Dye composition, liquid crystal composition and liquid crystal dimmable device thereof

Abstract

According to the liquid crystal dimmable device disclosed by the invention, through a specially-set functional layer and isolation layer structure, on one hand, the stability of the device to light and heat is improved, and on the other hand, the yield of large-size production is improved. Meanwhile, in combination with a specially set dye combination, high contrast and wide dimming range are realized.

Description

Technical Field

[0001] The present invention relates to the technical field of liquid crystal dimming, and in particular to a dye composition, a liquid crystal composition and a liquid crystal dimming device thereof. Background Art

[0002] Liquid crystal has been discovered by humans since 1888. Because its arrangement can change with the change of applied electric field, it has electrical response characteristics. Liquid crystal materials that form a certain degree of orderly arrangement through surface orientation and other methods have the function of modulating the light passing through it, that is, they have light modulation characteristics. It is precisely because of the electrical response and light modulation characteristics of liquid crystal materials that liquid crystal materials have been widely used in the display field since the 1960s and 1970s. In 1986, Professor West of the Liquid Crystal Institute of Kent State University in the United States publicly reported a liquid crystal dimming device (polymer dispersed liquid crystal, Polymer Dispersed Liquid Crystal, referred to as PDLC) in US Patent US4,685,771, which disperses liquid crystal in polymers. It has the modulation ability of two optical indicators, transmittance and haze. This technology has opened the prelude to the application of liquid crystal in the field of architectural privacy dimming and automotive dimming skylights.

[0003] In 1968, Heilmeier mixed dichroic dyes with liquid crystal materials to prepare guest-host (GH) type dye-liquid crystal mixture devices. Because the dye itself absorbs visible light in a certain band, GH-type film-based or glass-based devices can adjust the light transmittance at a certain color. Precisely because of its ability to modulate light transmittance, the guest-host dye liquid crystal system can be used in building curtain walls, partitions, car skylights, side windows, dimming glasses, virtual reality glasses and other products and optical devices that require dimming functions. By mixing dichroic dyes with different absorption bands, full spectrum absorption in the visible light range of 400-800nm ​​can be achieved. Therefore, the GH-type dimming device can present a nearly black or gray-black substrate, and the light transmittance of the black substrate can be adjusted by adjusting the applied voltage.

[0004] In the field of dimming film or dimming glass, the commonly used dichroic dyes are azo dyes, mainly because of their relatively simple synthesis route, relatively low cost, and their high light absorption efficiency and wide absorption band range. However, azo dyes often have average reliability when used in outdoor environments due to the high activity of the azo group to light. Another commonly used dichroic dye is anthraquinone, which generally shows better light stability and reliability than azo dyes. However, the synthesis cost of anthraquinone dyes is relatively high, and the light absorption efficiency and light absorption band range they show are generally smaller than those of azo dyes. Therefore, their wide application is limited.

[0005] At present, the contrast ratio of liquid crystal dimming devices on the market is generally low. The main reason is that the solubility of dichroic dye compositions on the market in liquid crystals is poor. To improve the contrast ratio, it is necessary to increase the proportion of dichroic dyes added to liquid crystals. Too high a proportion can easily cause dye precipitation during low-temperature storage and use of the device. In addition, the blocking of ultraviolet and infrared light in liquid crystal dimming devices on the market is generally insufficient, and ultraviolet and infrared light have a serious impact on the stability of dichroic dyes, resulting in insufficient reliability of liquid crystal dimming devices and a greatly shortened service life. Summary of the invention

[0006] In view of one or more of the above technical problems, the present invention discloses a liquid crystal dimmable device, which improves the light and heat stability of the device through a specially set functional layer and isolation layer structure, and improves the yield of large-scale production. At the same time, combined with a specially set dichroic dye composition, the solubility of the dichroic dye in the liquid crystal is improved, thereby achieving the optical goals of high contrast and wide dimming range.

[0007] In one aspect of the present invention, in some embodiments of the present invention, a liquid crystal dimmable light device is disclosed, wherein the structure comprises a first hard substrate, a first adhesive layer, a first functional layer, a first flexible substrate layer, a first isolation layer, a first conductive layer, a second isolation layer, a first orientation layer, a liquid crystal layer, a second orientation layer, a third isolation layer, a second conductive layer, a fourth isolation layer, a second flexible substrate layer, a second functional layer, a second adhesive layer, and a second hard substrate layer, wherein the liquid crystal layer comprises a dichroic dye liquid crystal composition and an edge sealant surrounding the dichroic dye liquid crystal composition. The dichroic dye liquid crystal composition comprises a liquid crystal material, a dichroic dye composition, a chiral agent, and an isolation ball.

[0008] Preferably, the first hard substrate layer and / or the second hard substrate layer is selected from any one of glass, acrylic plate or polycarbonate plate, and the inner and outer surfaces thereof may be provided with ultraviolet light and / or infrared light blocking layers.

[0009] Preferably, the first adhesive layer and / or the second adhesive layer is / are selected from any one of polyvinyl butyral, ethylene-vinyl acetate copolymer or optical adhesive.

[0010] Preferably, the first functional layer and / or the second functional layer is selected from any one of a hardened layer that enhances the scratch and wear resistance of the film surface, a coating that has a function of blocking ultraviolet light and / or infrared light, or a film layer that has a function of blocking water vapor in the environment.

[0011] Preferably, the first flexible substrate layer and / or the second flexible substrate layer is selected from any one of polyethylene terephthalate, polycarbonate or cellulose triacetate.

[0012] Preferably, any one of the first isolation layer, the second isolation layer, the third isolation layer and the fourth isolation layer is selected from any one of a silicon oxide coating layer, a silicon nitride coating layer or a silicon oxynitride coating layer. The above isolation layer plays a role in leveling the unevenness of the surface of the first flexible substrate layer and the second flexible substrate layer, secondly plays a role in enhancing the adhesion between the conductive layer and the flexible substrate, and thirdly plays a role in leveling the unevenness of the surface of the first conductive layer and the second conductive layer, reducing the risk of short circuit in large-sized devices and improving the yield rate.

[0013] Preferably, the first conductive layer and / or the second conductive layer is selected from any one of indium tin oxide, polyethylene dioxythiophene or nano silver.

[0014] Preferably, the first alignment layer and / or the second alignment layer may be a coating such as polyimide which can affect the arrangement of liquid crystal molecules after being aligned by friction or light. In addition, conductive polymer film layers similar to polyethylene dioxythiophene or other polymer film layers can form certain grooves under friction to anchor the liquid crystal due to their low surface hardness, and can also be used as the first alignment layer and the second alignment layer.

[0015] In another aspect of the present invention, in some embodiments of the present invention, the liquid crystal layer includes a dichroic dye liquid crystal composition and an edge sealant surrounding the dichroic dye liquid crystal composition. The dichroic dye liquid crystal composition includes a liquid crystal material, a dichroic dye composition, a chiral agent and spacer balls. The edge sealant serves to bond the upper and lower layers of the edge of the film material and prevent the dichroic dye liquid crystal composition from leaking out.

[0016] Preferably, the dichroic dye liquid crystal composition comprises 90-98% by weight of liquid crystal material, 1.5-7% by weight of dichroic dye composition, 0.2-3% by weight of spacer spheres and 0-6% by weight of chiral agent material.

[0017] Preferably, the liquid crystal material is selected from nematic liquid crystal materials.

[0018] Preferably, the diameter of the spacer ball is between 2.5 micrometers and 30 micrometers. The color can be transparent, white, a color close to the liquid crystal layer, or black.

[0019] Preferably, the chiral agent material is selected from S / R811, S / R5011, but is not limited thereto.

[0020] In another aspect of the present invention, the dichroic dye composition comprises the following compounds:

[0021] The compound of formula I accounts for 1% to 60% of the total weight of the dichroic dye composition, and the compound of formula I is the following compound:

[0022]

[0023] The compound of general formula II accounts for 1% to 65% of the total weight of the dichroic dye composition, and the compound of general formula II is the following compound:

[0024]

[0025] The compound of formula III accounts for 0% to 40% of the total weight of the dichroic dye composition, and the compound of formula III is the following compound:

[0026]

[0027] The compound of formula IV accounts for 1% to 60% of the total weight of the dichroic dye composition, and the compound of formula IV is the following compound:

[0028]

[0029] The compound of formula V accounts for 1% to 35% of the total weight of the dichroic dye composition, and the compound of formula V is the following compound:

[0030]

[0031] The compound of formula VI accounts for 1% to 35% of the total weight of the dichroic dye composition, and the compound of formula VI is the following compound:

[0032]

[0033] in,

[0034] R1 is selected from an alkyl group or an alkoxy group having 1 to 8 carbon atoms; R2 is selected from an alkyl group, an alkoxy group or an alkyl-substituted amino group having 1 to 8 carbon atoms; L1 and L2 are selected from -CH3 or -H; m is selected from 1 to 3; X1 is selected from -OC(O)- or -C(O)-O-;

[0035] R3 is selected from alkyl or alkoxy groups with 1 to 8 carbon atoms; R4 is selected from wherein L3 and L4 are selected from -CH3 or -H; L5, L6 and L7 are selected from alkyl groups of 1 to 3 carbon atoms or -H; L8 is selected from alkyl groups of 1 to 8 carbon atoms; n is selected from 1 to 3;

[0036] R5 and R6 are selected from alkyl or alkoxy groups of 1 to 8 carbon atoms; X3 is selected from -OC(O)- or -C(O)-O-; s is selected from 1 to 2;

[0037] R7 and R8 are selected from alkyl groups of 1 to 8 carbon atoms; X4 is selected from -OC(O)-, -C(O)-O- or -C6H4-; t is selected from 1 to 4;

[0038] R9, R 10 and R 11 Selected from alkyl or alkoxy groups having 1 to 9 carbon atoms.

[0039] Preferably, the weight percentage of the compound of general formula I in the dichroic dye composition is 5-50%; the weight percentage of the compound of general formula II in the dichroic dye composition is 5-60%; the weight percentage of the compound of general formula III in the dichroic dye composition is 0-35%; the weight percentage of the compound of general formula IV in the dichroic dye composition is 5-50%; the weight percentage of the compound of general formula V in the dichroic dye composition is 1.5-30%; the weight percentage of the compound of general formula VI in the dichroic dye composition is 1.5-30%.

[0040] Preferably, the compound of general formula I in the dichroic dye composition is selected from

[0041]

[0042]

[0043] One or more of;

[0044] The compound of formula II is selected from

[0045]

[0046] One or more of;

[0047] The compound of formula III is selected from

[0048]

[0049] One or more of;

[0050] The compound of formula IV is selected from

[0051]

[0052] One or more of;

[0053] The compound of formula V is selected from

[0054]

[0055]

[0056] One or more of;

[0057] The compound of formula VI is selected from

[0058]

[0059] One or more of .

[0060] Compared with the prior art, the present invention has the following beneficial effects:

[0061] The technical solution of the present invention obtains a high-contrast liquid crystal dimming device by mixing dichroic dye compounds of general formula I-VI, and improves the light and thermal stability of the device under ultraviolet and infrared light by adding a functional layer, and then avoids the yield loss caused by short circuit between the upper and lower conductive layers during large-scale mass production by setting an isolation layer. The present invention selects a dichroic dye compound containing an ester group -C(O)-O-, while maintaining a sufficient conjugated structure length, and utilizes the characteristics of the oxygen atom in the ester group and the liquid crystal compound to easily form hydrogen bonds, thereby greatly improving the solubility of the dichroic dye compound in the liquid crystal and thus significantly improving the contrast and low-temperature stability of the device. The present invention selects a dichroic dye compound containing a tetrahydroquinoline group, a dihydroquinoline group and a cyclohexyl group, introduces a flexible structure at the end of the rigid conjugated structure, while maintaining a sufficient conjugated structure length, the solubility of the dichroic dye compound in the liquid crystal is improved, thereby significantly improving the contrast and low-temperature stability of the device. The present invention selects dichroic dye compounds containing alkyl substituted amino groups at the end, on the one hand, utilizes the nitrogen atoms therein to form hydrogen bonds with liquid crystal compounds to improve the solubility and thus improve the contrast of the device, and on the other hand, utilizes the electronegativity of the nitrogen atoms to red-shift the absorption wavelength under the same conjugated structure length, thereby avoiding the disadvantage of low solubility caused by increasing the conjugated length of the dichroic dye compound molecules to absorb red light. In the present invention, by selecting anthraquinone dichroic dyes substituted with amino groups and hydroxy groups, the relatively better light and heat stability of the anthraquinone group is utilized to improve the light and heat stability of the overall liquid crystal dimming device, and at the same time, the amino groups and hydroxy groups are easily utilized to form hydrogen bonds with liquid crystal compounds to improve the solubility of the dichroic dye in the liquid crystal, thereby improving the contrast of the device. The present invention improves the contrast of the liquid crystal dimming device, improves the light and heat stability, and improves the yield in the large-scale production process, which is conducive to further promoting the large-scale application of liquid crystal dimming devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] Figure 1 The figure is a schematic diagram of the structure of a liquid crystal dimmable light device according to an embodiment of the present invention.

[0063] Reference numerals:

[0064] 101-first hard substrate layer, 102-first adhesive layer, 103-first functional layer, 104-first flexible substrate layer, 105-first isolation layer, 106-first conductive layer, 107-second isolation layer, 108-first orientation layer, 117-liquid crystal layer, 109-second orientation layer, 110-third isolation layer, 111-second conductive layer, 112-fourth isolation layer, 113-second flexible substrate layer, 114-second functional layer, 115-second adhesive layer, 116-second hard substrate layer, 120-liquid crystal material, 119-dichroic dye composition, 121-chiral agent, 118-isolation ball, 122-edge sealing glue. DETAILED DESCRIPTION

[0065] The scheme in the embodiment of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiment of the present invention. Obviously, the described embodiment is only a part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0066] Example 1

[0067] A liquid crystal dimmable device, the structure of which includes: Figure 1 The stacked arrangement shown is a first hard substrate layer 101, a first adhesive layer 102, a first functional layer 103, a first flexible substrate layer 104, a first isolation layer 105, a first conductive layer 106, a second isolation layer 107, a first orientation layer 108, a liquid crystal layer 117, a second orientation layer 109, a third isolation layer 110, a second conductive layer 111, a fourth isolation layer 112, a second flexible substrate layer 113, a second functional layer 114, a second adhesive layer 115, and a second hard substrate layer 116. The liquid crystal layer 117 includes a dichroic dye liquid crystal composition and an edge sealant 122 surrounding the dichroic dye liquid crystal composition. The dichroic dye liquid crystal composition includes a liquid crystal material 120, a dichroic dye composition 119, a chiral agent 121, and isolation balls 118.

[0068] The first hard base layer 101 and the second hard base layer 116 are made of low-emissivity (Low-E) glass.

[0069] The first adhesive layer 102 and the second adhesive layer 115 are made of polyvinyl butyral (PVB) material.

[0070] The first functional layer 103 and the second functional layer 114 are coating layers having the function of blocking ultraviolet light and / or infrared light.

[0071] The first flexible base layer 104 and the second flexible base layer 113 are made of polyethylene glycol terephthalate (PET) flexible resin film.

[0072] The first isolation layer 105 , the second isolation layer 107 , the third isolation layer 110 and the fourth isolation layer 112 are made of silicon oxide coating.

[0073] The first conductive layer 106 and the second conductive layer 111 are made of indium tin oxide (ITO).

[0074] The first alignment layer 108 and the second alignment layer 109 are made of polyimide (PI) coatings and are rubbed in parallel or anti-parallel directions to achieve horizontal alignment of the liquid crystals.

[0075] The liquid crystal material 120 in the dichroic dye liquid crystal composition uses the WKLC001 liquid crystal of Yantai Xianhua Company, the spacer ball 118 uses the 10 micron diameter of Aibang Technology, and the specific composition of the dichroic dye composition 119 is given in Table 1-Example 1. In the dichroic dye liquid crystal composition, by weight percentage, the liquid crystal material 120 accounts for 94%, the spacer ball 118 accounts for 1%, the chiral agent 121 uses S5011, accounting for 1%, and the dichroic dye composition 119 accounts for 4%.

[0076] The characteristic is that, within the absorption band range of 400-800nm, the dimming device can achieve a contrast ratio CR=14.3.

[0077] Example 2

[0078] A liquid crystal dimmable device, the structure of which includes: Figure 1 The stacked arrangement shown is a first hard substrate layer 101, a first adhesive layer 102, a first functional layer 103, a first flexible substrate layer 104, a first isolation layer 105, a first conductive layer 106, a second isolation layer 107, a first orientation layer 108, a liquid crystal layer 117, a second orientation layer 109, a third isolation layer 110, a second conductive layer 111, a fourth isolation layer 112, a second flexible substrate layer 113, a second functional layer 114, a second adhesive layer 115, and a second hard substrate layer 116. The liquid crystal layer 117 includes a dichroic dye liquid crystal composition and an edge sealant 122 surrounding the dichroic dye liquid crystal composition. The dichroic dye liquid crystal composition includes a liquid crystal material 120, a dichroic dye composition 119, a chiral agent 121, and isolation balls 118.

[0079] The first hard substrate layer 101 and the second hard substrate layer 116 are made of acrylic plates and can be in different colors. The inner and outer surfaces thereof have ultraviolet light and / or infrared light blocking layers.

[0080] The first adhesive layer 102 and the second adhesive layer 115 are made of ethylene-vinylacetate copolymer (EVA).

[0081] The first functional layer 103 and the second functional layer 114 are hardened layers that enhance the scratch and wear resistance of the film surface.

[0082] The first flexible base layer 104 and the second flexible base layer 113 are made of polycarbonate (PC) flexible resin films.

[0083] The first isolation layer 105 , the second isolation layer 107 , the third isolation layer 110 and the fourth isolation layer 112 are made of silicon dioxide coating.

[0084] The first conductive layer 106 is made of ITO, and the second conductive layer 111 is made of polyethylene dioxythiophene (poly (3, 4-ethylenedioxythiophene), PEDOT).

[0085] The first alignment layer 108 and the second alignment layer 109 are made of PI coating and are rubbed in parallel or anti-parallel directions to achieve vertical alignment of the liquid crystal.

[0086] The liquid crystal material 120 in the dichroic dye liquid crystal composition uses the LC051 liquid crystal of Jiangsu Hecheng Company, the spacer ball 118 uses the 18 micron diameter of Aibang Technology, and the specific composition of the dichroic dye composition 119 is given in Table 1-Example 2. In the dichroic dye liquid crystal composition, by weight percentage, the liquid crystal material 120 accounts for 93.5%, the spacer ball 118 accounts for 1.5%, the chiral agent 121 uses S5011, accounting for 0.5%, and the dichroic dye composition 119 accounts for 4.5%.

[0087] The characteristic is that, within the absorption band range of 400-800nm, the dimming device can achieve a contrast ratio CR=17.2.

[0088] Example 3

[0089] A liquid crystal dimmable device, the structure of which includes: Figure 1The stacked arrangement shown is a first hard substrate layer 101, a first adhesive layer 102, a first functional layer 103, a first flexible substrate layer 104, a first isolation layer 105, a first conductive layer 106, a second isolation layer 107, a first orientation layer 108, a liquid crystal layer 117, a second orientation layer 109, a third isolation layer 110, a second conductive layer 111, a fourth isolation layer 112, a second flexible substrate layer 113, a second functional layer 114, a second adhesive layer 115, and a second hard substrate layer 116. The liquid crystal layer 117 includes a dichroic dye liquid crystal composition and an edge sealant surrounding the dichroic dye liquid crystal composition. The dichroic dye liquid crystal composition includes a liquid crystal material 120, a dichroic dye composition 119, a chiral agent 121, and an isolation ball 118.

[0090] The first hard substrate layer 101 and the second hard substrate layer 116 are made of PC boards and can be of different colors. The inner and outer surfaces thereof have ultraviolet light and / or infrared light blocking layers.

[0091] The first adhesive layer 102 and the second adhesive layer 115 are made of optically clear adhesive (OCA).

[0092] The first functional layer 103 and the second functional layer 114 are film layers that can block water vapor in the environment.

[0093] The first flexible base layer 104 and the second flexible base layer 113 are made of triacetylcellulose (TAC).

[0094] The first isolation layer 105 , the second isolation layer 107 , the third isolation layer 110 and the fourth isolation layer 112 are made of a mixed coating of silicon oxide and nitride.

[0095] The first conductive layer 106 is made of nanosilver, and the second conductive layer 111 is made of PEDOT.

[0096] The first alignment layer 108 and the second alignment layer 109 are made of PEDOT coating and are rubbed in parallel or anti-parallel directions to achieve vertical alignment of the liquid crystal.

[0097] The liquid crystal material 120 in the dichroic dye liquid crystal composition uses the WK012 liquid crystal of Beijing Bayi Spacetime Company, the spacer ball 118 uses the 15 micron diameter of Nano Micro Technology, and the specific composition of the dichroic dye composition 119 is given in Table 1-Example 3. In the dichroic dye liquid crystal composition, by weight percentage, the liquid crystal material 120 accounts for 91%, the spacer ball 118 accounts for 1%, the chiral agent 121 uses S811, accounting for 4%, and the dichroic dye composition 119 accounts for 4%.

[0098] The characteristic is that, within the absorption band range of 400-800nm, the dimming device can achieve a contrast ratio CR=16.4.

[0099] Example 4

[0100] A liquid crystal dimmable device, the structure of which includes: Figure 1 The stacked arrangement shown is a first hard substrate layer 101, a first adhesive layer 102, a first functional layer 103, a first flexible substrate layer 104, a first isolation layer 105, a first conductive layer 106, a second isolation layer 107, a first orientation layer 108, a liquid crystal layer 117, a second orientation layer 109, a third isolation layer 110, a second conductive layer 111, a fourth isolation layer 112, a second flexible substrate layer 113, a second functional layer 114, a second adhesive layer 115, and a second hard substrate layer 116. The liquid crystal layer 117 includes a dichroic dye liquid crystal composition and an edge sealant 122 surrounding the dichroic dye liquid crystal composition. The dichroic dye liquid crystal composition includes a liquid crystal material 120, a dichroic dye composition 119, a chiral agent 121, and isolation balls 118.

[0101] The first hard substrate layer 101 and the second hard substrate layer 116 are made of glass material, and have ultraviolet light and / or infrared light blocking layers on their inner and outer surfaces.

[0102] The first adhesive layer 102 and the second adhesive layer 115 are made of PVB material.

[0103] The first functional layer 103 and the second functional layer 114 are selected to be film layers that have the function of blocking water vapor in the environment and blocking ultraviolet light.

[0104] The first flexible base layer 104 and the second flexible base layer 113 are made of PET flexible resin film.

[0105] The first isolation layer 105 , the second isolation layer 107 , the third isolation layer 110 and the fourth isolation layer 112 are made of silicon oxide coating.

[0106] PEDOT is used for the first conductive layer 106 and the second conductive layer 111 .

[0107] The first alignment layer 108 and the second alignment layer 109 are made of PEDOT coating and are rubbed in parallel or anti-parallel directions to achieve horizontal alignment of the liquid crystal.

[0108] The liquid crystal material 120 in the dichroic dye liquid crystal composition uses WK041 liquid crystal from Beijing Bayi Space Technology Co., Ltd., the spacer ball 118 uses 6 micron diameter from Nano Micro Technology, and the specific composition of the dichroic dye composition 119 is given in Table 1-Example 4. In the dichroic dye liquid crystal composition, by weight percentage, the liquid crystal material 120 accounts for 90%, the spacer ball 118 accounts for 2.5%, the chiral agent 121 uses R811, accounting for 5%, and the dichroic dye composition 119 accounts for 2.5%.

[0109] The characteristic is that, within the absorption band range of 400-800nm, the dimming device can achieve a contrast ratio CR=12.6.

[0110] Example 5

[0111] A liquid crystal dimmable device, the structure of which includes: Figure 1 The stacked arrangement shown is a first hard substrate layer 101, a first adhesive layer 102, a first functional layer 103, a first flexible substrate layer 104, a first isolation layer 105, a first conductive layer 106, a second isolation layer 107, a first orientation layer 108, a liquid crystal layer 117, a second orientation layer 109, a third isolation layer 110, a second conductive layer 111, a fourth isolation layer 112, a second flexible substrate layer 113, a second functional layer 114, a second adhesive layer 115, and a second hard substrate layer 116. The liquid crystal layer 117 includes a dichroic dye liquid crystal composition and an edge sealant 122 surrounding the dichroic dye liquid crystal composition. The dichroic dye liquid crystal composition includes a liquid crystal material 120, a dichroic dye composition 119, a chiral agent 121, and isolation balls 118.

[0112] The first hard base layer 101 and the second hard base layer 116 are made of low-emissivity glass.

[0113] The first adhesive layer 102 and the second adhesive layer 115 are made of PVB material.

[0114] The first functional layer 103 and the second functional layer 114 are selected from a hardening layer for enhancing the scratch and wear resistance of the film surface and a film layer with a UV light blocking function.

[0115] The first flexible base layer 104 and the second flexible base layer 113 are made of PC flexible resin film.

[0116] The first isolation layer 105 and the fourth isolation layer 112 are made of silicon oxide coating, and the second isolation layer 107 and the third isolation layer 110 are made of silicon nitride coating.

[0117] ITO is used for the first conductive layer 106 and the second conductive layer 111 .

[0118] The first alignment layer 108 and the second alignment layer 109 are made of PI coating and are rubbed in parallel or anti-parallel directions to achieve horizontal alignment of the liquid crystal.

[0119] The liquid crystal material 120 in the dichroic dye liquid crystal composition uses the WK041 liquid crystal of Beijing Bayi Space-Time Company, the spacer ball 118 uses the 25 micron diameter of Aibang Technology, and the specific composition of the dichroic dye composition 119 is given in Table 1-Example 5. In the dichroic dye liquid crystal composition, by weight percentage, the liquid crystal material 120 accounts for 91.7%, the spacer ball 118 accounts for 0.5%, the chiral agent 121 uses a combination of R5011 and R811, accounting for 1.8%, and the dichroic dye composition 119 accounts for 3.5%.

[0120] The characteristic is that, within the absorption band range of 400-800nm, the dimming device can achieve a contrast ratio CR=15.6.

[0121] Example 6

[0122] A liquid crystal dimmable device, the structure of which includes: Figure 1 The stacked arrangement shown is a first hard substrate layer 101, a first adhesive layer 102, a first functional layer 103, a first flexible substrate layer 104, a first isolation layer 105, a first conductive layer 106, a second isolation layer 107, a first orientation layer 108, a liquid crystal layer 117, a second orientation layer 109, a third isolation layer 110, a second conductive layer 111, a fourth isolation layer 112, a second flexible substrate layer 113, a second functional layer 114, a second adhesive layer 115, and a second hard substrate layer 116. The liquid crystal layer 117 includes a dichroic dye liquid crystal composition and an edge sealant 122 surrounding the dichroic dye liquid crystal composition. The dichroic dye liquid crystal composition includes a liquid crystal material 120, a dichroic dye composition 119, a chiral agent 121, and isolation balls 118.

[0123] The first hard substrate layer 101 and the second hard substrate layer 116 are made of PC boards and can be of different colors. The inner and outer surfaces thereof have ultraviolet light and / or infrared light blocking layers.

[0124] The first adhesive layer 102 and the second adhesive layer 115 are made of OCA.

[0125] The first functional layer 103 and the second functional layer 114 are hardened layers that enhance the scratch and wear resistance of the film surface and have colors.

[0126] The first flexible base layer 104 and the second flexible base layer 113 are made of PC flexible resin film.

[0127] The first isolation layer 105 and the fourth isolation layer 112 are not used in this embodiment, and the second isolation layer 107 and the third isolation layer 110 are silicon oxide coating layers.

[0128] ITO is used for the first conductive layer 106 and the second conductive layer 111 .

[0129] The first alignment layer 108 and the second alignment layer 109 are made of PI coating and are rubbed in parallel or anti-parallel directions to achieve vertical alignment of the liquid crystal.

[0130] The liquid crystal material 120 in the dichroic dye liquid crystal composition uses the WKLC001 liquid crystal of Yantai Xianhua Company, the spacer ball 118 uses the 5-micron diameter of Aibang Technology, and the specific composition of the dichroic dye composition 119 is given in Table 1-Example 6. In the dichroic dye liquid crystal composition, the liquid crystal material 120 accounts for 95.5% by weight, the spacer ball 118 accounts for 1.5%, the chiral agent 121 is not used in this embodiment, and the dichroic dye composition 119 accounts for 3%.

[0131] The characteristic is that, within the absorption band range of 400-800nm, the dimming device can achieve a contrast ratio CR=11.0.

[0132] Embodiment 7-9

[0133] A liquid crystal dimmable device, the structure of which includes: Figure 1 The stacked arrangement shown is a first hard substrate layer 101, a first adhesive layer 102, a first functional layer 103, a first flexible substrate layer 104, a first isolation layer 105, a first conductive layer 106, a second isolation layer 107, a first orientation layer 108, a liquid crystal layer 117, a second orientation layer 109, a third isolation layer 110, a second conductive layer 111, a fourth isolation layer 112, a second flexible substrate layer 113, a second functional layer 114, a second adhesive layer 115, and a second hard substrate layer 116. The liquid crystal layer 117 includes a dichroic dye liquid crystal composition and an edge sealant 122 surrounding the dichroic dye liquid crystal composition. The dichroic dye liquid crystal composition includes a liquid crystal material 120, a dichroic dye composition 119, a chiral agent 121, and isolation balls 118.

[0134] The first hard base layer 101 and the second hard base layer 116 are made of low-emissivity glass.

[0135] The first adhesive layer 102 and the second adhesive layer 115 are made of PVB material.

[0136] The first functional layer 103 and the second functional layer 114 are coating layers having the function of blocking ultraviolet light and / or infrared light.

[0137] The first flexible base layer 104 and the second flexible base layer 113 are made of PET flexible resin film.

[0138] The first isolation layer 105 and the fourth isolation layer 112 are not used in this embodiment, and the second isolation layer 107 and the third isolation layer 110 are silicon oxide coating layers.

[0139] ITO is used for the first conductive layer 106 and the second conductive layer 111 .

[0140] The first alignment layer 108 and the second alignment layer 109 are made of PI coating and are rubbed in parallel or anti-parallel directions to achieve horizontal alignment of the liquid crystal.

[0141] The liquid crystal material 120 in the dichroic dye liquid crystal composition uses the LC051 liquid crystal of Jiangsu Hecheng Company, the spacer ball 118 uses the 10 micron diameter of Aibang Technology, and the specific composition of the dichroic dye composition 119 is given in Table 1-Examples 7-9. In the dichroic dye liquid crystal composition, by weight percentage, the liquid crystal material 120 accounts for 92.1%, the spacer ball 118 accounts for 1%, the chiral agent 121 uses S5011, accounting for 0.9%, and the dichroic dye composition 119 accounts for 6%.

[0142] It is characterized in that, within the absorption band range of 400-800nm, the dimming device, Example 7 can achieve a contrast ratio CR=20.0, Example 8 can achieve a contrast ratio CR=19.0, and Example 9 can achieve a contrast ratio CR=22.2.

[0143] Table 1 Specific composition and test results of the dichroic dye composition of the embodiment

[0144]

[0145]

[0146] Note: T1-light transmittance in bright state; T2-light transmittance in dark state; CR-contrast ratio, CR=T1 / T2.

[0147] Comparative Example 1

[0148] The dichroic dye composition includes the following dye compounds (in weight percent):

[0149] 17.5%

[0150] 14.5% 23.7% 25.6% It accounts for 18.7%.

[0151] Comparative Example 2

[0152] The dichroic dye composition includes the following dye compounds (in weight percent):

[0153] 8.3%

[0154] Accounting for 24.4%,

[0155] 27.9%

[0156] 12.7%

[0157] It accounts for 26.7%.

[0158] The comparative examples were prepared into dichroic dye liquid crystal compositions according to the above components and proportions, wherein the liquid crystal materials, chiral agents, and spacer balls were selected the same as in Examples 7-9, and the addition ratio of the chiral agents and spacer balls was also the same as in Examples 7-9. The contrast CR of the dichroic dye liquid crystal compositions of each comparative example was tested, and the proportions and test results of the dichroic dye liquid crystal compositions of each example were summarized as shown in Table 2.

[0159] Table 2 Proportions and test results of dichroic dye compositions of Examples and Comparative Examples

[0160]

[0161] Table 3 shows the test results of whether the dichroic dye liquid crystal composition of each embodiment and comparative example is crystallized from the liquid crystal after being stored at low temperature for 100 hours.

[0162] Table 3 Low temperature storage test results of the embodiments and comparative examples

[0163]

[0164] It can be seen from the formulas of the embodiments and comparative examples and the data of Tables 2 and 3 that, compared with the comparative examples, the embodiments 1-9 of the present invention all show better low temperature stability, and no abnormality of crystallization occurs under the test conditions, which ensures that the liquid crystal dimming device can be stored at a lower temperature. In addition, due to the limitation of solubility, the dye composition in the comparative example cannot be added to the liquid crystal material at a higher ratio, which further leads to the low optical contrast of the liquid crystal dimming device. Since the dichroic dye compound containing ester group -C(O)-O- is selected in Examples 1 to 9 of the present invention, while maintaining a sufficient conjugated structure length, the characteristics of the oxygen atom in the ester group and the liquid crystal compound that easily forms hydrogen bonds are utilized, and the solubility of the dichroic dye compound in the liquid crystal is greatly improved, thereby significantly improving the contrast and low temperature stability of the device. For example, the structure of the D1-2 dye compound in Comparative Example 1 is close to that of the general formula I in the embodiment, and the main difference is the lack of an ester group, which limits its solubility in the liquid crystal material. In Examples 1 to 9 of the present invention, by selecting dichroic dye compounds containing tetrahydroquinoline groups, dihydroquinoline groups and cyclohexyl groups, a flexible structure is introduced at the end of the rigid conjugated structure, while maintaining a sufficient conjugated structure length, the solubility of the dichroic dye compound in the liquid crystal is improved, thereby significantly improving the contrast and low temperature stability of the device. At the same time, in Examples 1 to 9, by selecting dichroic dye compounds containing alkyl substituted amino groups at the end, on the one hand, the nitrogen atoms therein are used to form hydrogen bonds with the liquid crystal compound to improve the solubility and thus improve the contrast of the device, and on the other hand, the electronegativity of the nitrogen atom can be used to red-shift the absorption wavelength under the same conjugated structure length, thereby avoiding the disadvantage of low solubility caused by increasing the conjugated length of the dichroic dye compound molecule to absorb red light. For example, the structure of the D1-5 dye compound in Comparative Example 1 is similar to that of the general formula II in the embodiment, and the main differences are that the ester group is missing, and the tetrahydroquinoline group or dihydroquinoline group is not used at the end. Even if there is an amino group as the end group to generate hydrogen bonding, it still cannot effectively improve its solubility in the liquid crystal material. For example, the dye compounds D2-2 and D2-5 in Comparative Example 2 use a CN group with a greater electronegativity than the amino end group in Examples 1-9 in order to absorb red light. However, because their molecular structure does not incorporate a flexible ester group, a tetrahydroquinoline group, a dihydroquinoline group or a cyclohexyl group, their solubility in liquid crystal materials is poor.

[0165] In Examples 1 to 9 of the present invention, amino- and hydroxy-substituted anthraquinone dichroic dyes are selected to improve the light and heat stability of the overall liquid crystal dimming device by utilizing the relatively better light and heat stability of the anthraquinone group. At the same time, amino and hydroxyl groups are easily formed with liquid crystal compounds to improve the solubility of the dichroic dye in the liquid crystal, thereby improving the contrast of the device. Table 4 shows the light and heat stability of the dichroic dyes in Examples 1 to 9 of the present invention and Comparative Examples 1 to 2 using 1 mW / cm 2The contrast ratio CR changes before and after 500 hours of xenon lamp simulating sunlight irradiation. It is not difficult to find that with the introduction of anthraquinone dye compounds with better light and thermal stability, compared with the comparative example, the embodiment of the present invention shows a smaller contrast loss and significantly improves the light and thermal stability of the device.

[0166] Table 4 Light and heat stability test of examples and comparative examples

[0167]

[0168] The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. Any equivalent transformation made by using the description and content of the present invention, or directly or indirectly applied in other related technical fields, is also included in the patent protection scope of the present invention.

Claims

1. A dichroic dye composition, characterized in that Includes the following compounds: The compound of formula I accounts for 1% to 60% of the total weight of the dichroic dye composition, and the compound of formula I is the following compound: The compound of general formula II accounts for 1% to 65% of the total weight of the dichroic dye composition, and the compound of general formula II is the following compound: The compound of formula III accounts for 0% to 40% of the total weight of the dichroic dye composition, and the compound of formula III is the following compound: The compound of formula IV accounts for 1% to 60% of the total weight of the dichroic dye composition, and the compound of formula IV is the following compound: The compound of formula V accounts for 1% to 35% of the total weight of the dichroic dye composition, and the compound of formula V is the following compound: The compound of formula VI accounts for 1% to 35% of the total weight of the dichroic dye composition, and the compound of formula VI is the following compound: in, R1 is selected from an alkyl group or an alkoxy group having 1 to 8 carbon atoms; R2 is selected from an alkyl group, an alkoxy group or an alkyl-substituted amino group having 1 to 8 carbon atoms; L1 and L2 are selected from -CH3 or -H; m is selected from 1 to 3; X1 is selected from -OC(O)- or -C(O)-O-; R3 is selected from alkyl or alkoxy groups with 1 to 8 carbon atoms; R4 is selected from wherein L3 and L4 are selected from -CH3 or -H; L5, L6 and L7 are selected from alkyl groups of 1 to 3 carbon atoms or -H; L8 is selected from alkyl groups of 1 to 8 carbon atoms; n is selected from 1 to 3; R5 and R6 are selected from alkyl or alkoxy groups of 1 to 8 carbon atoms; X3 is selected from -OC(O)- or -C(O)-O-; s is selected from 1 to 2; R7 and R8 are selected from alkyl groups of 1 to 8 carbon atoms; X4 is selected from -OC(O)-, -C(O)-O- or -C6H4-; t is selected from 1 to 4; R9, R 10 and R 11 Selected from alkyl or alkoxy groups having 1 to 9 carbon atoms.

2. The dichroic dye composition according to claim 1, wherein The weight percentage of the compound of formula I in the dichroic dye composition is 5-50%; the weight percentage of the compound of formula II in the dichroic dye composition is 5-60%; The weight percentage of the compound of formula III in the dichroic dye composition is 0-35%; The weight percentage of the compound of formula IV in the dichroic dye composition is 5-50%; The weight percentage of the compound of formula V in the dichroic dye composition is 1.5-30%; The weight percentage of the compound of formula VI in the dichroic dye composition is 1.5-30%.

3. The dichroic dye composition according to claim 1 or 2, characterized in that The compound of formula I is selected from One or more of; The compound of formula II is selected from One or more of; The compound of formula III is selected from One or more of; The compound of formula IV is selected from One or more of; The compound of formula V is selected from One or more of; The compound of formula VI is selected from One or more of .

4. A dichroic dye liquid crystal composition, characterized in that: The dichroic dye liquid crystal composition comprises 90-98% by weight of a liquid crystal material, 1.5-7% by weight of the dichroic dye composition as described in any one of claims 1 to 3, 0.2-3% by weight of spacer spheres and 0-6% by weight of a chiral agent material.

5. A liquid crystal dimmable device, characterized in that: The liquid crystal dimmable light device comprises a first hard substrate, a first adhesive layer, a first functional layer, a first flexible substrate layer, a first isolation layer, a first conductive layer, a second isolation layer, a first orientation layer, a liquid crystal layer, a second orientation layer, a third isolation layer, a second conductive layer, a fourth isolation layer, a second flexible substrate layer, a second functional layer, a second adhesive layer, and a second hard substrate layer, wherein the liquid crystal layer comprises the dichroic dye liquid crystal composition as claimed in claim 4 and an edge sealing glue surrounding the dichroic dye liquid crystal composition.

6. The liquid crystal dimmable light device according to claim 5, characterized in that: The first hard substrate layer and / or the second hard substrate layer is selected from any one of glass, acrylic plate or polycarbonate plate, and the inner and outer surfaces of the first hard substrate layer and / or the second hard substrate layer are provided with ultraviolet light and / or infrared light blocking layers.

7. The liquid crystal dimmable device according to claim 5, characterized in that: The first adhesive layer and / or the second adhesive layer is / are selected from any one of polyvinyl butyral, ethylene-vinyl acetate copolymer or optical adhesive.

8. The liquid crystal dimmable light device according to claim 5, characterized in that: The first functional layer and / or the second functional layer is selected from any one of a hardening layer that enhances the scratch and wear resistance of the film surface, a coating that has a function of blocking ultraviolet light and / or infrared light, or a film layer that has a function of blocking water vapor in the environment.

9. The liquid crystal dimmable light device according to claim 5, characterized in that: The first flexible substrate layer and / or the second flexible substrate layer is / are selected from any one of polyethylene terephthalate, polycarbonate or cellulose triacetate.

10. The liquid crystal dimmable light device according to claim 5, characterized in that: Any one of the first isolation layer, the second isolation layer, the third isolation layer and the fourth isolation layer is selected from any one of a silicon oxide coating layer, a silicon nitride coating layer or a silicon oxynitride coating layer.

11. The liquid crystal dimmable device according to claim 5, characterized in that: The first conductive layer and / or the second conductive layer is / are selected from any one of indium tin oxide, polyethylene dioxythiophene or nano silver.

12. The liquid crystal dimmable device according to claim 5, characterized in that: The first alignment layer and / or the second alignment layer is / are selected from any one of polyimide and polyethylene dioxythiophene conductive polymers.

Images