CN107300818B - Liquid crystal composite film with writing display function and preparation method thereof - Google Patents
Liquid crystal composite film with writing display function and preparation method thereof Download PDFInfo
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- CN107300818B CN107300818B CN201710623210.XA CN201710623210A CN107300818B CN 107300818 B CN107300818 B CN 107300818B CN 201710623210 A CN201710623210 A CN 201710623210A CN 107300818 B CN107300818 B CN 107300818B
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- G—PHYSICS
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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
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- G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/139—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent
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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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- G—PHYSICS
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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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133784—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by rubbing
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- 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
- G02F1/13—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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13392—Gaskets; Spacers; Sealing of cells spacers dispersed on the cell substrate, e.g. spherical particles, microfibres
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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
- G02F1/13—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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13398—Spacer materials; Spacer properties
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Abstract
The invention belongs to the field of liquid crystal display, and particularly discloses a liquid crystal composite film with a writing display function and a preparation method thereof. This liquid crystal composite film with write and show function includes from last to down in proper order: the lower surface of the PET transparent film is plated with an ITO layer, the PVA insulating orientation layer, the liquid crystal/polymer/interval microsphere composite layer and the upper surface of the PET black film is plated with an ITO layer. According to the liquid crystal composite film with the writing display function and the preparation method thereof, due to the addition of the PVA insulating orientation layer, the two conducting layers are not in short circuit risk, so that the yield and the service life of the product are greatly improved, the production cost is reduced, the driving voltage of the liquid crystal film is reduced, and the key technical indexes such as the brightness, the contrast and the like of the film can be improved.
Description
Technical Field
The invention belongs to the field of liquid crystal display, and particularly relates to a liquid crystal composite film with a writing display function and a preparation method thereof.
Background
The liquid crystal composite film with the writing display function can replace writing tools such as blackboards or whiteboards and the like applied to the fields of education, office and the like in the future. Such a film utilizes the bistable property of liquid crystals and has the property of exhibiting a light-reflecting state under writing pressure, the writing being completely erased when a voltage is applied. Specifically, the film can realize perfect handwriting writing only by reflecting external light during writing, thereby realizing the purpose of reducing the power consumption of products. Secondly, only need can write with the instrument of similar fingertip when this kind of film is written, do not use any consumptive material, especially can let mr take the chalk dust that traditional chalk brought, ensure mr's healthy. Moreover, the film has good clearing effect and extremely high clearing efficiency, can clear by one key, and is far superior to the prior blackboard and whiteboard.
At present, the traditional liquid crystal composite film adopted by manufacturers for producing liquid crystal writing pads has the structure that a liquid crystal polymer is directly filled between a PET transparent film and a PET black film, and the structure has the advantages of simple production process and short production period, but has a plurality of defects, such as very small distance between two layers of ITO films, contact short circuit risk, low product yield, short service life, high driving voltage and the like. In order to overcome the defects of the traditional liquid crystal composite film, the conventional method is to increase the monomer content, reduce the risk by increasing the size of the solid microspheres and the polymer content, but the improvement is not obvious, and the increase of the size of the solid microspheres can increase the distance between ITO layers, so that the driving voltage can be increased; increasing the polymer content results in a decrease in the regularity of the liquid crystal alignment, which in turn affects the brightness of the liquid crystal reflection and the overall contrast, which greatly limits the use of liquid crystal writing tablets.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides the liquid crystal composite film with the writing display function and the preparation method thereof, wherein the two conductive layers do not have short circuit risk, the production cost is reduced, and the driving voltage of the liquid crystal film is reduced.
The invention is realized by the following technical scheme:
the utility model provides a liquid crystal composite film with write and show function, includes from last to down in proper order: the lower surface of the PET transparent film is plated with an ITO layer, the PVA insulating orientation layer, the liquid crystal/polymer/interval microsphere composite layer and the upper surface of the PET black film is plated with the ITO layer; the thickness of the PET transparent film plated with the ITO layer is 100-188 microns, the haze is 10% -30%, and the surface resistivity is 100-500 ohms; the thickness of the PET black film plated with the ITO layer is 188 microns, and the surface resistivity is 500 ohms at 100-; the thickness of the PVA insulating layer orientation layer is 0.1-5 microns; the thickness of the liquid crystal/polymer/spacing microsphere composite layer is equal to the diameter of the spacing microspheres.
The liquid crystal/polymer/interval microsphere composite layer comprises the following components in percentage by weight: the birefringence is more than 0.18, the clearing point is less than 135 ℃, the melting point is more than minus 40 ℃ and the nematic liquid crystal is 83-97%, the chiral compound is 2-3%, the ultraviolet polymerizable monomer is 1-12%, the photoinitiator is 0.1-1%, and the size of the spacing microsphere is 3-25 microns and 0.1-1%.
The spacing microspheres are polystyrene microspheres or polymethyl methacrylate microspheres; the nematic liquid crystal is one of SLC1717, SLC151512 or BNHR49000, the chiral compound is R5011, and the photoinitiator is IRGACURE 651.
The ultraviolet polymerizable monomer comprises the following components in percentage by weight: 0-12% of 3,5, 5-trimethyl hexyl acrylate, 0-12% of iso-glacial methacrylate, 0-12% of lauryl acrylate, 0-12% of ethylene glycol diacrylate and 0-12% of beta-hydroxyethyl methacrylate.
The preparation method of the liquid crystal composite film with the writing display function comprises the following steps:
(1) preparing a piece of PET transparent film with the lower surface plated with an ITO layer and a piece of PET black film with the same size as the PET transparent film and the upper surface plated with the ITO layer;
(2) preparing a PVA insulating orientation layer on the surface of the ITO layer on the lower surface of the PET transparent film;
(3) preparing a liquid crystal/polymer/interval microsphere composite layer between the PVA insulating orientation layer obtained in the step (2) and the ITO layer on the upper surface of the PET black film to obtain a liquid crystal composite film blank;
(4) cutting the liquid crystal composite film blank obtained in the step (3) into film square sheets; the length of the film square sheet is 0.1-1.25 m, and the width of the film square sheet is 0.1-1.25 m;
(5) placing one side of the PET transparent film of the film square sheet obtained in the step (4) upwards, using a high-precision film cutting machine to perform edge cutting treatment on the PET transparent film of each film square sheet, turning over the film square sheet, using the high-precision film cutting machine to perform edge cutting treatment on the PET black film, wherein the cut width of the PET transparent film and the PET black film is 0.1-5 cm during edge cutting so as to lead out a circuit;
(6) scrubbing the edge cutting position of the film square sheet by using the non-woven fabric soaked by ethanol until the liquid crystal/polymer/interval microsphere composite layer and the PVA insulating orientation layer are cleaned, so as to lead out a circuit;
(7) and (4) uniformly coating sealing glue on the edge cutting part of the film square sheet prepared in the step (6), and standing for 5-10 minutes after coating is finished to obtain the liquid crystal composite film with the writing and displaying functions.
The preparation method of the PVA insulating orientation layer comprises the following steps:
(2-1) dissolving a certain amount of PVA in hot water at the temperature of 90-100 ℃, heating for 4-7 hours, and preparing a PVA aqueous solution with the mass concentration of 1-20%;
(2-2) uniformly coating the PVA aqueous solution prepared in the step (1) on the surface of the ITO layer on the lower surface of the PET transparent film through a coating dryer, and controlling the thickness and concentration of the PVA aqueous solution coating layer TO control the thickness of the final PVA insulating layer; after coating, the coating is sent into vacuum heating equipment to be dried for 1 to 120 minutes under the vacuum condition of 80 to 100 ℃;
and (2-3) carrying out orientation treatment on the surface of the PVA insulating layer through a friction orientation device to enable the surface of the PVA to form parallel channels, wherein the orientation rate is 1-5 m/min, and the orientation times are 1-5 times, so that the PVA insulating orientation layer is obtained.
The preparation method of the liquid crystal/polymer/interval microsphere composite layer comprises the following steps:
the components of the liquid crystal/polymer/interval microsphere composite layer are mixed and injected between a PVA insulating orientation layer on the lower surface of a PET transparent film and an ITO layer on the upper surface of a PET black film through a full-automatic film laminating machine, and the mixture is subjected TO polymerization reaction by ultraviolet irradiation through an ultraviolet curing device and then is cured and molded TO form the liquid crystal/polymer/interval microsphere composite layer.
The mixing method of the components of the liquid crystal/polymer/interval microsphere composite layer comprises the following steps: mixing the components of the liquid crystal polymer together according to a certain proportion, mixing the components in an ultrasonic water bath at the temperature of 60-80 ℃ for 1-10 minutes, and then taking out the mixture and oscillating the mixture on an oscillator for 1-10 minutes.
Wherein, the ultraviolet wavelength irradiated by the ultraviolet light is 365 nanometers, the polymerization power is 1-10 milliwatts per square centimeter, the polymerization time is 1-60 minutes, and the production speed is 0.5-5 meters per minute.
The specific method for controlling the thickness of the final PVA insulating layer by controlling the thickness and concentration of the PVA aqueous solution coating in the step (2) comprises the following steps: the thickness of the PVA aqueous solution coating is controlled to be 10-100 microns, and the coating speed is controlled to be 1-5 m/min.
The properties and effects of the components adopted by the invention are as follows:
and (3) coating the ITO layer on the PET transparent film: the film is a transparent film with a certain haze, the haze is used for reducing reflection and improving the visual angle and the contrast of a display function, and the ITO conductive layer is used as one of electrodes for driving liquid crystal texture change.
PVA (polyvinyl alcohol) insulating orientation layer: the PVA insulating orientation layer solves the problem that two layers of electrodes are easy to contact and short-circuit, and the PVA material is easy to coat and erase and can be connected with a circuit after being erased; the PVA material has the other advantages that a regular channel can be formed simply by friction, the formation of the channel can be beneficial to the orientation of liquid crystal molecules along the channel direction, the orientation integrity is higher, the higher liquid crystal orientation integrity can effectively improve the light reflection rate, and further improve the writing brightness.
Liquid crystal: the liquid crystal composite film adopts a liquid crystal system which is different from the prior liquid crystal writing board patent and has three liquid crystal texture states, a planar liquid crystal texture is presented at a writing position by utilizing the pressure orientation effect, a nematic liquid crystal texture is presented when an electric field is applied, a smectic phase liquid crystal texture is presented after the electric field is removed, the liquid crystal use temperature range is wider, and the liquid crystal composite film is suitable for environments such as classrooms, offices, outdoors and the like.
Polymer (b): the liquid crystal composite film uses the polymerization monomer and the initiator, a polymer system is formed by ultraviolet initiated polymerization after film covering, the existence of the polymer system can play a role in anchoring the orientation state of liquid crystal, so that the planar texture presented by the liquid crystal texture under the action of pressure can be effectively maintained, the existence of the polymer system can anchor the function of the spacing microspheres, the microspheres can not be agglomerated again in the use process of the liquid crystal film, and the thickness of written notes can be adjusted by adjusting the number of the polymers.
Spacer microspheres: the spacing microspheres are used for controlling the thickness of the liquid crystal layer in the film covering process, and the thickness of written notes can be adjusted according to the number of the spacing microspheres.
And (3) coating the ITO layer on the PET black film: the ITO conductive layer is used as one of the electrodes for driving the liquid crystal texture change, and the black color is used for absorbing visible light, avoiding reflection and improving the contrast.
Chiral compound: the nematic liquid crystal is converted into cholesteric liquid crystal, and the cholesteric liquid crystal texture can present a plane texture under the action of pressing.
Ultraviolet polymerizable monomer: a polymer network is formed under the action of an initiator.
Photoinitiator (2): ultraviolet light is absorbed to initiate polymerization of the ultraviolet polymerizable monomers to form a polymer network.
The liquid crystal composite film with the writing display function and the preparation method thereof have the beneficial effects that:
(1) the advantages of the added insulating layer are that:
the PVA insulating layer is creatively introduced, so that the two ITO layers do not have short circuit risk, the yield and the service life of the product are greatly improved, and the driving voltage of the composite film is reduced; the PVA insulating layer has larger friction force than the ITO layer, has a limiting effect on the liquidity of the liquid crystal layer, and can effectively reduce the doping amount of polymers in the liquid crystal layer, thereby improving key technical indexes such as brightness, contrast and the like of the liquid crystal film; due to the addition of the PVA insulating layer, the small-size interval microspheres can be used, so that the use amount of liquid crystal can be effectively reduced, the production cost is reduced, and the driving voltage of the liquid crystal film is reduced.
(2) The advantages of rubbing orientation are used:
the orientation layer is arranged on the PET transparent film with the lower surface plated with the conductive layer, so that the PET transparent film is arranged and oriented along a bit channel left by friction after being subjected to external pressure, and the arrangement and orientation are more regular than those without the orientation layer, and further key technical indexes such as brightness, contrast and the like of the liquid crystal film can be improved.
(3) The advantage of using PVA as the insulating orientation layer:
the PVA material is selected because PVA is easy to coat, easy to form film, high in chemical stability, high in transparency, easy to clean, high in insulating property and easy to orient. Because the liquid crystal composite film has outstanding contribution to solving the problem of easy contact short circuit between two layers of electrodes, although the addition of the insulating layer plays an insulating role, the difficulty is caused by an external circuit of the electrodes. The PVA material can solve the problem, is easy to coat and erase, and can be connected with a circuit after being erased. The PVA material has the other advantages that a regular channel can be formed simply by friction, the formation of the channel can be beneficial to the orientation of liquid crystal molecules along the channel direction, the orientation integrity is higher, the higher liquid crystal orientation integrity can effectively improve the light reflection rate, further improve the writing brightness, and is very suitable for serving as an insulating orientation layer.
(4) The advantages of using nematic liquid crystal with wide temperature range and large birefringence (delta n):
the liquid crystal composite film adopts nematic liquid crystal with large birefringence (delta n), and according to a formula delta lambda ═ delta nP in a selective reflection mechanism, the adoption of the liquid crystal is proved to be capable of effectively reflecting a wider optical waveband, so that key technical indexes such as brightness, contrast and the like of the liquid crystal film can be improved; the liquid crystal system with three liquid crystal texture states is used, a planar liquid crystal texture is presented at a writing position by utilizing a pressure orientation effect, a nematic liquid crystal texture is presented when an electric field is applied, a smectic phase liquid crystal texture is presented after the electric field is removed, the liquid crystal service temperature range is wide, and the liquid crystal system is suitable for environments such as all classrooms, offices, outdoors and the like.
(5) The advantages of using a series of uv polymerizable monomers:
a series of ultraviolet polymerizable monomers can form a polymer network through ultraviolet polymerization, and can anchor the screw pitch of the chiral compound, so that the uneven distribution of the screw pitch of the chiral compound is ensured, and the reflection wave width is increased. In addition, the increase of the polymer network can make the handwriting thinner and obtain better writing effect.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a schematic view of the structure of the liquid crystal alignment at the writing point of the film according to the present invention;
FIG. 2 is a schematic diagram of the structure of the liquid crystal alignment when the thin film is applied with an electric field to erase the writing.
In the figure, 1, a PET transparent film with an ITO layer plated on the lower surface, 2, a PVA insulating orientation layer, 3, a liquid crystal/polymer/interval microsphere composite layer, and 4, a PET black film with an ITO layer plated on the upper surface.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited thereto, and the preparation methods in the examples are all conventional ones and will not be described in detail.
Example 1:
as shown in fig. 1-2, the liquid crystal composite film with writing display function of the present embodiment includes, from top to bottom: the PET film comprises a PET transparent film 1 with an ITO layer plated on the lower surface, a PVA insulating orientation layer 2, a liquid crystal/polymer/interval microsphere composite layer 3 and a PET black film 4 with an ITO layer plated on the upper surface.
The liquid crystal composite film with the writing display function has the following parameters of each layer structure:
in the liquid crystal composite film having a writing display function, the composition of the liquid crystal polymer layer was as follows (in 100 kg, the same applies hereinafter):
the particle size of the polystyrene microsphere is 3 microns.
The preparation method of the liquid crystal composite film with the writing display function comprises the following steps:
(1) preparing a piece of PET transparent film with the lower surface plated with an ITO layer and a piece of PET black film with the same size as the PET transparent film and the upper surface plated with the ITO layer;
(2) preparing a PVA insulating orientation layer on the surface of the ITO layer on the lower surface of the PET transparent film;
(3) preparing a liquid crystal/polymer/interval microsphere composite layer between the PVA insulating orientation layer obtained in the step (2) and the ITO layer on the upper surface of the PET black film to obtain a liquid crystal composite film blank;
(4) cutting the liquid crystal composite film blank obtained in the step (3) into film square sheets; the length of the film square piece is 1.25 meters, and the width of the film square piece is 1.1 meters;
(5) placing one side of the PET transparent film of the film square sheet obtained in the step (4) upwards, using a high-precision film cutting machine to perform edge cutting treatment on the PET transparent film of each film square sheet, turning over the film square sheet, using the high-precision film cutting machine to perform edge cutting treatment on the PET black film, wherein the cut width of the PET transparent film and the PET black film is 0.1-5 cm during edge cutting so as to lead out a circuit;
(6) scrubbing the cut part with non-woven fabric soaked with ethanol until the liquid crystal/polymer/interval microsphere composite layer and the PVA insulating orientation layer are cleaned away so as to lead out a circuit;
(7) and (4) uniformly coating 502 glue on the edge cutting part of the film square sheet prepared in the step (6), and standing for 9 minutes after coating is finished to obtain the liquid crystal composite film with the writing and displaying functions.
The preparation method of the PVA insulating orientation layer comprises the following steps:
(2-1) dissolving a certain amount of PVA in water at 90 ℃, heating for 4 hours, and preparing a PVA aqueous solution with the mass concentration of 3%;
(2-2) uniformly coating the PVA aqueous solution prepared in the step (1) on the surface of the I TO layer on the lower surface of the PET transparent film at a coating speed of 2 m/min by using a coating dryer, wherein the thickness of the PVA aqueous solution coating is 10 microns, and then heating and drying the PVA aqueous solution in a vacuum environment at the temperature of 80 ℃ for 10 min;
and (2-3) carrying out orientation treatment on the surface of the PVA insulating layer by using a rubbing orientation device, wherein the orientation rate is 5 m/min, and the orientation times are 5 times, so that parallel channels are formed on the surface of the PVA, and the PVA insulating orientation layer is obtained.
The preparation method of the liquid crystal polymer layer comprises the following steps:
(3-1) mixing the components of the liquid crystal/polymer/interval microsphere composite layer together according to a proportion, mixing the components in an ultrasonic water bath at the temperature of 60 ℃ for 10 minutes, and then taking out the mixture and oscillating the mixture on an oscillator for 10 minutes;
(3-2) injecting the mixed liquid crystal/polymer/interval microsphere composite layer components between a PVA insulating orientation layer on the lower surface of a PET transparent film and an ITO layer on the upper surface of a PET black film through a full-automatic film laminating machine, and curing and molding after ultraviolet light irradiation polymerization reaction by an ultraviolet light curing device to form a liquid crystal/polymer/interval microsphere composite layer; the wavelength of the ultraviolet light is 365 nanometers, the polymerization power is 10 milliwatts per square centimeter, the polymerization time is 5 minutes, and the production speed is 3 meters per minute.
Example 2:
as shown in fig. 1-2, the liquid crystal composite film with writing display function of the present embodiment includes, from top to bottom: the PET film comprises a PET transparent film 1 with an ITO layer plated on the lower surface, a PVA insulating orientation layer 2, a liquid crystal/polymer/interval microsphere composite layer 3 and a PET black film 4 with an ITO layer plated on the upper surface.
The liquid crystal composite film with the writing display function has the following parameters of each layer structure:
in the liquid crystal composite film having a writing display function, the composition of the liquid crystal polymer layer was as follows (in 100 kg, the same applies hereinafter):
the particle size of the polystyrene microsphere is 5 microns.
The preparation method of the liquid crystal composite film with the writing display function comprises the following steps:
(1) preparing a piece of PET transparent film with the lower surface plated with an ITO layer and a piece of PET black film with the same size as the PET transparent film and the upper surface plated with the ITO layer;
(2) preparing a PVA insulating orientation layer on the surface of the ITO layer on the lower surface of the PET transparent film;
(3) preparing a liquid crystal/polymer/interval microsphere composite layer between the PVA insulating orientation layer obtained in the step (2) and the ITO layer on the upper surface of the PET black film to obtain a liquid crystal composite film blank;
(4) cutting the liquid crystal composite film blank obtained in the step (3) into film square sheets; the length of the film square sheet is 0.5 meter, and the width of the film square sheet is 0.5 meter;
(5) placing one side of the PET transparent film of the film square sheet obtained in the step (4) upwards, using a high-precision film cutting machine to perform edge cutting treatment on the PET transparent film of each film square sheet, turning over the film square sheet, using the high-precision film cutting machine to perform edge cutting treatment on the PET black film, wherein the cut width of the PET transparent film and the PET black film is 0.1-5 cm during edge cutting so as to lead out a circuit;
(6) scrubbing the cut part with non-woven fabric soaked with ethanol until the liquid crystal/polymer/interval microsphere composite layer and the PVA insulating orientation layer are cleaned away so as to lead out a circuit;
(7) and (4) uniformly coating 502 glue on the edge cutting part of the film square sheet prepared in the step (6), and standing for 10 minutes after coating is finished to obtain the liquid crystal composite film with the writing and displaying functions.
The preparation method of the PVA insulating orientation layer comprises the following steps:
(2-1) dissolving a certain amount of PVA in water at the temperature of 90 ℃, heating for 7 hours, and preparing a PVA aqueous solution with the mass concentration of 15%;
(2-2) uniformly coating the PVA aqueous solution prepared in the step (1) on the surface of the I TO layer on the lower surface of the PET transparent film at a coating speed of 4 m/min by using a coating dryer, wherein the thickness of the PVA aqueous solution coating is 90 microns, and then heating and drying the PVA aqueous solution in a vacuum environment at the temperature of 80 ℃ for 10 minutes;
and (2-3) carrying out orientation treatment on the surface of the PVA insulating layer by using a rubbing orientation device, wherein the orientation rate is 5 m/min, and the orientation times are 2 times, so that parallel channels are formed on the surface of the PVA, and the PVA insulating orientation layer is obtained.
The preparation method of the liquid crystal polymer layer comprises the following steps:
(3-1) mixing the components of the liquid crystal/polymer/interval microsphere composite layer together according to a proportion, mixing for 4 minutes in an ultrasonic water bath at 60 ℃, and then taking out and oscillating for 10 minutes on an oscillator;
(3-2) injecting the mixed liquid crystal/polymer/interval microsphere composite layer components between a PVA insulating orientation layer on the lower surface of a PET transparent film and an ITO layer on the upper surface of a PET black film through a full-automatic film laminating machine, and curing and molding after ultraviolet light irradiation polymerization reaction by an ultraviolet light curing device to form a liquid crystal/polymer/interval microsphere composite layer; the wavelength of the ultraviolet light is 365 nanometers, the polymerization power is 5 milliwatts per square centimeter, the polymerization time is 40 minutes, and the production speed is 0.5 meter per minute.
Example 3:
as shown in fig. 1-2, the liquid crystal composite film with writing display function of the present embodiment includes, from top to bottom: the PET film comprises a PET transparent film 1 with an ITO layer plated on the lower surface, a PVA insulating orientation layer 2, a liquid crystal/polymer/interval microsphere composite layer 3 and a PET black film 4 with an ITO layer plated on the upper surface.
The liquid crystal composite film with the writing display function has the following parameters of each layer structure:
in the liquid crystal composite film having a writing display function, the composition of the liquid crystal polymer layer was as follows (in 100 kg, the same applies hereinafter):
the particle size of the polystyrene microsphere is 15 microns.
The preparation method of the liquid crystal composite film with the writing display function comprises the following steps:
(1) preparing a piece of PET transparent film with the lower surface plated with an ITO layer and a piece of PET black film with the same size as the PET transparent film and the upper surface plated with the ITO layer;
(2) preparing a PVA insulating orientation layer on the surface of the ITO layer on the lower surface of the PET transparent film;
(3) preparing a liquid crystal/polymer/interval microsphere composite layer between the PVA insulating orientation layer obtained in the step (2) and the ITO layer on the upper surface of the PET black film to obtain a liquid crystal composite film blank;
(4) cutting the liquid crystal composite film blank obtained in the step (3) into film square sheets; the length of the film square piece is 1.25 meters, and the width of the film square piece is 1.25 meters;
(5) placing one side of the PET transparent film of the film square sheet obtained in the step (4) upwards, using a high-precision film cutting machine to perform edge cutting treatment on the PET transparent film of each film square sheet, turning over the film square sheet, using the high-precision film cutting machine to perform edge cutting treatment on the PET black film, wherein the cut width of the PET transparent film and the PET black film is 0.1-5 cm during edge cutting so as to lead out a circuit;
(6) scrubbing the removed part with non-woven fabric soaked with ethanol until the liquid crystal/polymer/interval microsphere composite layer and the PVA insulating orientation layer are cleaned;
(7) and (4) uniformly coating 502 glue on the edge cutting part of the film square sheet prepared in the step (6), and standing for 6 minutes after coating is finished to obtain the liquid crystal composite film with the writing and displaying functions.
The preparation method of the PVA insulating orientation layer comprises the following steps:
(2-1) dissolving a certain amount of PVA in water at 90 ℃, heating for 7 hours, and preparing a PVA aqueous solution with the mass concentration of 3%;
(2-2) uniformly coating the PVA aqueous solution prepared in the step (1) on the surface of the I TO layer on the lower surface of the PET transparent film at a coating speed of 4 m/min by using a coating dryer, wherein the thickness of the PVA aqueous solution coating is 10 microns, and then heating and drying for 6 minutes in a vacuum environment at the temperature of 80 ℃;
and (2-3) carrying out orientation treatment on the surface of the PVA insulating layer by using a rubbing orientation device, wherein the orientation rate is 2 m/min, and the orientation times are 3 times, so that parallel channels are formed on the surface of the PVA, and the PVA insulating orientation layer is obtained.
The preparation method of the liquid crystal polymer layer comprises the following steps:
(3-1) mixing the components of the liquid crystal/polymer/interval microsphere composite layer together according to a ratio, mixing for 3 minutes in an ultrasonic water bath at 70 ℃, and then taking out and oscillating for 3 minutes on an oscillator;
(3-2) injecting the mixed liquid crystal/polymer/interval microsphere composite layer components between a PVA insulating orientation layer on the lower surface of a PET transparent film and an ITO layer on the upper surface of a PET black film through a full-automatic film laminating machine, and curing and molding after ultraviolet light irradiation polymerization reaction by an ultraviolet light curing device to form a liquid crystal/polymer/interval microsphere composite layer; the wavelength of the ultraviolet light is 365 nanometers, the polymerization power is 3 milliwatts per square centimeter, the polymerization time is 5 minutes, and the production speed is 5 meters per minute.
Example 4:
as shown in fig. 1-2, the liquid crystal composite film with writing display function of the present embodiment includes, from top to bottom: the PET film comprises a PET transparent film 1 with an ITO layer plated on the lower surface, a PVA insulating orientation layer 2, a liquid crystal/polymer/interval microsphere composite layer 3 and a PET black film 4 with an ITO layer plated on the upper surface.
The liquid crystal composite film with the writing display function has the following parameters of each layer structure:
in the liquid crystal composite film having a writing display function, the composition of the liquid crystal polymer layer was as follows (in 100 kg, the same applies hereinafter):
the particle size of the polystyrene microsphere is 25 micrometers.
The preparation method of the liquid crystal composite film with the writing display function comprises the following steps:
(1) preparing a piece of PET transparent film with the lower surface plated with an ITO layer and a piece of PET black film with the same size as the PET transparent film and the upper surface plated with the ITO layer;
(2) preparing a PVA insulating orientation layer on the surface of the ITO layer on the lower surface of the PET transparent film;
(3) preparing a liquid crystal/polymer/interval microsphere composite layer between the PVA insulating orientation layer obtained in the step (2) and the ITO layer on the upper surface of the PET black film to obtain a liquid crystal composite film blank;
(4) cutting the liquid crystal composite film blank obtained in the step (3) into film square sheets; the length of the film square piece is 1.25 meters, and the width of the film square piece is 1.1 meters;
(5) placing one side of the PET transparent film of the film square sheet obtained in the step (4) upwards, using a high-precision film cutting machine to perform edge cutting treatment on the PET transparent film of each film square sheet, turning over the film square sheet, using the high-precision film cutting machine to perform edge cutting treatment on the PET black film, wherein the cut width of the PET transparent film and the PET black film is 0.1-5 cm during edge cutting so as to lead out a circuit;
(6) scrubbing the removed part with non-woven fabric soaked with ethanol until the liquid crystal/polymer/interval microsphere composite layer and the PVA insulating orientation layer are cleaned;
(7) and (4) uniformly coating 502 glue on the edge cutting part of the film square sheet prepared in the step (6), and standing for 10 minutes after coating is finished to obtain the liquid crystal composite film with the writing and displaying functions.
The preparation method of the PVA insulating orientation layer comprises the following steps:
(2-1) dissolving a certain amount of PVA in water at 100 ℃, heating for 6 hours, and preparing a PVA aqueous solution with the mass concentration of 20%;
(2-2) uniformly coating the PVA aqueous solution prepared in the step (1) on the surface of the I TO layer on the lower surface of the PET transparent film at a coating speed of 1 m/min by using a coating dryer, wherein the coating thickness of the PVA aqueous solution is 100 microns, and then heating and drying the PVA aqueous solution in a vacuum environment at 100 ℃ for 100 minutes;
and (2-3) carrying out orientation treatment on the surface of the PVA insulating layer by using a rubbing orientation device, wherein the orientation rate is 3 m/min, and the orientation times are 3 times, so that parallel channels are formed on the surface of the PVA, and the PVA insulating orientation layer is obtained.
The preparation method of the liquid crystal polymer layer comprises the following steps:
(3-1) mixing the components of the liquid crystal/polymer/interval microsphere composite layer together according to a proportion, mixing for 1 minute in an ultrasonic water bath at the temperature of 80 ℃, and then taking out and oscillating for 1 minute on an oscillator;
(3-2) injecting the mixed liquid crystal/polymer/interval microsphere composite layer components between a PVA insulating orientation layer on the lower surface of a PET transparent film and an ITO layer on the upper surface of a PET black film through a full-automatic film laminating machine, and curing and molding after ultraviolet light irradiation polymerization reaction by an ultraviolet light curing device TO form a liquid crystal/polymer/interval microsphere composite layer; the wavelength of the ultraviolet light is 365 nanometers, the polymerization power is 1 milliwatt/square centimeter, the polymerization time is 1 minute, and the production speed is 0.5 meter/minute.
The model of the high-precision film cutting machine described in embodiments 1 to 4 is: GD1512 manufactured by Beijing clothing on digital science and technology Limited; the coating dryer is purchased from manufacturers: kangde New composite group GmbH.
The average value of each performance parameter of the liquid crystal composite film with the writing display function prepared in the embodiments 1-4 of the invention is as follows:
TABLE 1 Property parameters of the liquid crystal composite film of the present invention
As can be seen from the data in Table 1, the liquid crystal composite film with the writing and displaying functions of the invention has various performances superior to those of the products sold in the market, and is suitable for wide popularization and application.
Claims (9)
1. A liquid crystal composite film with writing display function is characterized in that: from last to including down in proper order: the lower surface of the PET transparent film is plated with an ITO layer, the PVA insulating orientation layer, the liquid crystal/polymer/interval microsphere composite layer and the upper surface of the PET black film is plated with the ITO layer; the thickness of the PET transparent film plated with the ITO layer is 100-188 microns, the haze is 10% -30%, and the surface resistivity is 100-500 ohms; the thickness of the PET black film plated with the ITO layer is 188 microns, and the surface resistivity is 500 ohms at 100-; the thickness of the PVA insulating layer orientation layer is 0.1-5 microns; the thickness of the liquid crystal/polymer/spacing microsphere composite layer is equal to the diameter of the spacing microspheres;
the liquid crystal/polymer/interval microsphere composite layer comprises the following components in percentage by weight: the birefringence is more than 0.18, the clearing point is less than 135 ℃, the melting point is more than minus 40 ℃ and the nematic liquid crystal is 83-97%, the chiral compound is 2-3%, the ultraviolet polymerizable monomer is 1-12%, the photoinitiator is 0.1-1%, and the size of the spacing microsphere is 3-25 microns and 0.1-1%.
2. The liquid crystal composite film with writing display function according to claim 1, wherein: the spacing microspheres are polystyrene microspheres or polymethyl methacrylate microspheres; the nematic liquid crystal is one of SLC1717, SLC151512 or BNHR49000, the chiral compound is R5011, and the photoinitiator is IRGACURE 651.
3. The liquid crystal composite film with writing display function according to claim 1, wherein: the ultraviolet polymerizable monomer comprises the following components in percentage by weight: 0-12% of 3,5, 5-trimethyl hexyl acrylate, 0-12% of iso-glacial methacrylate, 0-12% of lauryl acrylate, 0-12% of ethylene glycol diacrylate and 0-12% of beta-hydroxyethyl methacrylate.
4. A method for producing a liquid crystal composite film having a writing display function according to any one of claims 1 to 3, characterized by comprising: the method comprises the following steps:
(1) preparing a piece of PET transparent film with the lower surface plated with an ITO layer and a piece of PET black film with the same size as the PET transparent film and the upper surface plated with the ITO layer;
(2) preparing a PVA insulating orientation layer on the surface of the ITO layer on the lower surface of the PET transparent film;
(3) preparing a liquid crystal/polymer/interval microsphere composite layer between the PVA insulating orientation layer obtained in the step (2) and the ITO layer on the upper surface of the PET black film to obtain a liquid crystal composite film blank;
(4) cutting the liquid crystal composite film blank obtained in the step (3) into film square sheets; the length of the film square sheet is 0.1-1.25 m, and the width of the film square sheet is 0.1-1.25 m;
(5) placing one side of the PET transparent film of the film square sheet obtained in the step (4) upwards, using a high-precision film cutting machine to perform edge cutting treatment on the PET transparent film of each film square sheet, turning over the film square sheet, using the high-precision film cutting machine to perform edge cutting treatment on the PET black film, wherein the cut width of the PET transparent film and the PET black film is 0.1-5 cm during edge cutting so as to lead out a circuit;
(6) scrubbing the edge cutting position of the film square sheet by using the non-woven fabric soaked by ethanol until the liquid crystal/polymer/interval microsphere composite layer and the PVA insulating orientation layer are cleaned, so as to lead out a circuit;
(7) and (4) uniformly coating sealing glue on the edge cutting part of the film square sheet prepared in the step (6), and standing for 5-10 minutes after coating is finished to obtain the liquid crystal composite film with the writing and displaying functions.
5. The method for producing a liquid crystal composite film having a writing display function according to claim 4, wherein: the preparation method of the PVA insulating orientation layer comprises the following steps:
(2-1) dissolving a certain amount of PVA in hot water at the temperature of 90-100 ℃, heating for 4-7 hours, and preparing a PVA aqueous solution with the mass concentration of 1-20%;
(2-2) uniformly coating the PVA aqueous solution prepared in the step (1) on the surface of the ITO layer on the lower surface of the PET transparent film through a coating dryer, and controlling the thickness and concentration of the PVA aqueous solution coating layer to control the thickness of the final PVA insulating layer; after coating, the coating is sent into vacuum heating equipment to be dried for 1 to 120 minutes under the vacuum condition of 80 to 100 ℃;
and (2-3) carrying out orientation treatment on the surface of the PVA insulating layer through a friction orientation device to enable the surface of the PVA to form parallel channels, wherein the orientation rate is 1-5 m/min, and the orientation times are 1-5 times, so that the PVA insulating orientation layer is obtained.
6. The method for producing a liquid crystal composite film having a writing display function according to claim 4, wherein: the preparation method of the liquid crystal/polymer/interval microsphere composite layer comprises the following steps:
the components of the liquid crystal/polymer/interval microsphere composite layer are mixed and injected between a PVA insulating orientation layer on the lower surface of a PET transparent film and an ITO layer on the upper surface of a PET black film through a full-automatic film laminating machine, and the mixture is subjected to polymerization reaction by ultraviolet irradiation through an ultraviolet curing device and then is cured and molded to form the liquid crystal/polymer/interval microsphere composite layer.
7. The method for preparing a liquid crystal composite film having a writing display function according to claim 5, wherein: the specific method for controlling the thickness of the final PVA insulating layer by controlling the thickness and concentration of the PVA aqueous solution coating in the step (2-2) is as follows: the thickness of the PVA aqueous solution coating is controlled to be 10-100 microns, and the coating speed is controlled to be 1-5 m/min.
8. The method for preparing a liquid crystal composite film having a writing display function according to claim 6, wherein: the mixing method of the components of the liquid crystal/polymer/interval microsphere composite layer comprises the following steps: mixing the components of the liquid crystal polymer together according to a certain proportion, mixing the components in an ultrasonic water bath at the temperature of 60-80 ℃ for 1-10 minutes, and then taking out the mixture and oscillating the mixture on an oscillator for 1-10 minutes.
9. The method for preparing a liquid crystal composite film having a writing display function according to claim 6, wherein: the ultraviolet wavelength of the ultraviolet irradiation is 365 nm, the polymerization power is 1-10 milliwatt/square centimeter, the polymerization time is 1-60 minutes, and the production speed is 0.5-5 m/min.
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| CN108693668A (en) * | 2017-11-20 | 2018-10-23 | 山东蓝贝易书信息科技有限公司 | Wide temperature range, high contrast liquid crystal film board and preparation method |
| CN108717239B (en) * | 2017-11-20 | 2021-02-19 | 山东蓝贝易书信息科技有限公司 | Easy-to-heat-erase liquid crystal film writing board and preparation method thereof |
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| WO2020197441A1 (en) * | 2019-03-28 | 2020-10-01 | Евгений Борисович АЛЕКСАНДРОВ | Information input and display device for use underwater (variants) |
| CN110095909A (en) * | 2019-05-17 | 2019-08-06 | 嘉兴鸿画显示科技有限公司 | A kind of magnetic erazing type liquid crystal film board and preparation method thereof |
| CN110286511B (en) * | 2019-06-20 | 2022-02-15 | 湖南皓志纳米技术有限公司 | Liquid crystal handwriting board film containing large HTP value chiral agent and preparation method thereof |
| CN110531546B (en) * | 2019-07-26 | 2021-11-26 | 深圳市唯酷光电有限公司 | Cutting method of liquid crystal handwriting film and liquid crystal handwriting film |
| CN112230808A (en) * | 2020-10-20 | 2021-01-15 | 深圳市宝立创科技有限公司 | Electromagnetic screen liquid crystal handwriting board and preparation method thereof |
| CN114545698A (en) | 2020-11-25 | 2022-05-27 | 北京京东方光电科技有限公司 | Writing panel, preparation method thereof and writing board |
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| CN105954903A (en) * | 2016-07-20 | 2016-09-21 | 京东方科技集团股份有限公司 | Liquid crystal display panel and display method and display assembly thereof |
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