KR20170049851A - Polymer Dispersed Liquid Crystal Film Comprising UV Curable Resins With SiliconeBased Acrylate and UrethaneBased Acrylate And Preparing Methods Thereof - Google Patents
Polymer Dispersed Liquid Crystal Film Comprising UV Curable Resins With SiliconeBased Acrylate and UrethaneBased Acrylate And Preparing Methods Thereof Download PDFInfo
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- 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
- G02F1/13—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 liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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Abstract
The present invention relates to a polymer dispersed liquid crystal film comprising two or more kinds of photosetting resins excellent in liquid crystal, adhesive strength and optical properties, and a method for producing the same. The present invention is produced by mixing two or more types of photosetting resins having excellent adhesive strength and optical properties, thereby exhibiting improved effects such as haze and transparency, compared with a film prepared by incorporating one kind of a cured resin. In addition, the present invention is applicable to various industrial products fields such as smart windows, TVs, and automobiles that require transparent and opaque functions.
Description
The present invention relates to a polymer dispersed liquid crystal film comprising a liquid crystal, a silicon-based acrylate photocurable resin and a urethane-based acrylate photocurable resin, and a method for producing the same.
Polymer dispersed liquid crystal (PDLC) is a polymer dispersed liquid crystal (PDLC) in which droplets of a liquid crystal having a micro size are dispersed in a polymer matrix, so that a voltage is applied in response to a voltage applied from the outside without using a polarizer The liquid crystal is aligned in the direction of the electric field applied with the liquid crystal and is aligned with the direction of the transmitted light to transmit the light and the liquid crystal is irregularly arranged in the state in which the voltage is not applied and does not coincide with the traveling direction of the transmitted light It causes scattering of light. In other words, it can be said that it is a device which can transmit light in accordance with whether or not a voltage is applied, so that it can be controlled in a transparent state and opaque state.
Generally, a PDLC film is formed by forming a polymer dispersed liquid crystal composition including liquid crystal, oligomer, monomer, photoinitiator and additives, between two transparent substrate plates having a transparent electrode layer formed thereon, and heating and drying the polymer dispersed liquid crystal layer formed between the transparent substrate plates Ultraviolet rays are irradiated to form a polymer material matrix through a curing reaction, and liquid crystals of liquid crystal are dispersed in a polymer material matrix.
Meanwhile, 'Smart Window' refers to a window that freely adjusts the transmittance of sunlight coming from the outside to reduce energy loss and improve energy efficiency, thereby providing a pleasant environment for the user and simultaneously satisfying sensibility and functionality. Smart Window was a passive method that shields or transmits solar light of a certain wavelength by incorporating specific substances into glass by chemical vapor deposition method or sputtering method. Recently, however, active windows are being used to adjust the transmittance of visible light by artificially using liquid crystal. It can be switched instantly with simple on / off switch operation. When the outside temperature goes up, the window automatically becomes darker and the outside heat is prevented from penetrating into the inside of the building. When the outside temperature falls, the room temperature becomes transparent and the outside heat flows into the inside of the building. In other words, by adjusting the solar absorption rate according to the external temperature, it saves energy according to the season. Smart window is widely applied not only to transportation of automobiles, buses, airplanes and trains, but also to information display fields such as houses, interior, and display semiconductors by using ultraviolet shielding property, visible light control function and infrared ray reflection characteristic have. As a result, SmartWind, as a future technology for energy saving and high functionality, continuously develops its applications in advanced countries such as the US, Europe, and Japan, and is actually commercialized in some fields.
The conventional polymer dispersed liquid crystal composition contains one type of photo-curable resin and can improve the optical characteristics of the PDLC film by controlling the curing rate of the curable resin or adjusting the content of liquid crystal and resin. However, such a simple method alone has limitations in improving the clarity, haze, and adhesive strength performance of the PDLC film.
Currently, Korean Patent Laid-Open No. 10-2015-0097327 entitled " Prepolymer Composition for Polymer Dispersion Type Liquid Crystal Composite Film, Polymer Dispersed Liquid Crystal Composite Film and Polymer Dispersed Liquid Crystal Film Using the Same, " Smart Window Film and Smart with Improved Adhesion Durability and Transmittance Uniformity A method for manufacturing a window film United States Patent Application Publication No. 10-2015-0083949 and U.S. Patent Publication No. 2010-0279125 disclose a substrate-free polymer dispersed liquid crystal; fiber, fabric, and device thereof; and methods thereof ", a number of reports have reported that a single type of photo-curable resin is used in the production of a polymer dispersed liquid crystal film, but no technology using two types of photo-curing resins has been reported yet.
The present inventors have made efforts to develop a method capable of simultaneously improving the light transmittance, haze and adhesive strength of polymer dispersed liquid crystal films. As a result, it has been found that the urethane-based acrylate photocurable resin and the silicon- The present inventors have accomplished the present invention by confirming that a polymer dispersed liquid crystal film excellent in light transmittance, haze and adhesive strength can be prepared from a polymer dispersed liquid crystal film prepared by one conventional photocurable resin.
Accordingly, an object of the present invention is to provide a polymer dispersed liquid crystal film comprising a liquid crystal, a silicon-based acrylate photocurable resin and a urethane-based acrylate photocurable resin.
Another object of the present invention is to provide a method for manufacturing a liquid crystal display, comprising the steps of: (a) mixing a liquid crystal, a silicon-based acrylate photocurable resin and a urethane-based acrylate photocurable resin to prepare a mixture for a polymer dispersed liquid crystal film liquid crystal layer; (b) applying the polymer dispersed liquid crystal film liquid crystal layer mixture prepared in the step (a) to a first transparent substrate having a transparent electrode layer and then forming a second transparent substrate having a transparent electrode layer thereon to prepare a polymer dispersed liquid crystal film Producing; And (c) photo-curing the produced polymer dispersed liquid crystal film with ultraviolet rays.
It is another object of the present invention to provide a polymer dispersed liquid crystal film produced by a method of producing a polymer dispersed liquid crystal film.
Another object of the present invention is to provide a smart window including a polymer dispersed liquid crystal film produced by a method of producing a polymer dispersed liquid crystal film.
According to one aspect of the present invention, there is provided a polymer dispersed liquid crystal film comprising a liquid crystal, a silicon-based acrylate photocurable resin and a urethane-based acrylate photocurable resin.
The present inventors prepared a film by mixing a urethane-based acrylate photocurable resin and a silicon-based acrylate photocurable resin with a liquid crystal in order to develop a method capable of simultaneously improving light permeability, haze and adhesive strength of a polymer dispersed liquid crystal film. As a result, it was confirmed that the polymer dispersed liquid crystal film made of one photocurable resin was superior in light transmittance, haze and adhesive strength.
The term " polymer dispersed liquid crystal film " in the present specification includes a polymer dispersed liquid crystal layer including a liquid crystal and a polymer photo-curable resin, and the polymer dispersed liquid crystal layer is formed between two transparent substrates including a transparent electrode layer Means a film in which a polymer dispersed liquid crystal layer is located.
In order to improve the reliability and optical characteristics of the polymer dispersed liquid crystal film, the present invention is characterized in that two kinds of resins having excellent reliability characteristics and excellent optical and electrical properties, namely, a urethane acrylate photocurable resin and a silicone acrylate photocurable resin And a photo-curable resin is mixed. The droplet size of the liquid crystal in the polymer dispersed liquid crystal layer is adjusted by the difference in the curing speed of the curable resin to further improve the optical property value.
In the present invention, any liquid crystal used in the art can be used without limitation, but a nematic, a smectic or a cholesteric liquid crystal can be used. Preferably, the liquid crystal used in the present invention Is a nematic liquid crystal. For example, currently available German EM or E7, E63 from Merck, and ROTN 404 from Hoffman La Roche can be used.
According to a preferred embodiment of the present invention, the present invention comprises a liquid crystal comprising 50-70 wt%, a urethane-based acrylate photocurable resin 20-40 wt%, and a silicone-based acrylate photocurable resin 10-20 wt% 50 to 60% by weight of a liquid crystal, 35 to 40% by weight of a urethane-based acrylate photocurable resin, and 15 to 20% by weight of a silicone-based acrylate photocurable resin.
In the present invention, the content of the liquid crystal in the polymer dispersed liquid crystal layer is preferably 50 to 70% by weight, and most preferably 50 to 60% by weight. In addition, the remaining content excluding the content of the liquid crystal is the content of the photocurable resin.
In the specification of the present invention, the term " oligomer " means a molecule formed by repeatedly connecting one or more kinds of atoms or atom groups (these are called constituent units) to several to ten, Refers to an oligomer, which varies with increasing or decreasing number of constituent units. The oligomer is a compound that determines the water resistance and adhesion by causing a polymerization reaction instantaneously by bonding with a monomer which is one of the main components of the resin.
In the present invention, any urethane-based acrylate photocurable resin that can be used in the art can be used without limitation, but the urethane-based acrylate photocurable resin in the present invention is preferably urethane acrylate.
In addition, any silicone-based acrylate photocurable resin that can be used in the present invention can be used without limitation in the present invention, but silicon-based acrylate photocurable resin in the present invention is preferably silicon acrylate.
The content of the oligomer in the present invention is preferably 40 to 90% by weight based on the total amount of the photocurable resin component.
In the specification of the present invention, the term " Monomer " means a compound which is used as a reactive diluent of an oligomer to impart workability of a resin formulation and to be polymerized itself by ultraviolet irradiation to act as a crosslinking agent between polymers , Oligomers and photoinitiators.
In the present invention, monomers can be used, and any monomers available in the polymer dispersed liquid crystal film in the art can be used without limitation.
Preferably, the monomers used in the present invention are monofunctional or polyfunctional hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), 1,6-hexanediol acrylate (HDDA), tripropylene glycol di Acrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), acrylic acid (AA) and 2-propenyic acid 2-carboxyethyl.
The content of the monomer used in the present invention is preferably about 10 to 60% by weight based on the total amount of the components of the curable resin. If the amount is less than 10% by weight, the curing rate is lowered. If the amount exceeds 60% do.
In the specification of the present invention, the term " photoinitiator " is added to UV resin (here, all paint, coationg, ink, paint, adhesive and sealant using ultraviolet rays are collectively called) Absorbing and initiating the polymerization half. Depending on the type of resin, the photoinitiator is used to initiate photopolymerization by converting the monomer, oligomer and free radicals into the polymeric material after curing by adding the energy required for photopolymerization.
In the present invention, a photoinitiator may be included. As such photoinitiator, compounds known to be commonly used in the art may be used without limitation. For example, benzophenone, benzoyl methyl benzoate benzoate, acetophenone, 2,4-diheptyl thioxanthone, 2-chloro thioxanthone, ethyl anthraquinone, 1- (1-Hydroxy-cyclohexyl-phenyl-ketone, Irgacure 184 available from Ciba Co., Ltd. as a commercial product).
Preferably, the photoinitiator used in the present invention is selected from the group consisting of benzophenone, benzoyl methyl benzoate, acetophenone, 2,4-diethyl thioxanthone, At least one photoinitiator selected from the group consisting of 2-chloro thioxanthone, ethyl anthraquinone and 1-hydroxy-cyclohexyl-phenyl-ketone, .
The content of the photoinitiator used in the present invention may be about 0.01-5% by weight based on the total amount of the curable resin component. If the content of the photoinitiator is large, the curing rate is too high and the unreacted initiator remains to deteriorate the weatherability. If the content is less than 0.01% by weight, the unreacted material is produced and the physical properties are deteriorated.
According to another aspect of the present invention, there is provided a process for producing a liquid crystal display, comprising the steps of: (a) mixing a liquid crystal, a silicone acrylate photocurable resin and a urethane acrylate photopolymerizable resin to prepare a mixture for a polymer dispersed liquid crystal film liquid crystal layer; (b) applying the polymer dispersed liquid crystal film liquid crystal layer mixture prepared in the step (a) to a first transparent substrate having a transparent electrode layer and then forming a second transparent substrate having a transparent electrode layer thereon to prepare a polymer dispersed liquid crystal film Producing; And (c) photo-curing the produced polymer dispersed liquid crystal film with ultraviolet rays.
Step (a) of the present invention is a step of producing a polymer dispersed liquid crystal film liquid crystal layer (refer to FIG. 1), which is a step of mixing a liquid crystal, a silicone acrylate photocurable resin and a urethane acrylate photocurable resin . The photocurable resin used in the present invention preferably contains an oligomer, a monomer, and a photoinitiator.
In the present invention, oligomers, monomers and photoinitiators contained in the photocurable resin are the same as those used in the polymer dispersed liquid crystal film, and duplicated description thereof is omitted in order to avoid excessive description in the specification.
The method for producing a polymer dispersed liquid crystal film according to the present invention is characterized by using two types of photo-curable resins which exhibit different adhesive strengths and optical characteristics. The photocurable resin is characterized in that curing conditions such as heat curing and UV curing are different or curing rates are different under the same curing conditions. Among them, two or more kinds of resins are UV curing type resins, It is preferable to make a difference of several seconds to several tens of seconds. By using such characteristics, the droplet size of the liquid crystal in the polymer dispersed liquid crystal layer can be adjusted to further improve the optical property value.
The step (a) of the present invention is characterized in that liquid crystal, urethane-based acrylate photocurable resin and silicon-based acrylate photocurable type repair are mixed at an optimal mixing ratio.
According to a preferred embodiment of the present invention, the step (a) is a step of mixing 50-70% by weight of liquid crystal, 20-40% by weight of urethane-based acrylate photocurable resin and 10-20% by weight of silicone- More preferably 50-60% by weight of liquid crystals, 35-40% by weight of urethane-based acrylate photocurable resin and 15-20% by weight of silicone-based acrylate photocurable resin.
In the step (b) of the present invention, the transparent electrode layer is positioned or coated on the surface of the first transparent substrate, and the polymer dispersed liquid crystal layer mixture prepared by the step (a) is injected thereinto, 2 transparent substrate to produce a polymer dispersed liquid crystal film. It is preferable that the first transparent substrate and the second transparent substrate have a transparent electrode layer, and any transparent substrate used in the art can be used without limitation.
Preferably, the transparent electrode layer in the step (b) is at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO 2 ), carbon nanotubes, (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), and tin oxide (SnO 2 ), and more preferably at least one selected from the group consisting of indium tin oxide And more preferably a transparent electrode layer composed of at least one compound selected from the group consisting of indium tin oxide (ITO) and indium zinc oxide (IZO), and most preferably indium tin oxide (ITO) As shown in FIG.
According to another aspect of the present invention, there is provided a polymer dispersed liquid crystal film produced by the above polymer dispersed liquid crystal film production method.
Since the present invention is a polymer dispersed liquid crystal film produced by the method of producing a polymer dispersed liquid crystal film, the description common to both of them is omitted in order to omit the description of the present invention.
According to another aspect of the present invention, there is provided a smart window including a polymer dispersed liquid crystal film produced by the method of producing a polymer dispersed liquid crystal film.
The present invention relates to a smart window including a polymer dispersed liquid crystal film produced by the above-described method for producing a polymer dispersed liquid crystal film, wherein a process for manufacturing a film into a smart window or a manufacturing method thereof is manufactured by a method known in the art .
Disclosed is a polymer dispersed liquid crystal film comprising two or more kinds of photosetting resins excellent in liquid crystal, adhesive strength and optical properties, and a method for producing the same.
The present invention is produced by mixing two or more types of photocurable resins having excellent adhesive strength and optical properties, thereby exhibiting improved effects on properties such as haze and permeability, compared with films prepared by incorporating one type of cured resin.
In addition, the present invention is applicable to various industrial products fields such as smart windows, TVs, and automobiles that require transparent and opaque functions.
1 is a schematic view of a polymer dispersed liquid crystal layer in a polymer dispersed liquid crystal film produced by the present invention.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .
Example 1: PDLC film production with excellent adhesive strength and optical properties
(Ebecryl 350, Allnex) containing 57.1% by weight of a nematic liquid crystal compound (E7, Merck), 30.1% by weight of a urethane-based acrylate photocurable resin containing a urethane acrylate oligomer (Ebecryl 8210, Allnex) And 12.9% by weight of a silicone-based acrylate photocurable resin were mixed to prepare a polymer dispersed liquid crystal composition.
Liquid crystal, urethane Acrylate Photocurable resin and silicone system Acrylate PDLC film manufacture with photocurable resin
The polymer dispersed liquid crystal composition was coated on one side of a transparent substrate (PET film) having a transparent electrode layer (ITO: Indium Tin Oxide) formed thereon, and then the same transparent substrate as the transparent substrate on which the transparent electrode layer was formed was coated with a roller And the polymer dispersed liquid crystal composition was coated thereon. Then, a transparent base plate including the prepared polymer dispersed liquid crystal layer was irradiated with ultraviolet rays to cure the polymer dispersed liquid crystal layer to manufacture a PDLC film including a nematic liquid crystal, a urethane acrylate photocurable resin and a silicone acrylate photocurable resin Respectively.
PDLC film manufacture comprising nematic liquid crystal and urethane-based acrylate photocurable resin
A polymer dispersed liquid crystal composition was prepared by mixing 57% by weight of a nematic liquid crystal compound and 43% by weight of a urethane-based acrylate photocurable resin.
PDLC film manufacture comprising nematic liquid crystal and silicon-based acrylate photocurable resin
A polymer dispersed liquid crystal composition was prepared by mixing 57% by weight of a nematic liquid crystal compound and 43% by weight of a silicone-based acrylate photopolymerizable resin.
Comparative Example 1: Comparison of optical characteristics
Table 1 shows the optical characteristics of a urethane-based acrylate photocurable resin (A) such as adhesion strength, a silicon-based acrylate photocurable resin (B) having excellent optical properties, and a PDLC film produced by mixing the A and B resins together As a result, it was found that the haze and the permeability characteristics were improved when two kinds of resins A and B were mixed together, as compared with the case of using the resins A and B alone (Table 1).
As shown in Table 1, it was found that when the two kinds of resins were mixed together in the case of haze, both the ON and OFF states were improved compared with the cases where the resins A and B alone were used, However, it was confirmed that it was greatly improved in the OFF state.
B: PDLC film containing silicon-based acrylate photocurable resin and nematic liquid crystal
A + B: Urethane-based acrylate Photocurable resin, silicon-based acrylate Photocurable resin and PDLC film containing nematic liquid crystal
Comparative Example 2: Comparison of adhesion strength
The adhesion strength of the film can be confirmed by Table 2, and it can be seen that the adhesive strength of the A resin is higher than that of the B resin. In addition, the adhesive strength when mixed with the liquid crystal is higher than that of the resin B, even though the adhesion strength of the resin A is much lower than that of the resin alone. It can be seen that the adhesion strength of the film (A + B) prepared by mixing the two kinds of resins with liquid crystal was slightly higher than that when A and B were used alone.
B resin: silicon-based acrylate photo-curable resin having excellent optical properties
A: PDLC film containing urethane-based acrylate photocurable resin and nematic liquid crystal
B: PDLC film containing silicon-based acrylate photocurable resin and nematic liquid crystal
A + B: Urethane-based acrylate Photocurable resin, silicon-based acrylate Photocurable resin and PDLC film containing nematic liquid crystal
In conclusion, the polymer dispersed liquid crystal film of the present invention exhibits both excellent optical and adhesive strength characteristics when used alone by mixing a resin having excellent adhesive strength and a resin having excellent optical properties.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the present invention. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (17)
(b) applying the polymer dispersed liquid crystal film liquid crystal layer mixture prepared in step (a) to a first transparent substrate having a transparent electrode layer and then forming a second transparent substrate having a transparent electrode layer thereon to prepare a polymer dispersed liquid crystal film Producing; And
(c) photo-curing the prepared polymer dispersed liquid crystal film with ultraviolet light.
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| KR101909541B1 (en) * | 2017-11-14 | 2018-10-18 | (주)이노큐디 | Method for fabricating Quantum Dot Film, Quantum Dot Film prepared thereby, Wavelength Converting Film and Diaplay comprising the Film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101909541B1 (en) * | 2017-11-14 | 2018-10-18 | (주)이노큐디 | Method for fabricating Quantum Dot Film, Quantum Dot Film prepared thereby, Wavelength Converting Film and Diaplay comprising the Film |
| US11634627B2 (en) | 2017-11-14 | 2023-04-25 | Inno Qd Co., Ltd | Method for manufacturing quantum dot film comprising encapsulated quantum dots uniformly dispersed therein, quantum dot film manufactured thereby and wavelength conversion sheet and display comprising same |
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