CN105062505A - Polymer liquid crystal composition, liquid crystal handwriting display device and preparation method - Google Patents

Polymer liquid crystal composition, liquid crystal handwriting display device and preparation method Download PDF

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CN105062505A
CN105062505A CN201510417500.XA CN201510417500A CN105062505A CN 105062505 A CN105062505 A CN 105062505A CN 201510417500 A CN201510417500 A CN 201510417500A CN 105062505 A CN105062505 A CN 105062505A
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liquid crystal
oligopolymer
monomer
polymer liquid
display device
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CN105062505B (en
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何应军
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Howeasy Board Shenzhen Technology Co ltd
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Shenzhen Jingshiyuan Technology Co ltd
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Priority to PCT/CN2016/083957 priority patent/WO2017008585A1/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1334Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • GPHYSICS
    • G06COMPUTING; CALCULATING OR COUNTING
    • G06FELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)
  • Human Computer Interaction (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention discloses a polymer liquid crystal composition and a liquid crystal handwriting display device using the same, wherein the polymer liquid crystal composition comprises a polymer and liquid crystal which are mutually soluble, and the polymer comprises 30-70 parts of oligomer monomer; 0.5-3 parts of a photoinitiator; 30-70 parts of oligomer; 0.1-1 part of adhesion force reinforcing agent; 5-50 parts of diluent, and also discloses a preparation method of the liquid crystal handwriting device. The liquid crystal handwriting display device adopting the polymer and the bistable cholesteric liquid crystal has high display contrast, low driving voltage and sensitive writing, does not need power consumption in the writing display process, only uses power at the refreshing moment, and can refresh the writing for hundreds of thousands of times, thereby being an environment-friendly writing display device.

Description

Polymer liquid crystal composite and liquid crystal hand writing display device and preparation method
Technical field
The invention belongs to field of liquid crystal display, relate in particular to the preparation method of a kind of liquid crystal hand writing display device polymer liquid crystal composite and hand writing display device.
Background technology
Liquid crystal is a kind of state of matter between solid and liquid, the mobility of existing liquid has again the order of crystal to a certain extent, according to the arrangement mode of molecule, can be divided into nematic, smectic type, cholesteric three major types, wherein cholesteryl liquid crystal is flats, arrangement stratification, in layer, molecule is parallel to each other, molecular long axis is parallel to layer plane, and the molecular long axis direction of different layers slightly changes, and the normal direction along layer is arranged in helicoidal structure.The pitch of thread of cholesteric liquid crystal is about 300nm, magnitude same as visible wavelength, this spiral apart from changing with the difference of the distortion power of outside temperature, current field condition, liquid crystal, therefore the method for available adjustment pitch to external world light modulate.
In recent years, people utilize the opticity of cholesteric liquid crystal, selectivity, light scattering, the feature developments such as circular polarization dichroism have gone out various new display device, hand writing display device is exactly make use of a kind of display unit that cholesteryl liquid crystal bistable characteristic develops, so-called bistable state refers to two stable states not needing extra electric field namely to exist: plane state and Focal conic state, two stable states can when stable without maintenance when extra electric field, show on state of or dark-state respectively, when being subject to certain pressure, the liquid crystal molecule arrangement of force part changes, produce Bragg reflection effect, the track of record pressure, display screen only needs faint electric current when driving and refreshing, thus achieve the reduce power consumption of product.But in prior art, bistable cholesteric liquid crystal hand writing display device display comparison degree is lower, driving voltage is higher, thus energy consumption is higher, and liquid crystal and the cohesive force between polymkeric substance and upper and lower film are not by force, hand writing display device breakage easy to crack.
Summary of the invention
For this reason, technical problem to be solved by this invention is in prior art, bistable cholesteric liquid crystal hand writing display device display comparison degree is lower, driving voltage is high, liquid crystal and polymkeric substance and up and down between film cohesive force strong, handwriting device breakage easy to crack thus propose a kind of hand-written liquid crystal indicator polymer liquid crystal composition and method of making the same.
For solving the problems of the technologies described above, technical scheme of the present invention is:
The invention provides a kind of polymer liquid crystal composite, it comprises the polymkeric substance and liquid crystal that dissolve each other, and wherein, described polymkeric substance, with parts by weight, comprises following component:
Oligopolymer monomer 30-70 part;
Light trigger 0.5-3 part;
Oligopolymer 30-70 part;
Adhesive promoter 0.1-1 part;
Thinner 5-50 part.
As preferably, described composition with weight part and, comprise following component:
Oligopolymer monomer 40-60 part;
Light trigger 1-2 part;
Oligopolymer 40-60 part;
Adhesive promoter 0.4-0.8 part;
Thinner 20-40 part.
As preferably, the mass ratio of described polymkeric substance and liquid crystal is 15%-60%:85%-40%.
As preferably, described oligopolymer monomer is one or more in monofunctional acrylates's esters monomer, simple function group methacrylate-based monomer, bifunctional acrylate's class monomer, bifunctional methacrylate-based monomer, trifunctional group acrylate's class monomer and multi-functional acrylate's class monomer.
As preferably, described oligopolymer is one or more in urethane acrylate oligomer, polyester acrylate oligomers, polyether acrylate oligomer and unsaturated polyester ester oligomer, and the shore hardness of described oligopolymer after solidification polymerization is between 10A-50D.
As preferably, described light trigger is 2,4,6, one or more in-trimethylbenzoy-dipheny phosphorus oxide, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone; Described adhesive promoter is one or both in 2-HEMA phosphoric acid ester, Tricyclodecane Dimethanol dimethacrylate; Described thinner is the acrylate monomer that viscosity is less than 200CPS.
As preferably, described liquid crystal is bistable cholesteric liquid crystal.
Present invention also offers a kind of method preparing described polymer liquid crystal composite, comprise the steps:
(1) under darkroom or gold-tinted environment, oligopolymer monomer is added reaction vessel, then at room temperature add oligopolymer, adhesive promoter and thinner in turn and the mixture obtained is stirred;
(2) add light trigger, be stirred to described light trigger and be dissolved in the mixture obtained in step (1) completely, obtain polymkeric substance;
(3) under darkroom or gold-tinted environment, described polymkeric substance and described bistable cholesteric liquid crystal are mixed at 15-35 DEG C the two and dissolve each other, become the mixed solution of clarification;
(4) add in the mixed solution of clarification in step (3) particle diameter be the pad of 2-20 μm every powder, be stirred to described pad and be uniformly distributed in described mixed solution every powder, obtain described polymer liquid crystal composite.
Further, the invention provides a kind of liquid crystal hand writing display device, it comprises described polymer liquid crystal composite.
Present invention also offers a kind of method preparing described liquid crystal hand writing display device, comprise the steps:
(1) adopt roll-in method or coating method to be coated between two ITO conducting films or conductive glass by described polymer liquid crystal composite, obtain the hand-written film work in-process of liquid crystal;
(2) by the described work in-process in step (1) through illuminance be 0.1-5MW/cm 2, wavelength is the UV-irradiation 1-5min of 200-400nm, obtains the hand-written film of liquid crystal solidified;
(3) hand-written for described liquid crystal film is cut into desired size, and be linked and packed with driving circuit, plate shell, obtain described liquid crystal hand writing display device.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) polymer liquid crystal composite of the present invention comprises the polymkeric substance and liquid crystal that dissolve each other, wherein, described polymkeric substance comprises following component: oligopolymer monomer, light trigger, oligopolymer, adhesive promoter and thinner, this method for producing polymer is simple, gentle, is beneficial to suitability for industrialized production; The liquid crystal hand writing display device display comparison degree that have employed polymkeric substance of the present invention and bistable cholesteric liquid crystal is high, driving voltage is low, it is sensitive to write, and described hand writing display device does not need power consumption in the procedure for displaying write, the moment electricity consumption only refreshed, writing refreshing can reach millions of time, be a kind of environment-friendly type write display unit.
(2) preparation method of liquid crystal hand writing display device of the present invention, technique is simple, easy handling, described liquid crystal hand writing display device is in preparation process, with the addition of pad every powder, it can support described polymkeric substance and liquid crystal, polymkeric substance and liquid crystal are coated with evenly between ITO conducting film and ITO conductive glass, thus make the interval between ITO conducting film and ito glass even.And adopt polymkeric substance described in ultraviolet light polymerization, and define the space of 1-10 μm in the curing process, cholesteryl liquid crystal interval is scattered among polymkeric substance by this, simultaneously also ITO conducting film and/or ITO conductive glass to be bonded in together, add the firmness of device, solve that polymkeric substance and liquid crystal and upper and lower intermembranous cohesive force in prior art are strong, the problem of hand writing display device breakage easy to crack.
Accompanying drawing explanation
Fig. 1 is the pressure sensitive figure of liquid crystal hand writing display device of the present invention;
Fig. 2 is the voltage refreshing figure of liquid crystal hand writing display device of the present invention.
Embodiment
In order to make content of the present invention be more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Embodiment 1
The present embodiment provides a kind of polymer liquid crystal composite, and it comprises mass ratio is the polymkeric substance that dissolves each other of 15%:85% and cholesteryl liquid crystal, and wherein said polymkeric substance, with parts by weight, comprises following component:
Oligopolymer monomer: lauric acid acrylate 30 parts, its molecular formula is:
Light trigger: 2,4,6 ,-trimethylbenzoy-dipheny phosphorus oxide 0.5 part, its molecular formula is:
Oligopolymer: the model purchased from Changxing, Taiwan Chemical Co., Ltd. is the oligopolymer 30 parts of 6127, after its solidification, hardness is 90A;
Thinner: viscosity is the ethoxyethoxyethyl acrylate 5 parts of 150CPS, and its molecular formula is:
Adhesive promoter: 2-HEMA phosphoesterase 30 .1 part, described 2-HEMA phosphoric acid ester molecular formula is:
The present embodiment additionally provides the preparation method of described polymer liquid crystal composite, comprises the steps:
(1) in darkroom, lauric acid acrylate is added reaction vessel, at 20 DEG C, then adds 6127 in turn, 2-HEMA phosphoric acid ester and ethoxyethoxyethyl acrylate the mixture obtained is stirred;
(2) add 2,4,6 ,-trimethylbenzoy-dipheny phosphorus oxide, be stirred to described 2,4,6 ,-trimethylbenzoy-dipheny phosphorus oxide is dissolved in the mixture obtained in step (1) completely, obtains polymkeric substance;
(3) under gold-tinted environment, described polymkeric substance and described bistable cholesteric liquid crystal are mixed at 15 DEG C the two and dissolve each other, become the mixed solution of clarification;
(4) add in the mixed solution of clarification in step (3) particle diameter be the pad of 2 μm every powder, be stirred to described pad and be uniformly distributed in described mixed solution every powder, obtain described polymer liquid crystal composite.
Further, the present embodiment additionally provides a kind of liquid crystal hand writing display device, and it comprises described polymer liquid crystal composite.
The preparation method of described liquid crystal hand writing display device, comprises the steps:
(1) adopt roll-in method to be coated between two ITO conducting films by described polymer liquid crystal composite, obtain the hand-written film work in-process of liquid crystal;
(2) by the described work in-process in step (1) through illuminance be 0.1MW/cm 2, wavelength peak is the UV-irradiation 1min of 200nm, obtains the hand-written film of liquid crystal solidified;
(3) hand-written for described liquid crystal film is cut into desired size, and be linked and packed with driving circuit, plate shell, obtain described liquid crystal hand writing display device.
Embodiment 2
The present embodiment provides a kind of polymer liquid crystal composite, and it comprises mass ratio is the polymkeric substance that dissolves each other of 60%:40% and cholesteryl liquid crystal, and wherein said polymkeric substance, with parts by weight, comprises following component:
Oligopolymer monomer: 2-(p-cumyl-phenoxy group)-ethyl propylene acid esters 30 parts, tetrahydrofurfuryl acrylate 40 parts, wherein, described 2-(p-cumyl-phenoxy group)-ethyl propylene acid ester molecules formula is:
Described tetrahydrofurfuryl acrylate molecule formula is:
Light trigger: 1-hydroxyl-cyclohexyl-phenyl ketone 3 parts, its molecular formula is:
Oligopolymer: the model purchased from Changxing, Taiwan Chemical Co., Ltd. is the oligopolymer 20 parts of 6070, after its solidification, hardness is 87A, and model is the oligopolymer 20 parts of DR-028FS, and after its solidification, hardness is 85A, model is the oligopolymer 30 parts of 6113, and after its solidification, hardness is 40A;
Thinner: viscosity is the 2-phenoxyethyl acrylate 50 parts of 180CPS, and its molecular formula is:
Adhesive promoter: Tricyclodecane Dimethanol dimethacrylate 1 part, its molecular formula is:
The present embodiment additionally provides the preparation method of described polymer liquid crystal composite, comprises the steps:
(1) in darkroom, 2-(p-cumyl-phenoxy group)-ethyl propylene acid esters and tetrahydrofurfuryl acrylate are added reaction vessel, then at 25 DEG C, add 6070 in turn, DR-028FS, 6113, Tricyclodecane Dimethanol dimethacrylate and 2-phenoxyethyl acrylate, and the mixture obtained to be stirred;
(2) add 1-hydroxyl-cyclohexyl-phenyl ketone, be stirred to described 1-hydroxyl-cyclohexyl-phenyl ketone and be dissolved in completely in the mixture obtained in step (1), obtain polymkeric substance;
(3) under gold-tinted environment, described polymkeric substance and described bistable cholesteric liquid crystal are mixed at 40 DEG C the two and dissolve each other, become the mixed solution of clarification;
(4) add in the mixed solution of clarification in step (3) particle diameter be the pad of 20 μm every powder, be stirred to described pad and be uniformly distributed in described mixed solution every powder, obtain described polymer liquid crystal composite.
Further, the present embodiment additionally provides a kind of liquid crystal hand writing display device, and it comprises described polymer liquid crystal composite.
The preparation method of described liquid crystal hand writing display device, comprises the steps:
(1) adopt roll-in method to be coated between an ITO conducting film and an ITO conductive glass by described polymer liquid crystal composite, obtain the hand-written film work in-process of liquid crystal;
(2) by the described work in-process in step (1) through illuminance be 5MW/cm 2d, wavelength peak are the UV-irradiation 5min of 400nm, obtain the hand-written film of liquid crystal solidified;
(3) hand-written for described liquid crystal film is cut into desired size, and be linked and packed with driving circuit, plate shell, obtain described liquid crystal hand writing display device.
Embodiment 3
The present embodiment provides a kind of polymer liquid crystal composite, and it comprises mass ratio is the polymkeric substance that dissolves each other of 40%:60% and cholesteryl liquid crystal, and wherein said polymkeric substance, with parts by weight, comprises following component:
Oligopolymer monomer: stearic acid acrylate 20 parts, isobornyl methacrylate 30 parts, wherein, the molecular formula of described stearic acid acrylate is:
The molecular formula of described isobornyl methacrylate is:
Light trigger: 1.5 parts, 2-hydroxy-2-methyl-1-phenyl-1-acetone, its molecular formula is:
Oligopolymer: the model purchased from Changxing, Taiwan Chemical Co., Ltd. is the oligopolymer 20 parts of DR-U390, after its solidification, hardness is 70A, and model is the oligopolymer 10 parts of 6148, and after its solidification, hardness is 21A, model is the oligopolymer 20 parts of 6176, and after its solidification, hardness is 21A;
Thinner: viscosity is ethoxyethoxyethyl acrylate 20 parts, the 2-phenoxyethyl acrylate 10 parts of 100CPS;
Adhesive promoter: 2-HEMA phosphoesterase 30 .3 part, Tricyclodecane Dimethanol dimethacrylate 0.3 part.
The present embodiment additionally provides the preparation method of described polymer liquid crystal composite, comprises the steps:
(1) in darkroom, stearic acid acrylate and isobornyl methacrylate are added reaction vessel, then add in turn at 20 DEG C DR-U390,6148,6176,2-HEMA phosphoric acid ester, cyclodecane dimethanol dimethacrylate, ethoxyethoxyethyl acrylate and 2-phenoxyethyl acrylate, and the mixture obtained to be stirred;
(2) add 2-hydroxy-2-methyl-1-phenyl-1-acetone, be stirred to described 2-hydroxy-2-methyl-1-phenyl-1-acetone and be dissolved in completely in the mixture obtained in step (1), obtain polymkeric substance;
(3) under gold-tinted environment, described polymkeric substance and described bistable cholesteric liquid crystal are mixed at 25 DEG C the two and dissolve each other, become the mixed solution of clarification;
(4) add in the mixed solution of clarification in step (3) particle diameter be the pad of 10 μm every powder, be stirred to described pad and be uniformly distributed in described mixed solution every powder, obtain described polymer liquid crystal composite.
Further, the present embodiment additionally provides a kind of liquid crystal hand writing display device, and it comprises described polymer liquid crystal composite.
The preparation method of described liquid crystal hand writing display device, comprises the steps:
(1) adopt coating method to be coated between two ITO conducting films by described polymer liquid crystal composite, obtain the hand-written film work in-process of liquid crystal;
(2) by the described work in-process in step (1) through illuminance be 3MW/cm 2, peak wavelength is the UV-irradiation 3min of 400nm, obtains the hand-written film of liquid crystal solidified;
(3) hand-written for described liquid crystal film is cut into desired size, and be linked and packed with driving circuit, plate shell, obtain described liquid crystal hand writing display device.
Embodiment 4
The present embodiment provides a kind of polymer liquid crystal composite, and it comprises mass ratio is the polymkeric substance that dissolves each other of 35%:65% and cholesteryl liquid crystal, and wherein said polymkeric substance, with parts by weight, comprises following component:
Oligopolymer monomer: 2-(p-cumyl-phenoxy group)-ethyl propylene acid esters 5 parts, tetrahydrofurfuryl acrylate 40 parts,
Light trigger: 2,4,6 ,-trimethylbenzoy-dipheny phosphorus oxide 1 part;
Oligopolymer: the model purchased from Changxing, Taiwan Chemical Co., Ltd. is the oligopolymer 40 parts of 6148, after its solidification, hardness is 21A, and model is the oligopolymer 10 parts of 6113, and after its solidification, hardness is 40A;
Thinner: viscosity is the 2-phenoxyethyl acrylate 5 parts of 180CPS;
Adhesive promoter: 2-HEMA phosphoesterase 30 .3 part.
The present embodiment additionally provides the preparation method of described polymer liquid crystal composite, comprises the steps:
(1) in darkroom, 2-(p-cumyl-phenoxy group)-ethyl propylene acid esters and tetrahydrofurfuryl acrylate are added reaction vessel, at 25 DEG C, then add 6148 in turn, 6113,2-HEMA phosphoric acid ester and 2-phenoxyethyl acrylate the mixture obtained is stirred;
(2) add 2,4,6 ,-trimethylbenzoy-dipheny phosphorus oxide, be stirred to described 2,4,6 ,-trimethylbenzoy-dipheny phosphorus oxide is dissolved in the mixture obtained in step (1) completely, obtains polymkeric substance;
(3) under gold-tinted environment, described polymkeric substance and described bistable cholesteric liquid crystal are mixed at 23 DEG C the two and dissolve each other, become the mixed solution of clarification;
(4) add in the mixed solution of clarification in step (3) particle diameter be the pad of 4.5 μm every powder, be stirred to described pad and be uniformly distributed in described mixed solution every powder, obtain described polymer liquid crystal composite.
Further, the present embodiment additionally provides a kind of liquid crystal hand writing display device, and it comprises described polymer liquid crystal composite.
The preparation method of described liquid crystal hand writing display device, comprises the steps:
(1) adopt roll-in method to be coated between two ITO conducting films by described polymer liquid crystal composite, obtain the hand-written film work in-process of liquid crystal;
(2) by the described work in-process in step (1) through illuminance be 1MW/cm 2d, wavelength peak are the UV-irradiation 3min of 400nm, obtain the hand-written film of liquid crystal solidified;
(3) hand-written for described liquid crystal film is cut into desired size, and be linked and packed with driving circuit, plate shell, obtain described liquid crystal hand writing display device.
Embodiment 5
The present embodiment provides a kind of polymer liquid crystal composite, and it comprises mass ratio is the polymkeric substance that dissolves each other of 50%:50% and cholesteryl liquid crystal, and wherein said polymkeric substance, with parts by weight, comprises following component:
Oligopolymer monomer: trimethylolpropane trimethacrylate 40 parts, its molecular formula is:
Light trigger: 2,4,6 ,-trimethylbenzoy-dipheny phosphorus oxide 0.5 part, 1-hydroxyl-cyclohexyl-phenyl ketone 0.5 part;
Oligopolymer: the model purchased from Changxing, Taiwan Chemical Co., Ltd. is the oligopolymer 20 parts of 6115, after its solidification, hardness is 70A, and model is the oligopolymer 20 parts of DR-U367-1, and after its solidification, hardness is 25A;
Thinner: viscosity is the 2-phenoxyethyl acrylate 20 parts of 150CPS;
Adhesive promoter: Tricyclodecane Dimethanol dimethacrylate 0.4 part.
The present embodiment additionally provides the preparation method of described polymer liquid crystal composite, comprises the steps:
(1) under gold-tinted environment, trimethylolpropane trimethacrylate is added reaction vessel, then at 25 DEG C, add 6115 in turn, DR-U367-1, Tricyclodecane Dimethanol dimethacrylate and 2-phenoxyethyl acrylate, and the mixture obtained to be stirred;
(2) 2 are added, 4,6,-trimethylbenzoy-dipheny phosphorus oxide and 1-hydroxyl-cyclohexyl-phenyl ketone, be stirred to described 2,4,6,-trimethylbenzoy-dipheny phosphorus oxide and 1-hydroxyl-cyclohexyl-phenyl ketone are dissolved in the mixture obtained in step (1) completely, obtain polymkeric substance;
(3) in darkroom, described polymkeric substance and described bistable cholesteric liquid crystal are mixed at 25 DEG C the two and dissolve each other, become the mixed solution of clarification;
(4) add in the mixed solution of clarification in step (3) particle diameter be the pad of 15 μm every powder, be stirred to described pad and be uniformly distributed in described mixed solution every powder, obtain described polymer liquid crystal composite.
Further, the present embodiment additionally provides a kind of liquid crystal hand writing display device, and it comprises described polymer liquid crystal composite.
The preparation method of described liquid crystal hand writing display device, comprises the steps:
(1) adopt coating method to be coated between two ITO conducting films by described polymer liquid crystal composite, obtain the hand-written film work in-process of liquid crystal;
(2) by the described work in-process in step (1) through illuminance be 4MW/cm 2, peak wavelength is the UV-irradiation 5min of 400nm, obtains the hand-written film of liquid crystal solidified;
(3) hand-written for described liquid crystal film is cut into desired size, and be linked and packed with driving circuit, plate shell, obtain described liquid crystal hand writing display device.
Embodiment 6
The present embodiment provides a kind of polymer liquid crystal composite, and it comprises mass ratio is the polymkeric substance that dissolves each other of 30%:70% and cholesteryl liquid crystal, and wherein said polymkeric substance, with parts by weight, comprises following component:
Oligopolymer monomer: lauric acid acrylate 20 parts, isobornyl methacrylate 40 parts;
Light trigger: 1-hydroxyl-cyclohexyl-phenyl ketone 2 parts;
Oligopolymer: the model purchased from Changxing, Taiwan Chemical Co., Ltd. is the oligopolymer 30 parts of 6101, after its solidification, hardness is 80A, and model is the oligopolymer 30 parts of DR-U384, and after its solidification, hardness is 69A;
Thinner: viscosity is the 2-phenoxyethyl acrylate 40 parts of 180CPS;
Adhesive promoter: 2-HEMA phosphoesterase 30 .8 part.
The present embodiment additionally provides the preparation method of described polymer liquid crystal composite, comprises the steps:
(1) in darkroom, lauric acid acrylate, isobornyl methacrylate are added reaction vessel, then at 20 DEG C, add 6101 in turn, DR-U384,2-HEMA phosphoric acid ester and 2-phenoxyethyl acrylate, and the mixture obtained to be stirred;
(2) add 1-hydroxyl-cyclohexyl-phenyl ketone, be stirred to described 1-hydroxyl-cyclohexyl-phenyl ketone and be dissolved in completely in the mixture obtained in step (1), obtain polymkeric substance;
(3) in darkroom, described polymkeric substance and described bistable cholesteric liquid crystal are mixed at 25 DEG C the two and dissolve each other, become the mixed solution of clarification;
(4) add in the mixed solution of clarification in step (3) particle diameter be the pad of 15 μm every powder, be stirred to described pad and be uniformly distributed in described mixed solution every powder, obtain described polymer liquid crystal composite.
Further, the present embodiment additionally provides a kind of liquid crystal hand writing display device, and it comprises described polymer liquid crystal composite.
The preparation method of described liquid crystal hand writing display device, comprises the steps:
(1) adopt coating method to be coated between two panels ITO conductive glass by described polymer liquid crystal composite, obtain the hand-written film work in-process of liquid crystal;
(2) by the described work in-process in step (1) through illuminance be 3MW/cm 2, peak wavelength is the UV-irradiation 5min of 400nm, obtains the hand-written film of liquid crystal solidified;
(3) hand-written for described liquid crystal film is cut into desired size, and be linked and packed with driving circuit, plate shell, obtain described liquid crystal hand writing display device.
Experimental example
1. test the reflectivity curve of described liquid crystal handwriting device under different pressures intensity, result as shown in Figure 1, as can be seen from the figure, only have when described liquid crystal handwriting device is applied write pressure be greater than certain value time, reflectivity is just enough high, and human eye just can identify the vestige write; This is because when pressure exceedes certain value, the arrangement of liquid crystal there occurs change, thus written portion is different from other parts color, and human eye can identify, illustrate that liquid crystal handwriting device pressure sensibility of the present invention is higher.
2. test the changing conditions of described liquid crystal handwriting device remaining ghost under different voltage; result as shown in Figure 2; as can be seen from the figure; when being energized to two conductive layers of described liquid crystal handwriting device; the arrangement of liquid crystal changes again; along with voltage raises; write ghost to reduce gradually; written trace returns to the color local the same with other; reach the effect eliminating written trace; can find out from test result, liquid crystal handwriting device of the present invention driving voltage when knowing written trace is low, and current consumption is little.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.

Claims (10)

1. a polymer liquid crystal composite, is characterized in that, comprises the polymkeric substance and liquid crystal that dissolve each other, and wherein, described polymkeric substance, with parts by weight, comprises following component:
Oligopolymer monomer 30-70 part;
Light trigger 0.5-3 part;
Oligopolymer 30-70 part;
Adhesive promoter 0.1-1 part;
Thinner 5-50 part.
2. polymer liquid crystal composite according to claim 1, is characterized in that, described composition with weight part and, comprise following component:
Oligopolymer monomer 40-60 part;
Light trigger 1-2 part;
Oligopolymer 40-60 part;
Adhesive promoter 0.4-0.8 part;
Thinner 20-40 part.
3. polymer liquid crystal composite according to claim 1 and 2, is characterized in that, the mass ratio of described polymkeric substance and liquid crystal is 15%-60%:85%-40%.
4. polymer liquid crystal composite according to claim 3, it is characterized in that, described oligopolymer monomer is one or more in monofunctional acrylates's esters monomer, simple function group methacrylate-based monomer, bifunctional acrylate's class monomer, bifunctional methacrylate-based monomer, trifunctional group acrylate's class monomer and multi-functional acrylate's class monomer, and the molecular weight of described oligopolymer monomer is between 100-1000.
5. polymer liquid crystal composite according to claim 4, it is characterized in that, described oligopolymer is one or more in urethane acrylate oligomer, polyester acrylate oligomers, polyether acrylate oligomer and unsaturated polyester ester oligomer, and described oligopolymer shore hardness is after hardening between 10A-60D.
6. polymer liquid crystal composite according to claim 5, it is characterized in that, described light trigger is 2,4,6, one or more in-trimethylbenzoy-dipheny phosphorus oxide, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone; Described adhesive promoter is one or both in 2-HEMA phosphoric acid ester, Tricyclodecane Dimethanol dimethacrylate; Described thinner is the acrylate monomer that viscosity is less than 200CPS.
7. the polymer liquid crystal composite according to any one of claim 4-6, is characterized in that, described liquid crystal is bistable cholesteric liquid crystal.
8. prepare a method for the polymer liquid crystal composite described in any one of 1-7, it is characterized in that, comprise the steps:
(1) under darkroom or gold-tinted environment, oligopolymer monomer is added reaction vessel, then at room temperature add oligopolymer, adhesive promoter and thinner in turn and the mixture obtained is stirred;
(2) add light trigger, be stirred to described light trigger and be dissolved in the mixture obtained in step (1) completely, obtain polymkeric substance;
(3) under darkroom or gold-tinted environment, described polymkeric substance and described bistable cholesteric liquid crystal are mixed at 15-35 DEG C the two and dissolve each other, become the mixed solution of clarification;
(4) add in the mixed solution of clarification in step (3) particle diameter be the pad of 2-20 μm every powder, be stirred to described pad and be uniformly distributed in described mixed solution every powder, obtain described polymer liquid crystal composite.
9. a liquid crystal hand writing display device, is characterized in that, comprises the polymer liquid crystal composite described in any one of claim 1-7.
10. prepare a method for liquid crystal hand writing display device according to claim 9, it is characterized in that, comprise the steps:
(1) adopt roll-in method or coating method to be coated between two ITO conducting films or conductive glass by described polymer liquid crystal composite, obtain the hand-written film work in-process of liquid crystal;
(2) by the described work in-process in step (1) through illuminance be 0.1-5MW/cm2, wavelength is the UV-irradiation 1-5min of 200-400nm, obtains the hand-written film of liquid crystal solidified;
(3) hand-written for described liquid crystal film is cut into desired size, and be linked and packed with driving circuit, plate shell, obtain described liquid crystal hand writing display device.
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