CN113917757B - Light valve device containing liquid polymer with nonlinear structure, liquid polymer with nonlinear structure and preparation method thereof - Google Patents
Light valve device containing liquid polymer with nonlinear structure, liquid polymer with nonlinear structure and preparation method thereof Download PDFInfo
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- CN113917757B CN113917757B CN202111424523.5A CN202111424523A CN113917757B CN 113917757 B CN113917757 B CN 113917757B CN 202111424523 A CN202111424523 A CN 202111424523A CN 113917757 B CN113917757 B CN 113917757B
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/155—Electrodes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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Abstract
The invention provides a light valve device containing liquid polymer with a nonlinear structure, 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, wherein the first transparent electrode and the second transparent electrode are oppositely arranged; the light management layer comprises a polymer matrix; the polymer matrix having dispersed therein droplets of a suspending medium; the suspension medium comprises a liquid polymer of nonlinear structure. Compared with the prior art, the polymerized monomer of the liquid polymer with the nonlinear structure added by the invention contains the multifunctional methacrylate and/or the multifunctional acrylate, so that the obtained liquid polymer molecule with the nonlinear structure is of a net structure, which is beneficial to providing protection effect for solid light control particles, enhancing the stability of the solid light control particles and further enabling the light valve device to have better high-temperature stability.
Description
Technical Field
The invention belongs to the technical field of light valves, and particularly relates to a light valve device containing a liquid polymer with a nonlinear structure, the liquid polymer with the nonlinear structure and a preparation method thereof.
Background
A light valve is a device that can adjust the transmittance of light passing through itself, and particularly, in the present invention, a light valve refers to a device capable of controlling 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 an Alternating Current (AC) voltage applied to the medium. The light valve has the advantages of actively regulating and controlling light transmittance and saving energy, and the device can be used as intelligent windows of spacecrafts, high-speed rails, automobiles, buildings and the like, rearview mirrors of automobiles, sunglasses, displays and the like. Depending on the substrate of the light valve, the light valve includes a light valve having a plastic sheet such as PET as a substrate, which is referred to herein as a dimming film, and a light valve having glass as a substrate, which is referred to herein as a dimming glass. The dimming film is glued and then is called a dimming glass component.
Eighty-seven years ago, light valve devices comprising nanoparticles were invented. Although suspended particle dimming films have been developed successfully for many years, the stability of such dimming films has been a major concern. In practical applications, it is required that the dimming film still has stable and excellent dimming performance under a long-term high-temperature environment.
In view of the prior art, stable dimming performance of the dimming film under a long-term high-temperature environment is still a bottleneck for limiting the suspended particle light valve. Therefore, it is desirable to invent a light valve dimming technique that is more stable in high temperature environments.
Disclosure of Invention
In view of the above, the present invention provides a light valve device containing a liquid polymer with a nonlinear structure, which has better high temperature stability, the liquid polymer with a nonlinear structure, and a preparation method thereof.
The present invention provides a light valve device comprising a liquid polymer having a nonlinear structure, comprising:
a first transparent substrate having a first surface and a second surface,
a first transparent electrode formed on the first transparent substrate,
a second transparent substrate having a first transparent surface,
a second transparent electrode formed on the second transparent substrate, the first transparent electrode and the second transparent electrode being disposed opposite to each other, and
a light control layer disposed between the first transparent electrode and the second transparent electrode; the light management layer comprises a polymer matrix;
wherein, suspending medium liquid drops are scattered in the polymer matrix, solid light control particles are distributed in the suspending medium liquid drops,
the suspension medium comprises a liquid polymer of nonlinear structure; the nonlinear structure liquid polymer comprises a unit A, a unit B and a unit C; the unit A is selected from methacrylate monomers and/or acrylate monomers; the unit B is selected from a multifunctional methacrylate monomer and/or a multifunctional acrylate monomer; the unit C is selected from hydroxy methacrylate monomers and/or hydroxy acrylate monomers; the mass ratio of the monomers forming unit a, unit B and unit C is 1: (0.01-0.5): (0 to 0.5).
Preferably, the monomers of unit A are of formula (I):
CH 2 =crcoo-R' formula (I);
wherein R is CH 3 Or H; r' is C n H 2n+1 N is an integer of 1 to 18.
Preferably, the monomers of unit B are of formula (II):
(CH 2 ＝CR 1 COOCH 2 ) m -R 1 ' formula (II);
wherein R is 1 Is CH 3 Or H; r is R 1 ' C a H 2a+2-m O b M is an integer of 2 to 10, a and b are each independently an integer of 0 to 10, and a is not less than b.
Preferably, the monomers of unit C are of formula (III):
CH 2 ＝CR 2 COO-R 2 ' formula (III);
wherein R is 2 Is CH 3 Or H; r is R 2 ' C q H 2q -OH, q is an integer from 1 to 8.
Preferably, the peak molecular weight of the nonlinear structure liquid polymer is 2000 to 7000.
Preferably, the mass ratio of the total mass of the suspension medium and the solid light control particles to the polymer matrix is 1: (1-10); the mass ratio of the nonlinear structure liquid polymer in the suspension medium to the total mass of the suspension medium is 1: (1-5); the mass ratio of the suspension medium to the solid light control particles is 1: (0.05-0.2).
Preferably, the solid light control particles are selected from one or more of oxide nanorods, perovskite nanorods and polyiodide nanorods; the particle length of the solid light control particles is 50-800 nm; the aspect ratio of the solid light control particles is 2-30;
The suspension medium further comprises a non-conductive liquid;
the non-conductive liquid is at least one selected from fluorocarbon organic compounds, phthalic acid esters, benzene tricarboxylic acid esters, dodecylbenzene, polybutene oil, polyacrylate, polymethacrylate, epoxidized soybean oil and epoxidized linseed oil; among them, the phthalate may be dioctyl terephthalate, di (2-ethylhexyl) isophthalate, dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, etc.; the trimellitate may be methyl trimellitate, trioctyl trimellitate, triisodecyl trimellitate, etc.
The polymer matrix is formed by crosslinking and curing a silicone oil polymer matrix precursor with unsaturated bonds.
Preferably, the first transparent substrate and the second transparent substrate comprise glass plates; or the first transparent substrate and the second transparent substrate comprise transparent plastic sheets;
the first transparent electrode comprises at least one of PEDOT, ITO, FTO, AZO, FZO, IZO, GZO, a nano Ag wire, conductive graphene and a nano Cu wire; the second transparent electrode includes at least one of PEDOT, ITO, FTO, AZO, FZO, IZO, GZO, a nano Ag wire, conductive graphene, and a nano Cu wire.
Preferably, the surface of the first transparent electrode, which is not in contact with the first transparent substrate, and/or the surface of the second transparent electrode, which is not in contact with the second transparent substrate, are covered with an insulating layer.
The invention also provides a preparation method of the light valve device, which comprises the following steps:
providing solid light control particles;
providing a suspension medium;
mixing the solid light control particles with the suspension medium to form a mixture of suspension media containing solid light control particles;
providing a polymer matrix precursor;
mixing an initiator for initiating the cross-linking and curing of the polymer matrix precursor, a mixture of the suspension medium containing the solid light control particles and the polymer matrix precursor to obtain a light control layer matrix emulsion;
coating the light control layer matrix emulsion on a first transparent electrode of a first transparent substrate to form a light control layer wet film;
covering a second transparent electrode on a second transparent substrate on the light control layer wet film;
and carrying out cross-linking curing on the light control layer wet film to obtain the light valve device.
The invention also provides a liquid polymer with a nonlinear structure, which comprises a unit A, a unit B and a unit C; the unit A is selected from methacrylate monomer units and/or acrylate monomers; the unit B is selected from a multifunctional methacrylate monomer and/or a multifunctional acrylate monomer; the unit C is selected from hydroxy methacrylate monomers and/or hydroxy acrylate monomers; the mass ratio of the monomers forming unit a, unit B and unit C is 1: (0.01-0.5): (0 to 0.5).
The invention also provides a preparation method of the liquid polymer with the nonlinear structure, which comprises the following steps:
mixing monomers forming a unit A, a unit B and a unit C, a molecular weight regulator, a free radical polymerization initiator and a solvent in a protective atmosphere, and heating to perform polymerization reaction to obtain a liquid polymer with a nonlinear structure; the mass ratio of the monomers of the unit A, the unit B and the unit C is 1: (0.01-0.5): (0 to 0.5).
Preferably, the molecular weight regulator is a mercaptan compound; the mercaptan compound is selected from hexanethiol; the mass of the molecular weight regulator is 5% -10% of the monomer mass of the unit A;
the free radical polymerization initiator is selected from azo initiators; the azo initiator is selected from azodiisobutyronitrile; the mass of the free radical polymerization initiator is 0.5-1% of the monomer mass of the unit A;
the polymerization reaction is specifically carried out by heating to 50-70 ℃ for reaction for 15-30 h, and then continuously heating to reflux for 2-4 h.
The invention also provides a dimming glass component comprising a first glass plate and a second glass plate, a light valve device as described above 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-clamping layer is arranged between the first glass plate and the light valve device, and/or
A second glue layer is arranged between the second glass plate and the light valve device.
The invention provides a light valve device containing liquid polymer with a nonlinear structure, 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, wherein the first transparent electrode and the second transparent electrode are oppositely arranged; the light management layer comprises a polymer matrix; wherein, suspension medium liquid drops are dispersed in the polymer matrix, and solid light control particles are distributed in the suspension medium liquid drops; the suspension medium comprises a liquid polymer of nonlinear structure; the nonlinear structure liquid polymer comprises a unit A, a unit B and a unit C; the unit A is selected from methacrylate monomers and/or acrylate monomers; the unit B is selected from a multifunctional methacrylate monomer and/or a multifunctional acrylate monomer; the unit C is selected from hydroxy methacrylate monomers and/or hydroxy acrylate monomers; the mass ratio of the monomers of the unit A, the unit B and the unit C is 1: (0.01-0.5): (0 to 0.5). Compared with the prior art, the polymerized monomer of the liquid polymer with the nonlinear structure added by the invention contains the multifunctional methacrylate and/or the multifunctional acrylate, so that the obtained liquid polymer molecule with the nonlinear structure is of a net structure, which is beneficial to providing protection effect for solid light control particles, enhancing the stability of the solid light control particles and further enabling the light valve device to have better high-temperature stability.
Experiments show that the light valve device manufactured by the liquid polymer with the nonlinear structure has the high-temperature stability of 2380 hours at 105 ℃, and compared with the corresponding high-temperature stability of 97 hours at 105 ℃ of the light valve manufactured by the liquid polymer with the linear structure of the comparative example, the light valve device manufactured by the liquid polymer with the nonlinear structure has the advantages of remarkably improving the high-temperature stability of the light valve, overcoming the defect of poor high-temperature stability of the light valve in the prior art, obtaining better technical effect and having good application prospect.
Drawings
FIG. 1 is a schematic diagram of a liquid polymer molecular structure with a nonlinear structure provided by the invention;
FIG. 2 is a schematic diagram of a light valve device according to the present invention;
FIG. 3 is a molecular weight and distribution diagram of the nonlinear structured liquid polymer obtained in example 4 provided by the present invention;
fig. 4 is a FTIR spectrum of the liquid polymer of nonlinear structure obtained in example 4 provided by the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a liquid polymer with a nonlinear structure, which comprises a unit A, a unit B and a unit C; the unit A is selected from methacrylate monomers and/or acrylate monomers; the unit B is selected from a multifunctional methacrylate monomer and/or a multifunctional acrylate monomer; the unit C is selected from hydroxy methacrylate monomers and/or hydroxy acrylate monomers; the mass ratio of the monomers of the unit A, the unit B and the unit C is 1: (0.01-0.5): (0 to 0.5).
Wherein the monomers of unit A are preferably of formula (I):
CH 2 =crcoo-R' formula (I);
wherein R is CH 3 Or H; r' is C n H 2n+1 N is an integer of 1 to 18, preferably an integer of 2 to 18, more preferably an integer of 4 to 16, and most preferably an integer of 6 to 12.
The monomer of the unit B is shown as a formula (II):
(CH 2 ＝CR 1 COOCH 2 ) m -R 1 ' formula (II);
wherein R is 1 Is CH 3 Or H; r is R 1 ' C a H 2a+2-m O b M is an integer of 2 to 10, preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and most preferably an integer of 2 to 4; a and b are each independently integers of 0 to 10, and a is not less than b; in the present invention, a is preferably an integer of 0 to 8, more preferably an integer of 0 to 6, still more preferably an integer of 0 to 4; the term "b" is preferably an integer of 0 to 8, more preferably an integer of 0 to 6, still more preferably an integer of 0 to 4, and most preferably an integer of 0 to 3. In the embodiment provided by the invention, the monomer forming the monomer unit B is one or more of diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate and octaethylene glycol dimethacrylate.
The monomer of the unit C is shown as a formula (III):
CH 2 ＝CR 2 COO-R 2 ' formula (III);
wherein R is 2 Is CH 3 Or H; r is R 2 ' C q H 2q -OH, q is an integer from 1 to 8, preferably an integer from 1 to 7, more preferably an integer from 1 to 6, still more preferably an integer from 1 to 5, still more preferably an integer from 2 to 4, most preferably 2 or 3.
The mass ratio of the monomers of unit a, unit B and unit C is preferably 1: (0.01-0.5): (0 to 0.5), more preferably 1: (0.05-0.5): (0 to 0.4), and more preferably 1: (0.1-0.3): (0 to 0.3), most preferably 1: (0.1-0.2): (0 to 0.15); in the embodiment provided by the invention, the mass ratio of the monomers of the unit A, the unit B and the unit C is specifically 1:0.2:0. 1:0.2:0.15 or 1:0.13:0.086.
the peak molecular weight of the nonlinear structured liquid polymer is preferably 2000 to 7000, more preferably 2300 to 6900.
The dynamic viscosity of the nonlinear structure liquid polymer at 20 ℃ is preferably 1400-24000 cp.
The invention also provides a preparation method of the liquid polymer with the nonlinear structure, which comprises the following steps: mixing monomers of the unit A and the unit B with the unit C, a molecular weight regulator, a free radical polymerization initiator and a solvent in a protective atmosphere, and heating to perform polymerization reaction to obtain a liquid polymer with a nonlinear structure; the mass ratio of the monomers of the unit A, the unit B and the unit C is 1: (0.01-0.5): (0 to 0.5).
The source of all the raw materials is not particularly limited, and the raw materials are commercially available.
Mixing monomers of the unit A, the unit B and the unit C, a molecular weight regulator, a free radical polymerization initiator and a solvent in a protective atmosphere; the protective atmosphere is a protective atmosphere well known to those skilled in the art, and is not particularly limited, and argon is preferred in the present invention; the types and the proportions of the monomers of the unit A, the unit B and the unit C are the same as those described above, and are not repeated here; the molecular weight regulator is preferably a mercaptan compound, more preferably hexanethiol; the mass of the molecular weight regulator is preferably 5-10%, more preferably 6-9%, even more preferably 7-9%, and most preferably 8% of the mass of the monomer of the unit A; the radical polymerization initiator is preferably an azo-type initiator, more preferably azobisisobutyronitrile; the mass of the radical polymerization initiator is preferably 0.5% to 1%, more preferably 0.6% to 0.9%, still more preferably 0.7% to 0.9%, and most preferably 0.8% of the mass of the monomer of the unit A; the solvent is a solvent well known to those skilled in the art, and is not particularly limited, and toluene is preferred in the present invention; the mixing is preferably carried out with stirring; the rotational speed of the mixing is preferably 100 to 500rpm, more preferably 200 to 400pm, still more preferably 200 to 300rpm; in the present invention, it is preferable to mix the monomers of the unit A, the unit B and the unit C, the molecular weight regulator and the solvent in a protective atmosphere, heat them to a reaction temperature, and then add a radical polymerization initiator; the radical polymerization initiator is preferably dissolved in a solvent and then added.
Mixing and heating to perform polymerization reaction; in the invention, the polymerization reaction is preferably carried out by heating to 50-70 ℃ for 15-30 h, then continuously heating to reflux and keeping the reflux for 2-4 h; more preferably, heating to 55-65 ℃ for reaction for 18-25 h, and then continuing heating to reflux for 2-4 h; and heating to 60 ℃ to react for 20-21 h, and then continuously heating to reflux and keeping the reflux for 3h.
After the polymerization reaction, preferably cooling, and removing the solvent to obtain a liquid polymer with a nonlinear structure; the method for removing the solvent is preferably rotary evaporation; the temperature of the rotary steaming is preferably 90-110 ℃, more preferably 95-105 ℃ and still more preferably 105 ℃; the time of the rotary steaming is preferably 2 to 5 hours, more preferably 3 to 4 hours.
The invention also provides a light valve device containing the liquid polymer with the nonlinear structure, 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, the first transparent electrode and the second transparent electrode are oppositely arranged, and a light control layer arranged between the first transparent electrode and the second transparent electrode; the light management layer comprises a polymer matrix; wherein, suspension medium liquid drops are dispersed in the polymer matrix, and solid light control particles are distributed in the suspension medium liquid drops. The suspension medium comprises a liquid polymer of nonlinear structure; the nonlinear structure liquid polymer comprises a unit A, a unit B and a unit C; the unit A is selected from methacrylate monomers and/or acrylate monomers; the unit B is selected from a multifunctional methacrylate monomer and/or a multifunctional acrylate monomer; the unit C is selected from hydroxy methacrylate monomers and/or hydroxy acrylate monomers; the mass ratio of the monomers of the unit A, the unit B and the unit C is 1: (0.01-0.5): (0 to 0.5).
The light valve device provided by the invention is preferably an electrically-induced dimming film with adjustable dark state and bright state; the energizing mode is preferably alternating current; the alternating current 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 may be transparent substrates well 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.
The first transparent substrate is provided with a first transparent electrode; the second transparent substrate is provided with a second transparent electrode; 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 PEDOT, ITO, FZO, IZO, GZO, AZO, a nano Ag wire, conductive graphene and a nano Cu wire; the second transparent electrode comprises at least one of PEDOT, ITO, FZO, IZO, GZO, AZO, nano Ag wires, conductive graphene and nano Cu wires.
The first transparent substrate and the first transparent electrode formed on the first transparent substrate form a first conductive substrate; the second transparent substrate and the second transparent electrode formed on the second transparent substrate form a second conductive substrate; in the present invention, the first conductive substrate and the second conductive substrate are each independently preferably at least one of ITO conductive glass, FTO conductive glass, FZO conductive glass, IZO (IndiumZinc 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, and transparent electrode covered with an insulating layer.
A light control layer is arranged between the two transparent electrodes; the thickness of the light control layer is preferably 10 to 200 μm, more preferably 20 to 180 μm, still more preferably 30 to 150 μm, and most preferably 40 to 100 μm; in the embodiment provided by the invention, the thickness of the light control layer is specifically 80 μm.
The light management layer comprises a polymer matrix; the polymer matrix is preferably crosslinked and cured from a silicone oil polymer matrix precursor having an unsaturated bond, more preferably crosslinked and UV-cured from a silicone oil polymer matrix precursor having an unsaturated bond.
The polymer matrix having dispersed therein a suspending medium; in the present invention, the suspension medium is preferably dispersed in the polymer matrix in the form of droplets; the suspension medium comprises a liquid polymer of nonlinear structure; the nonlinear structure liquid polymer is the same as that described above and will not be described in detail herein; the suspension medium preferably further comprises a non-conductive liquid, more preferably further comprises at least one of fluorocarbon organic compounds, phthalates, trimellitates, dodecylbenzene, polybutene oil, polyacrylate, polymethacrylate, epoxidized soybean oil and epoxidized linseed oil. Among them, the phthalate may be dioctyl terephthalate, di (2-ethylhexyl) isophthalate, dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, etc.; the trimellitate may be methyl trimellitate, trioctyl trimellitate, triisodecyl trimellitate, etc. The mass ratio of the nonlinear structure liquid polymer in the suspension medium to the total mass of the suspension medium is preferably 1: (1 to 5), more preferably 1: (1 to 3), and more preferably 1: (1-2), most preferably 1: (1-1.56).
The suspension medium is dispersed with solid light control particles; the mass ratio of the suspension medium to the solid light control particles is preferably 1: (0.05 to 0.2), more preferably 1: (0.05-0.1); in the embodiment provided by the invention, the mass ratio of the suspension medium to the solid light control particles is specifically 1:0.074; the solid light control particles are preferably one or more of oxide nanorods, perovskite nanorods and polyiodide nanorods; the particle length of the solid light control particles is preferably 50-800 nm, more preferably 100-600 nm, still more preferably 200-500 nm, still more preferably 240-480 nm, still more preferably 260-450 nm, and most preferably 260-435 nm; in the embodiment provided by the invention, the particle length of the solid light control particles is specifically 280nm; the solid light-controlling particles are rod-shaped in morphology, and thus have a certain aspect ratio, and in the present invention, the particle aspect ratio of the solid light-controlling particles is preferably 2 to 30, more preferably 2 to 20, still more preferably 4 to 10; in the embodiment provided by the invention, the particle aspect ratio of the solid light control particles is specifically 4.
The ratio of the total mass of the suspension medium and the solid light control particles to the mass of the polymer in the polymer matrix layer in the light valve device provided by the invention is preferably 1: (1 to 10) is more preferably 1: (1.5 to 8), and more preferably 1: (1.8 to 6), most preferably 1: (2-5).
The added polymer monomer of the nonlinear structure liquid polymer contains the polyfunctional methacrylate and/or polyfunctional acrylate, so that the obtained nonlinear structure liquid polymer molecule is of a net structure (shown in figure 1), which is beneficial to providing protection effect for solid light control particles, enhancing the stability of the solid light control particles and further enabling the light valve device to have better high-temperature stability.
Referring to fig. 2, the light valve manufactured by the present invention includes a first transparent electrode G10, a second transparent electrode G10, and an active layer G20 disposed between the first transparent electrode and the second transparent electrode for controlling light transmittance, wherein the active layer G20 is a polymer matrix layer; a suspension medium G30 is distributed in the polymer matrix layer G20, and solid light control particles G40 are dispersed in the suspension medium G30. When no electric field is applied (off state), the particles G40 in the suspending medium G30 exhibit random dispersion due to brownian motion, at which time the light beam entering the light valve is absorbed and/or scattered, and the light valve is poorly light-transmissive and relatively dark. When an electric field is applied (on state), the particles G40 are polarized by the electric field and aligned in a direction in which the electric fields are parallel to each other, so that most of the light can pass through the light valve, and the light valve is effectively enhanced in light transmittance and relatively transparent.
The invention also provides a preparation method of the light valve device, which comprises the following steps:
providing solid light control particles;
providing a suspension medium;
mixing the solid light control particles with the suspension medium to form a mixture of suspension media containing solid light control particles;
providing a polymer matrix precursor;
mixing an initiator for initiating the cross-linking and curing of the polymer matrix precursor, a mixture of the suspension medium containing the solid light control particles and the polymer matrix precursor to obtain a light control layer matrix emulsion;
coating the light control layer matrix emulsion on a first transparent electrode of a first transparent substrate to form a light control layer wet film;
covering a second transparent electrode on a second transparent substrate on the light control layer wet film;
and carrying out cross-linking curing on the light control layer wet film to obtain the light valve device.
The solid light control 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 those described above, and are not described herein again.
Mixing the solid light control particles with the suspension medium to form a mixture of suspension media containing solid light control particles; the mass ratio of the suspension medium to the solid light control particles is preferably 1: (0.04 to 0.3), more preferably 1: (0.05 to 0.2), most preferably 1: (0.055-0.15).
Providing a polymer matrix precursor; the polymer matrix precursor is preferably a silicone oil having an unsaturated bond.
Mixing an initiator for initiating the cross-linking and curing of the polymer matrix precursor, a mixture of the suspension medium containing the solid light control particles and the polymer matrix precursor to obtain a light control layer matrix emulsion; the initiator is preferably a photoinitiator; the invention can select the type of the photoinitiator according to actual needs, and is not particularly limited, and the photoinitiator 819 is specifically selected in the embodiment of the invention; the mass of the photoinitiator is preferably 0.05 to 1%, more preferably 0.1 to 0.6%, still more preferably 0.2 to 0.5% of the mass of the polymer matrix precursor.
Coating the light control layer matrix emulsion on a first transparent electrode of a first transparent substrate to form a light control layer wet film; covering a second transparent electrode on the second transparent substrate on the light control layer wet filmApplying; and carrying out cross-linking curing on the light control layer wet film to obtain the light valve device. The crosslinking curing is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen; the cross-linking curing is preferably ultraviolet curing; the power of the ultraviolet curing is preferably 500-1000W/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The time for the crosslinking curing is preferably 10 to 120 seconds, more preferably 20 to 80 seconds.
The present invention also provides a dimming glass assembly comprising a first glass plate and a second glass plate, a light valve device as described above being 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 glue layer is arranged between the first glass plate and the light valve device, and/or a second glue layer is arranged between the second glass plate and the light valve device.
To further illustrate the present invention, the following examples are provided to illustrate a light valve device comprising a liquid polymer having a nonlinear structure, the liquid polymer having a nonlinear structure, and a method for preparing the same.
The reagents used in the examples below are all commercially available.
Example 1: preparation of solid light-controlling particles
Into a 3 liter three neck round bottom glass flask was charged 300 grams of an isoamyl acetate solution containing 21.2 weight percent nitrocellulose (1/4 sec SS), 60 grams I 2 700 g of isoamyl acetate, 40 g of anhydrous CaI 2 And heated to 42 ℃. Equal I 2 After dissolution, 60 grams of absolute methanol, 8.5 grams of distilled water, and 40 grams of 2, 5-pyrazine dicarboxylic acid dihydrate were added to a three-necked round bottom glass flask. The reaction was heated at 42℃with stirring for 4 hours and then cooled naturally.
The reaction solution was centrifuged at 1350g for 0.5 hours to remove large particle products. The supernatant was centrifuged at 18000g for 5 hours, and the supernatant was discarded to obtain blue solid light control particles. The blue solid light-controlling particles were thoroughly dispersed with 2.5 liters of isoamyl acetate.
SEM characterization showed that the blue solid light-controlling particle had a particle length of 280nm, a particle width of 70nm and a particle aspect ratio of 4.
Example 2: preparation of liquid polymers of nonlinear structure
And (3) setting up a 250mL three-necked bottle, a stirring device, a reflux device, a thermometer, an argon device and a water bath pot. The argon valve was opened and a pass of argon was maintained throughout the reaction. 47.08 g of dodecyl methacrylate, 9.15 g of diethylene glycol dimethacrylate are introduced into a three-necked flask, 3.820 g of 1-hexanethiol are added as molecular weight regulator, and finally 38 g of toluene are added as solvent.
Stirring the solution at 200 rpm; after argon is introduced for 20 minutes, the water bath kettle is opened for heating, and the reaction temperature is controlled to be 60 ℃. At this temperature, a solution of 0.380 g azobisisobutyronitrile in 20mL toluene was added to a three necked flask and the reaction was started. The reaction time was 21 hours. Heating was then continued to reflux and maintained at reflux for 3 hours.
And (5) cooling after the reaction is finished. The solution was poured into a round bottom flask and distilled at 100deg.C for 3 hours to remove the solvent and unreacted starting materials, giving a liquid polymer product of nonlinear structure (called LP-2). The peak molecular weight (Mp) was 6900 as determined by gel chromatography (GPC); the dynamic viscosity at 20 degrees celsius was 12300cp as measured with a rotational viscometer; the measurement results are shown in Table 1.
Into a 250 ml round bottom glass flask, 40 g of LP-2 was added, and 250 ml of the isoamyl acetate dispersion of the blue solid light controlling particles prepared in the above example 1 was added in portions, isoamyl acetate was removed by a rotary evaporator, and finally the treatment was continued at 80 ℃ for 3 hours by using the rotary evaporator, the mass of the solid light controlling particles was calculated after weighing, then an appropriate amount of LP-2 was added, and uniformly mixed, so that the solid light controlling particles/LP-2=1/8, and the suspension containing the solid light controlling particles was referred to as LCP-2.
Example 3: preparation of liquid polymers of nonlinear structure
The procedure of example 2 was followed except that dodecyl methacrylate was replaced with dodecyl acrylate. The liquid polymer product resulting in a nonlinear structure is called LP-3. The suspension of solid light-controlling particles obtained after addition of the solid light-controlling particles is referred to as LCP-3.
The LP-3 peak molecular weight (Mp) prepared in example 3 was determined to be 2900 by gel chromatography (GPC); the dynamic viscosity at 20 degrees celsius was 1400cp as measured with a rotational viscometer; the measurement results are shown in Table 1.
Example 4: preparation of liquid polymers of nonlinear structure
And (3) setting up a 250mL three-necked bottle, a stirring device, a reflux device, a thermometer, an argon device and a water bath pot. The argon valve was opened and a pass of argon was maintained throughout the reaction. 31.08 g of n-hexyl methacrylate, 6.15 g of ethylene glycol dimethacrylate and 4.80 g of hydroxyethyl methacrylate are added to a three-necked flask; 3.82 g of 1-hexanethiol were added as molecular weight regulator, and finally 38 g of toluene were added as solvent.
Stirring the solution at 200 rpm; after argon is introduced for 20 minutes, the water bath kettle is opened for heating, and the reaction temperature is controlled to be 60 ℃. At this temperature, a solution of 0.380 g azobisisobutyronitrile in 20mL toluene was added to a three necked flask and the reaction was started. The reaction time was 21 hours. Heating was then continued to reflux and maintained at reflux for 3 hours.
And (5) cooling after the reaction is finished. The solution was poured into a round bottom flask and distilled at 100deg.C for 3 hours to remove the solvent and unreacted starting materials, giving a liquid polymer product of nonlinear structure (called LP-4).
The liquid polymer product LP-4 of the nonlinear structure obtained in example 4 was analyzed by gel chromatography to obtain a molecular weight distribution chart shown in FIG. 3. As can be seen from FIG. 3, the peak molecular weight (Mp) was 5723 by gel chromatography (GPC); the dynamic viscosity at 20 degrees celsius was 24000cp measured with a rotational viscometer; the measurement results are shown in Table 1.
The liquid polymer product LP-4 of nonlinear structure obtained in example 4 was analyzed by infrared spectroscopy to obtain the FTIR spectrum of LP-4 as shown in FIG. 4: therein 3521.0cm -1 Is the telescopic vibration absorption peak of hydroxyl group, 2924.0cm -1 ，2854.0cm -1 Is a methylene telescopic vibration absorption peak of 1731.6cm -1 Is an ester carbonyl telescopic vibration absorption peak of 1466.9cm -1 Is methylene groupC-H bending absorption peak of 1378.4m -1 Is C-H symmetrical bending vibration absorption peak of methyl group, 1239.6cm -1 And 1152.3cm -1 Is C-O telescopic vibration absorption peak; 721.9m -1 Is the internal rocking absorption peak of methylene basal plane in long-chain alkyl.
Into a 250 ml round bottom glass flask, 40 g of LP-4 was added, and 250 ml of the isoamyl acetate dispersion of the blue solid light controlling particles prepared in the above example 1 was added in portions, isoamyl acetate was removed by a rotary evaporator, and finally the treatment was continued at 80 ℃ for 3 hours using a rotary evaporator, the mass of the solid light controlling particles was calculated after weighing, then an appropriate amount of LP-4 was added, and uniformly mixed, so that solid light controlling particles/LP-4=1/8, and a suspension containing blue solid light controlling particles was obtained, which was referred to as LCP-4.
Example 5: preparation of liquid polymers of nonlinear structure
The procedure of example 4 was followed except that diethylene glycol dimethacrylate was used instead of ethylene glycol dimethacrylate. The liquid polymer product resulting in a nonlinear structure is called LP-5. The peak molecular weight (Mp) was 3700 as determined by gel chromatography (GPC); the dynamic viscosity at 20 degrees celsius was 8000cp as measured with a rotational viscometer; the measurement results are shown in Table 1. The suspension of solid light-controlling particles obtained after addition of the solid light-controlling particles is referred to as LCP-5.
Example 6: preparation of liquid polymers of nonlinear structure
The procedure of example 5 was followed except that 47.08 g of dodecyl methacrylate was used instead of n-hexyl methacrylate. The liquid polymer product resulting in a nonlinear structure is called LP-6. The peak molecular weight (Mp) was 2700 as measured by gel chromatography (GPC); the dynamic viscosity at 20 degrees celsius was 18000cp as measured with a rotational viscometer; the measurement results are shown in Table 1.
The suspension of solid light-controlling particles obtained after addition of the solid light-controlling particles is referred to as LCP-6.
Example 7: preparation of liquid polymers of nonlinear structure
The procedure of example 6 was followed except that trimethylolpropane trimethacrylate was used instead of diethylene glycol dimethacrylate. The liquid polymer product resulting in a nonlinear structure is called LP-7. The peak molecular weight (Mp) was 2300 as determined by gel chromatography (GPC); dynamic viscosity at 20 degrees celsius was 3600cp measured with a rotational viscometer; the measurement results are shown in Table 1. The suspension of solid light-controlling particles obtained after addition of the solid light-controlling particles is referred to as LCP-7.
Example 8: preparation of liquid polymers of nonlinear structure
The procedure of example 6 was followed except that pentaerythritol tetramethyl acrylate was used in place of diethylene glycol dimethacrylate. The liquid polymer product resulting in a nonlinear structure is called LP-8. The peak molecular weight (Mp) was measured as 3300 by gel chromatography (GPC); the dynamic viscosity at 20 degrees celsius was 4600cp measured with a rotational viscometer; the measurement results are shown in Table 1. The suspension of solid light-controlling particles obtained after addition of the solid light-controlling particles is referred to as LCP-8.
Example 9: preparation of liquid polymers of nonlinear structure
The procedure of example 4 was followed except that ethylene glycol dimethacrylate was replaced with octaethylene glycol dimethacrylate. The liquid polymer product resulting in a nonlinear structure is called LP-9. The peak molecular weight (Mp) was 6500 as determined by gel chromatography (GPC); the dynamic viscosity at 20℃was 15000cp by a rotational viscometer; the measurement results are shown in Table 1. The suspension of solid light-controlling particles obtained after addition of the solid light-controlling particles is referred to as LCP-9.
Example 10: preparation of liquid polymers of nonlinear structure
The procedure of example 4 was followed except that hydroxypropyl methacrylate was used in place of hydroxyethyl methacrylate. The liquid polymer product resulting in a nonlinear structure is called LP-10. The peak molecular weight (Mp) was 5800 as determined by gel chromatography (GPC); the dynamic viscosity at 20℃was 5100cp as measured by a rotational viscometer. The suspension of solid light-controlling particles obtained after adding the solid light-controlling particles is called LCP-10; the measurement results are shown in Table 1.
Comparative example 1: preparation of liquid polymers of Linear Structure
The procedure of example 2 was followed except that 9.15 g of diethylene glycol dimethacrylate was replaced with 4.8 g of hydroxyethyl methacrylate. The liquid polymer product resulting in a linear structure is referred to as LP-1. The peak molecular weight (Mp) was measured by gel chromatography (GPC) to be 3100; the dynamic viscosity at 20 degrees celsius was 1400cp as measured with a rotational viscometer; the measurement results are shown in Table 1. The suspension of solid light-controlling particles obtained after addition of the solid light-controlling particles was designated LCP-1.
Comparative example 2: preparation of a Silicone oil Polymer matrix precursor having unsaturated bonds
To a 1L three neck round bottom glass flask was added 108g of hydroxy terminated dimethyl diphenyl 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, the middle part is provided with mechanical stirring, and the other side is provided with a thermometer. The reaction mixture in the three-necked round bottom glass flask was heated to reflux for 30min, and when a small amount of water was present in the water separator, a solution of 0.26g stannous octoate in 20mL of n-heptane was added. Then, 6g of 3-acryloxypropyl trimethoxysilane was added dropwise for about 5 minutes. Then reacting for 2 hours under the reflux condition, and then immediately adding 60mL of trimethylmethoxysilane as a reaction terminator; the reaction was stopped for 2h and then rapidly cooled to room temperature. 100mL of ethanol and the cooled reaction solution 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 15min. The resulting mixture was poured into a 2L separating funnel, and after standing for several hours, delamination occurred. The lower layer liquid is taken out, and then the lower layer liquid is treated for 3 hours at 70 ℃ by a rotary evaporator to remove low-boiling-point substances, and finally the organic silicone oil with unsaturated bonds, namely the polymer matrix precursor, is obtained.
Comparative example 3: manufacture of LV-1 light valve from LCP-1
0.03 g of photoinitiator 819,2.0 g of solid particle suspension LCP-1,1 g of linear structured liquid polymer LP-1 and 7.0 g of unsaturated bond-containing silicone oil polymer matrix precursor prepared in comparative example 2 were crosslinked and mixed uniformly to obtain a matrix emulsion of the optical control layer.
Doctor blade type automatic coating coater (MSK-AFA-III type, MTI Co) for the above prepared light control layer matrix emulsionThe preparation) was coated on a PET/ITO transparent electrode with a thickness of 80. Mu.m, and another PET/ITO transparent electrode was coated on the wet film of the light control layer to obtain a wet film containing the light control layer. Curing with X200-150 UV curing machine manufactured by Aventk company under nitrogen atmosphere for 1 min, with UV power of 700W/m 2 Thus obtaining the LV-0 light valve.
When no voltage was applied (off state), LV-1 exhibited a blue hue and the total light transmittance was 0.7%. When a 220 v ac power of 50 hz was applied (on state), LV-1 became clear and the total light transmittance was 69.5%. The specific results are shown in Table 2.
In this comparative example, a transparent conductive film (transparent electrode) was formed on a substrate of a plastic sheet.
The polymer matrix precursor is crosslinked and cured to form a polymer matrix.
Accordingly, the present application also provides a method of manufacturing a light valve, comprising:
providing solid light control particles;
providing a suspension medium;
mixing the solid light control particles with the suspension medium to form a mixture of suspension media containing solid light control particles;
providing a polymer matrix precursor;
mixing an initiator for initiating the cross-linking and curing of the polymer matrix precursor, a mixture of the suspension medium containing the solid light control particles and the polymer matrix precursor to obtain a light control layer matrix emulsion;
coating the light control layer matrix emulsion on a first transparent electrode of a first transparent substrate to form a light control layer wet film;
covering a second transparent electrode on a second transparent substrate on the light control layer wet film; and (3) performing cross-linking curing on the light control layer wet film to obtain the light valve shown in figure 1.
Example 11: manufacture of LV-2 light valves from LCP-2
Was manufactured and tested as in comparative example 3 except that LCP-2 was used instead of LCP-1 and LP-2 was used instead of LP-1, referred to as LV-2, with specific results shown in Table 2.
Example 12: manufacture of LV-3 light valves from LCP-3
Was manufactured and tested as in comparative example 3 except that LCP-3 was used instead of LCP-1 and LP-3 was used instead of LP-1, referred to as LV-3, with specific results shown in Table 2.
Example 13: manufacture of LV-4 light valves from LCP-4
Was manufactured and tested as in comparative example 3 except that LCP-4 was used instead of LCP-1 and LP-4 was used instead of LP-1, referred to as LV-4, with specific results shown in Table 2.
Example 14: manufacture of LV-5 light valves from LCP-5
Was made and tested as in comparative example 3 except that 2 grams of LCP-5 was used instead of 2 grams of LCP-1 and 1 gram of dioctyl phthalate was used instead of 1 gram of LP-1, designated LV-5, with the specific results shown in Table 2.
Example 15: manufacture of LV-6 light valve from LCP-6
Was made and tested as in comparative example 3 except that 2 grams of LCP-6 was used instead of 2 grams of LCP-1 and 1 gram of dioctyl phthalate was used instead of 1 gram of LP-1, designated LV-6, with the specific results shown in Table 2.
Example 16: manufacture of LV-7 light valve from LCP-7
Was made and tested as in comparative example 3 except that 2 grams of LCP-7 was used instead of 2 grams of LCP-1 and 1 gram of dinonyl phthalate was used instead of 1 gram of LP-1, designated LV-7, with the specific results shown in Table 2.
Example 17: manufacture of LV-8 light valve from LCP-8
Was made and tested as in comparative example 3 except that 2 grams of LCP-8 was used instead of 2 grams of LCP-1,1 gram of triisodecyl trimellitate was used instead of 1 gram of LP-1, designated LV-8, with the specific results shown in Table 2.
Example 18: manufacture of LV-9 light valve from LCP-9
Was made and tested as in comparative example 3 except that 2 grams of LCP-9 was used instead of 2 grams of LCP-1,0.5 grams of LP-9 and 0.5 grams of triisodecyl trimellitate was used instead of 1 gram of LP-1, referred to as LV-9, with specific results shown in Table 2.
Example 19: manufacture of LV-10 light valves from LCP-10
Was made and tested as in comparative example 3 except that 2 grams of LCP-10 was used instead of 2 grams of LCP-1,0.5 grams of dibutyl phthalate and 0.5 grams of triisodecyl trimellitate was used instead of 1 gram of LP-1, referred to as LV-10, with specific results shown in Table 2.
Evaluation of liquid polymers of nonlinear structure
LV light valve devices were prepared from the liquid polymer solid light control particle suspensions of nonlinear structures prepared in comparative example 1 and examples 2 to 10, respectively, and were placed in an oven at an air temperature of 105℃to determine the high temperature stability of the different light valve devices. Taking out from the oven after a certain time, standing for 1 hour at room temperature, and testing the total light transmittance before and after the power-on of 220V. As the placing time of the oven is prolonged, the full light transmittance Ton of the electrified state is gradually reduced; the required oven high temperature holding time for the power on state total light transmittance ton=50% is the high temperature settling time of the light valve device, and the results are shown in table 2.
TABLE 1 comparison of liquid Polymer Properties of nonlinear Structure
Table 2 comparison of the stability to high temperatures of the samples
Comparing the high temperature stability time of LV-1 and LV-2 to LV-10 in Table 2, it can be found that the high temperature stability of 105 ℃ of the light valve made of the liquid polymer with the nonlinear structure reaches 2380 hours, and compared with the corresponding high temperature stability of 105 ℃ of the light valve made of the liquid polymer with the linear structure of the comparative example, the high temperature stability of the light valve with the nonlinear structure is remarkably improved, the defect of poor high temperature stability of the light valve in the prior art is overcome, the better technical effect is obtained, the application prospect is good, and the great significance is achieved.
The present application is described above as an embodiment of a light valve having a transparent plastic sheet as a substrate, i.e., a dimming film. Obviously, the inventive idea is also fully applicable to light valves with glass as substrate, i.e. dimming glass.
The type of transparent electrode using glass as a substrate is not particularly limited, and is a conventional conductive glass well 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, ATO (Antimony Tin Oxide, antimony doped tin oxide) conductive glass, or the like.
In addition, the application also provides a dimming glass component, which comprises a first glass plate and a second glass plate, and a dimming film arranged between the first glass plate and the second glass plate; wherein: and a first adhesive clamping layer is arranged between the first glass plate and the dimming film, and/or a second adhesive clamping layer is arranged between the second glass plate and the dimming film.
In the present application, the types of the first glass plate and the second glass plate are not particularly limited, and the transparent glass for the conventional light-adjusting glass assembly, which is well known to those skilled in the art, may be common glass such as inorganic glass and organic glass, or may be 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-clamping layer and the second adhesive-clamping layer are not particularly limited, and are conventional adhesive-clamping layers for light-adjusting glass assemblies, which are well known to those skilled in the art, and may be EVA adhesive films, TPU adhesive films, PVB adhesive films, or functional adhesive films, such as UV-blocking EVA adhesive films, UV-blocking TPU adhesive films, UV-blocking PVB adhesive films, and the like.
In the present invention, the manner of manufacturing the light-adjusting glass assembly is not particularly limited, and may be a conventional glue-clamping manner of the light-adjusting glass assembly in the art, such as glue-clamping in a laminator, or glue-clamping in an autoclave or a glue-clamping box/furnace.
The above examples are given for illustration only and do not limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the 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.
Claims (11)
1. A light valve device comprising a liquid polymer having a nonlinear structure, comprising:
A first transparent substrate having a first surface and a second surface,
a first transparent electrode formed on the first transparent substrate,
a second transparent substrate having a first transparent surface,
a second transparent electrode formed on the second transparent substrate, the first transparent electrode and the second transparent electrode being disposed opposite to each other, and
a light control layer disposed between the first transparent electrode and the second transparent electrode; the light management layer comprises a polymer matrix;
wherein, suspending medium liquid drops are scattered in the polymer matrix, solid light control particles are distributed in the suspending medium liquid drops,
wherein the suspension medium comprises a liquid polymer of nonlinear structure; the nonlinear structure liquid polymer comprises a unit A, a unit B and a unit C; the unit A is selected from methacrylate monomers and/or acrylate monomers; the unit B is selected from a multifunctional methacrylate monomer and/or a multifunctional acrylate monomer; the unit C is selected from hydroxy methacrylate monomers and/or hydroxy acrylate monomers; the mass ratio of the monomers forming unit a, unit B and unit C is 1: (0.01-0.5): (0 to 0.5).
2. A light valve device according to claim 1, wherein the monomers of unit a are of formula (I):
CH 2 =crcoo-R' formula (I);
wherein R is CH 3 Or H; r' is C n H 2n+1 N is an integer of 1 to 18.
3. The light valve device of claim 1, wherein the monomer of unit B is represented by formula (II):
(CH 2 ＝CR 1 COOCH 2 ) m -R 1 ' formula (II);
wherein R is 1 Is CH 3 Or H; r is R 1 ' C a H 2a+2-m O b M is an integer of 2 to 10, a and b are each independently an integer of 0 to 10, a is not less than b, and 2a+2-m is an integer of 0 or more.
4. A light valve device as claimed in claim 1, characterized in that the monomer of unit C is represented by formula (III):
CH 2 ＝CR 2 COO-R 2 ' formula (III);
wherein R is 2 Is CH 3 Or H; r is R 2 ' C q H 2q -OH, q is an integer from 1 to 8.
5. A light valve device as claimed in claim 1, characterized in that the peak molecular weight of the liquid polymer of the nonlinear structure is 2000-7000.
6. A light valve device as claimed in claim 1, characterized in that the mass ratio of the total mass of the suspension medium and the solid light controlling particles to the polymer matrix is 1: (1-10); the mass ratio of the nonlinear structure liquid polymer in the suspension medium to the total mass of the suspension medium is 1: (1-5); the mass ratio of the suspension medium to the solid light control particles is 1: (0.05-0.2).
7. The light valve device of claim 1, wherein the solid light control particles are selected from one or more of oxide nanorods, perovskite nanorods, and polyiodide nanorods; the particle length of the solid light control particles is 50-800 nm; the aspect ratio of the solid light control particles is 2-30;
The suspension medium further comprises a non-conductive liquid;
the non-conductive liquid is at least one selected from fluorocarbon organic compounds, phthalic acid esters, benzene tricarboxylic acid esters, dodecylbenzene, polybutene oil, polyacrylate, polymethacrylate, epoxidized soybean oil and epoxidized linseed oil;
the polymer matrix is formed by crosslinking and curing a silicone oil polymer matrix precursor with unsaturated bonds.
8. The light valve device of claim 1, wherein the first transparent substrate and the second transparent substrate comprise glass sheets; or the first transparent substrate and the second transparent substrate comprise transparent plastic sheets;
the first transparent electrode comprises at least one of PEDOT, ITO, FTO, AZO, FZO, IZO, GZO, a nano Ag wire, conductive graphene and a nano Cu wire; the second transparent electrode includes at least one of PEDOT, ITO, FTO, AZO, FZO, IZO, GZO, a nano Ag wire, conductive graphene, and a nano Cu wire.
9. A light valve device as claimed in claim 1, characterized in that the surface of the first transparent electrode which is not in contact with the first transparent substrate and/or the surface of the second transparent electrode which is not in contact with the second transparent substrate is covered with an insulating layer.
10. A method of manufacturing a light valve device as claimed in claim 1, comprising:
providing solid light control particles;
providing a suspension medium;
mixing the solid light control particles with the suspension medium to form a mixture of suspension media containing solid light control particles;
providing a polymer matrix precursor;
mixing an initiator for initiating the cross-linking and curing of the polymer matrix precursor, a mixture of the suspension medium containing the solid light control particles and the polymer matrix precursor to obtain a light control layer matrix emulsion;
coating the light control layer matrix emulsion on a first transparent electrode of a first transparent substrate to form a light control layer wet film;
covering a second transparent electrode on a second transparent substrate on the light control layer wet film;
and carrying out cross-linking curing on the light control layer wet film to obtain the light valve device.
11. A dimming 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-clamping layer is arranged between the first glass plate and the light valve device, and/or
A second glue layer is arranged between the second glass plate and the light valve device.
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| CN110088650A (en) * | 2016-12-28 | 2019-08-02 | Dic株式会社 | Dispersion and ink composition for ink jet, light conversion layer and the liquid crystal display element for using it |
| CN113568196A (en) * | 2021-07-30 | 2021-10-29 | 浙江精一新材料科技有限公司 | Light valve, method for manufacturing light valve, and light control glass assembly |
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