ii) a The time for crosslinking and curing is preferably 10-120 s, and more preferably 20-80 s.

The invention also provides a dimming glass assembly, which comprises a first glass plate, a second glass plate and the light valve device arranged between the first glass plate and the second glass plate; the first transparent substrate and the second transparent substrate are transparent plastic sheets; and a first adhesive layer is arranged between the first glass plate and the light valve device, and/or a second adhesive layer is arranged between the second glass plate and the light valve device.

To further illustrate the present invention, the following detailed description of a light valve device, solid light-controlling particles and a method for making the same according to the present invention will be provided in conjunction with examples.

The reagents used in the following examples are all commercially available.

Comparative example 1: preparation of blue solid light-controlling particles

The mass ratio of the raw materials is elementary iodine: metal iodide: metal organic complex: nitrogen-containing organic ligands: nitrocellulose is 1: 0.66: 0: 0.66: 1.

into a 250 ml three-neck round bottom glass flask was added 30 g of isoamyl acetate solution containing 21.2 wt% nitrocellulose (SS1/4S), 6g of I₂70 g of isoamyl acetate, 4 g of anhydrous CaI₂And heated to 42 ℃. Etc. I₂After dissolution, 6 grams of anhydrous methanol, 0.85 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 particles of the product. The supernatant was centrifuged at 18000g for 5 hours, and the supernatant was discarded to obtain blue solid light-controlling particles. The blue solid light-controlling particles were thoroughly dispersed with 250 ml of isoamyl acetate.

SEM characterization results show that the blue solid light-controlling particle has a particle length of 280nm, a particle width of 70nm and a particle aspect ratio of 4.

40 g of TDTM (tridecyl trimellitate) was added in portions to a 250 ml round bottom glass flask and the isoamyl acetate dispersion of blue solid light-controlling particles prepared above was added, the isoamyl acetate was removed by a rotary evaporator, and finally the treatment was continued at 80 ℃ for 3 hours using the rotary evaporator. After weighing, the mass of the solid light-controlling particles was calculated, and then an appropriate amount of TDTM was added and mixed uniformly so that the solid light-controlling particles/TDTM became 1/12, and the thus obtained suspension containing blue solid light-controlling particles was referred to as LCP-0.

Example 1: preparation of red solid light-controlling particles

The mass ratio of the raw materials is elementary iodine: metal iodide: metal organic complex: nitrogen-containing organic ligands: nitrocellulose is 1: 0.5: 0.16: 0.66: 1.

into a 250 ml three-neck round bottom glass flask was added 30 g of isoamyl acetate solution containing 21.2 wt% nitrocellulose (SS1/4S), 6g of I₂70 g of isoamyl acetate,3 g of anhydrous CaI₂1 g of ferrocene, and heating to 42 ℃. Etc. I₂After dissolution, 6 grams of anhydrous methanol and 4 grams of 2, 5-pyrazine dicarboxylic 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. The supernatant was centrifuged at 18000G for 5 hours, and the supernatant was discarded to obtain red solid light-controlling particles. The red solid light-controlling particles were thoroughly dispersed with 250 ml of isoamyl acetate.

The SEM characterization result is shown in FIG. 2, which shows that the red solid light-controlling particle has a particle length of 310nm, a particle width of 68nm, and an aspect ratio of 4.5.

40 g of TDTM (tridecyl trimellitate) was added to a 250 ml round bottom glass flask, and the isoamyl acetate dispersion of the red solid light-controlling particles prepared above was added in portions, the isoamyl acetate was removed by a rotary evaporator, and finally, the treatment was continued at 80 ℃ for 3 hours by using a rotary evaporator, and after weighing, the mass of the solid light-controlling particles was calculated, and then an appropriate amount of TDTM was added thereto and mixed uniformly so that the solid light-controlling particles/TDTM became 1/12, and the thus obtained suspension containing red solid light-controlling particles was referred to as LCP-1.

Example 2: preparation of grey solid light-controlling particles

Following the procedure of example 1, except that 1.0 g of Co (acac)₂Instead of 1 g of ferrocene, the reaction was heated with stirring at 46 ℃ for 2 hours. SEM characterization results showed that the gray solid light-controlling particles had a particle length of 328nm, a particle width of 72nm, and a particle aspect ratio of 4.5. The resulting suspension of grey solid light-controlling particles was designated LCP-2.

Example 3: preparation of grey solid light-controlling particles

Following the procedure of example 1, except that 1.0 g of Ni (acac)₂Instead of 1 g of ferrocene, the reaction was heated with stirring at 45 ℃ for 2 hours. SEM characterization results showed that the gray solid light-controlling particles had a particle length of 298nm, a particle width of 62nm, and a particle aspect ratio of 4.8. The resulting suspension of grey solid light-controlling particles was designated LCP-3.

Example 4: preparation of green solid light-controlling particles

Following the procedure of example 1, except that 1.0 g of Fe (acac)₃Instead of 1 g of ferrocene, the reaction was heated with stirring at 50 ℃ for 4 hours. SEM characterization results show that the green solid light-controlling particle has a particle length of 265nm, a particle width of 59nm and a particle aspect ratio of 4.5. The resulting suspension of green solid light-controlling particles was designated LCP-4.

Example 5: preparation of grey solid light-controlling particles

Following the procedure of example 1, except substituting 0.1 g of copper phthalocyanine for 1 g of ferrocene, the reaction was stirred with heating at 42 ℃ for 2 hours. SEM characterization results showed that the gray solid light-controlling particles had a particle length of 411nm, a particle width of 82nm, and a particle aspect ratio of 5.0. The resulting suspension of grey solid light-controlling particles was designated LCP-5.

Example 6: preparation of grey solid light-controlling particles

The reaction was carried out by following the procedure of example 1 except that 0.1 g of copper porphyrin was used instead of 1 g of ferrocene, and the reaction was heated and stirred at 52 ℃ for 5 hours. SEM characterization results showed that the gray solid light-controlling particles had a particle length of 432nm, a particle width of 78nm, and a particle aspect ratio of 5.5. The resulting suspension of grey solid light-controlling particles was designated LCP-6.

Comparative example 2: preparation of Silicone oil Polymer matrix precursor having unsaturated bond

To a 1L three neck round bottom glass flask was added 108g of hydroxy terminated dimethyldiphenyl polysiloxane and 380mL of n-heptane. One side of the three-neck round bottom glass flask is connected with a water separator and a condenser pipe, the middle part is provided with a mechanical stirrer, and the other side is provided with a thermometer. The reaction solution in the three-neck round bottom glass flask was heated to reflux for 30min, and when a small amount of water was present in the trap, a solution of 0.26g stannous octoate in 20mL n-heptane was added. 6g of 3-acryloxypropyltrimethoxysilane were then added dropwise over a period of about 5 minutes. Then carrying out condensation reaction for 2 hours, and immediately adding 60mL of trimethyl methoxy silane as a reaction terminator; the reaction was terminated for 2h and then rapidly cooled to room temperature. 100mL of ethanol and the reaction solution which had been cooled were mixed and stirred in a 2L beaker, and the reaction flask was rinsed with 60mL of heptane and poured into the beaker. After mixing well, 400mL of methanol was added and stirred for 15 min. The resulting mixture was poured into a 2L separatory funnel and allowed to stand for several hours before separation. The lower layer liquid was taken out and then treated at 70 ℃ for 3 hours by a rotary evaporator to remove low boiling substances, and finally, silicone oil having unsaturated bonds, i.e., a polymer matrix precursor, was obtained.

Comparative example 3: fabrication of LV-0 light valves from LCP-0

0.03 g of the photoinitiator 819, 3.0 g of the solid light-controlling particle suspension LCP-0 and 7.0 g of the above-mentioned silicone oil polymer matrix precursor having an unsaturated bond prepared in comparative example 2 were uniformly mixed to obtain a light-controlling layer matrix emulsion.

The above-prepared optical control layer substrate emulsion was coated on a PET/ITO transparent electrode with a thickness of 80 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-0 light valve.

When no voltage is applied (off state), LV-0 shows a blue color tone and the total light transmittance is 0.7%. The spectrum is shown in FIG. 3, and the absorption peak is at 630nm and shows blue tone. When 50 Hz 110V AC was applied (on state), LV-0 became clear and the total light transmission was 69.5%. Specific results are shown in table 1.

In this embodiment, a transparent conductive film (transparent electrode) is formed on a base of a plastic sheet.

The polymer matrix precursor forms a polymer matrix after crosslinking and curing.

Accordingly, the present application also provides a method of manufacturing a light valve, comprising:

providing solid light-controlling particles;

providing a suspension medium;

mixing the solid light-controlling particles with the suspension medium to form a mixture of suspension medium containing solid light-controlling particles;

providing a polymer matrix precursor;

mixing an initiator for initiating crosslinking and curing of the polymer matrix precursor, the mixture of the suspension medium containing the solid light-controlling particles and the polymer matrix precursor to obtain a light-controlling layer matrix emulsion;

coating the matrix emulsion of the light control layer on a first transparent electrode of a first transparent substrate to form a wet film of the light control layer;

covering a second transparent electrode on a second transparent substrate on the wet film of the light control layer; and crosslinking and curing the wet film of the light control layer to obtain the light valve shown in FIG. 1.

Example 7: fabrication of LV-1 light valves from LCP-1

Comparative example 3 was made and tested except that LCP-1 was used instead of LCP-0, designated as LV-1, with the specific results shown in Table 1. The UV-visible spectrum of LV-1 in the dark state is shown in FIG. 3, and the light valve shows a red tone with an absorption peak at 535nm compared to LV-0.

Example 8: fabrication of LV-2 light valves from LCP-2

Comparative example 3 was made and tested except that LCP-2 was used instead of LCP-0, designated as LV-2, with the specific results shown in Table 1. The LV-2 dark UV-visible spectrum is shown in FIG. 3, with no significant absorption peak compared to LV-0 and the light valve in a grey tone.

Example 9: fabrication of LV-3 light valves from LCP-3

Comparative example 3 was made and tested except that LCP-3 was used instead of LCP-0, designated as LV-3, with the specific results shown in Table 1.

Example 10: fabrication of LV-4 light valves from LCP-4

Comparative example 3 was made and tested except that LCP-4 was used instead of LCP-0, designated as LV-4, with the specific results shown in Table 1.

Example 11: fabrication of LV-5 light valves from LCP-5

Comparative example 3 was made and tested except that LCP-5 was used instead of LCP-0, designated as LV-5, with the specific results shown in Table 1.

Example 12: fabrication of LV-6 light valves from LCP-6

Comparative example 3 was made and tested except that LCP-6 was used instead of LCP-0, designated LV-6, with the specific results shown in Table 1.

Comparison of LV-0 with LV-1 to LV-6 demonstrated that the non-blue solid light-controlling particle light valves still maintained the light-controlling properties of the comparative example light valves.

Table 1: light valve performance comparison table

Tests show that the total light transmittance of the non-blue light valve reaches 69.1%, in a CIELab color coordinate, L is 33.72, a is 0.15, and b is-0.81, so that the defect that the dark state of the light valve is blue tone in the prior art is effectively overcome.

The present invention has been described above by way of example with a light valve having a transparent plastic sheet as a substrate, i.e., a light adjusting film. It is obvious that the inventive idea is also fully applicable to light valves with glass as substrate, i.e. dimming glasses.

The kind of the transparent electrode using glass as a substrate is not particularly limited, and may be conventional conductive glass known to those skilled in the art, and may be ITO conductive glass, FTO conductive glass, FZO conductive glass, izo (indium zinc oxide) conductive glass, GZO (ga.zno) conductive glass, AZO (Al-doped ZnO) conductive glass, or the like.

In addition, the application also provides a dimming glass assembly, which comprises a first glass plate, a second glass plate and a dimming film arranged between the first glass plate and the second glass plate; wherein: be provided with first clamp glue film between first glass board and the above-mentioned membrane of adjusting luminance, and/or be provided with the second between second glass board and the above-mentioned membrane of adjusting luminance and press from both sides the glue film.

In the present invention, the types of the first glass plate and the second glass plate are not particularly limited, and may be transparent glass for a conventional light control glass assembly, which is well known to those skilled in the art, and may be common glass such as inorganic glass and organic glass, or functional glass such as UV-blocking glass, IR-blocking glass, Low-E glass, tempered glass, or antibacterial glass.

In the present invention, the types of the first adhesive interlayer and the second adhesive interlayer are not particularly limited, and are known to those skilled in the art as the adhesive interlayer for the conventional dimming glass assembly, and the adhesive interlayer may be an EVA adhesive film, a TPU adhesive film, a PVB adhesive film, or a functional adhesive film, such as a UV-blocking EVA adhesive film, a UV-blocking TPU adhesive film, a UV-blocking PVB adhesive film, and the like.

In the present invention, the manner of manufacturing the dimming glass assembly is not particularly limited, and may be a conventional laminating manner of the dimming glass assembly in the art, such as laminating in a laminating machine, or laminating in an autoclave or a laminating box/furnace.

In conclusion, the non-blue solid light-controlling particles are obtained by using different metal organic complexes or different reaction conditions, the total light transmittance of the light valve manufactured by the non-blue solid light-controlling particles reaches 69.1%, 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 above examples are for illustrative purposes only and do not limit the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention. All chemicals used in the examples were purchased from Sigma Aldrich, unless otherwise indicated. In all of these examples, all parts and percentages are by weight unless otherwise indicated. The transmittance of the LV light valve was measured with an Oceanview spectrometer and the chromatic aberration data was measured with an LS171 chromatometer of the forest technology.