CN109782505A - A kind of reflective film and preparation method thereof with light erasing function - Google Patents
A kind of reflective film and preparation method thereof with light erasing function Download PDFInfo
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- CN109782505A CN109782505A CN201711120169.0A CN201711120169A CN109782505A CN 109782505 A CN109782505 A CN 109782505A CN 201711120169 A CN201711120169 A CN 201711120169A CN 109782505 A CN109782505 A CN 109782505A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 121
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 26
- -1 helicene compound Chemical class 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 14
- 230000003098 cholesteric effect Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 150000003384 small molecules Chemical class 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 77
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 12
- 230000005684 electric field Effects 0.000 claims description 11
- 239000004988 Nematic liquid crystal Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- 238000004020 luminiscence type Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000002086 nanomaterial Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
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- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 210000000232 gallbladder Anatomy 0.000 claims description 2
- UOYPNWSDSPYOSN-UHFFFAOYSA-N hexahelicene Chemical class C1=CC=CC2=C(C=3C(=CC=C4C=CC=5C(C=34)=CC=CC=5)C=C3)C3=CC=C21 UOYPNWSDSPYOSN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 150000003431 steroids Chemical class 0.000 claims description 2
- 125000005429 oxyalkyl group Chemical group 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
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- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002983 circular dichroism Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 150000003573 thiols Chemical class 0.000 description 1
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- Liquid Crystal (AREA)
- Liquid Crystal Substances (AREA)
Abstract
本发明公开了一种具有光擦除功能的反射薄膜及其制备方法，所述薄膜包括：在ITO薄膜之中灌注光响应胆甾相液晶复合体系，压制形成液晶薄膜；所述光响应胆甾相液晶复合体系包括主体小分子液晶材料、手性螺烯类化合物、手性化合物、可聚合单体和光引发剂。本发明通过简单的工艺，所制备的反射显示薄膜具备高亮度与高对比度的压力书写反射显示功能，大面积电擦除功能和小面积选定区域的光擦除功能。
The invention discloses a reflective film with light erasing function and a preparation method thereof. The film comprises: pouring a light-responsive cholesteric liquid crystal composite system into an ITO film, and pressing to form a liquid crystal film; the light-responsive cholesteric phase liquid crystal film is formed by pressing; The phase liquid crystal composite system includes a host small molecule liquid crystal material, a chiral helicene compound, a chiral compound, a polymerizable monomer and a photoinitiator. Through a simple process, the prepared reflective display film has the pressure writing reflective display function of high brightness and high contrast, a large-area electric erasing function and a small-area selected area optical erasing function.
Description
Technical field
The invention belongs to liquid crystal intelligence and display material applied technical field, and specifically, the present invention provides one kind to have
The reflective film and preparation method thereof of light erasing function.
Background technique
Since 21st century, as social economy develops rapidly, global non-renewable energy resources are increasingly depleted, the energy
Imbalance between supply and demand is outstanding day by day, and the service efficiency for how improving the energy becomes a global problem, and energy-saving and environment-friendly theory is
Penetrate into the every aspect of human society life.
In the past 20 years, liquid crystal material flourishes always.From the electronic watch to come into vogue, LCD TV, mobile phone are arrived, then is arrived
Present Electronic Paper, e-book, liquid crystal using more and more extensive in people's daily life.Therefore, develop energy-efficient liquid
Brilliant display technology is of great significance.
For cholesteric liquid crystal molecule due to its unique helicoidal structure, it is various special to have under different alignment conditions
Optical characteristics, such as selective reflecting, circular dichroism, optical activity, beam divergence property.These optical characteristics make cholesteric liquid crystal exist
Numerous areas has a wide range of applications, and is frequently used to the optical device that preparation has energy-saving environmental-protection function.In consideration of it, applicant
A kind of reflective film with light erasing function is developed, this reflective film has high brightness and the pressure of high contrast is write
Reflect display function, the light erasing function of large area electrically erasable function and small area selection area.
Summary of the invention
It is an object of that present invention to provide a kind of reflective films and preparation method thereof with light erasing function, by simple
Technique, prepared film has high brightness and the pressure of high contrast writes reflection display function, large area electrically erasable function
Function is wiped with the light of small area selection area.
In order to achieve the above objectives, present invention employs the following technical solutions:
A kind of reflective film with light erasing function, the film include:
Photoresponse cholesteric liquid crystal compound system, the liquid that compacting is formed with a thickness of 2 μm -50 μm are perfused among ito thin film
Brilliant film；
The photoresponse cholesteric liquid crystal compound system includes that the main body that mass fraction is 60.0wt%-95.0wt% is small
Chiral spiral shell vinyl compound, the mass fraction 0.2wt%- that molecular liquid crystal material, mass fraction are 0.1wt%-15.0wt%
The chipal compounds of 30.0wt%, the liquid crystal liquid crystal property polymerisable monomer of 0.0wt%-20.0wt%, 0.0wt%-20.0wt% it is non-
The photoinitiator of liquid crystal liquid crystal property polymerisable monomer and 0.1wt%-5.0wt%.
Preferably, the chipal compounds are selected from one of S811, R811, S1011, R1011, S5011 and R5011
Or it is several.
Further, the photoresponse cholesteric liquid crystal compound system further includes up-conversion luminescence nanomaterial, it is described on
The matrix of Illuminant nanometer material is converted as one of NaYF4, NaGdF4 and NaYbF4 ingredient simple substance or Multiple components complex nucleus
Shell structure, the doping with rare-earth ions element in mesostroma includes one or more of Yb, Tm, Er, Ho, Nd and Mn.
The present invention also provides the preparation method of the above-mentioned reflective film with light erasing function, the preparation method includes
Following steps:
1) by mass fraction be 60.0wt%-95.0wt% main body small molecule liquid crystal material, mass fraction be
The chiral spiral shell vinyl compound of 0.1wt%-15.0wt%, the chipal compounds that mass fraction is 0.2wt%-30.0wt%,
The liquid crystal liquid crystal property polymerisable monomer of 0.0wt%-20.0wt%, the non-liquid crystal property polymerisable monomer of 0.0wt%-20.0wt% and
The photoinitiator mixture of 0.1wt%-5.0wt% is uniform and obtains having the mixed liquid crystal of very wide cholesteric phase temperature range compound
System；
2) photoresponse cholesteric liquid crystal compound system is pressed into liquid crystal film with plastics ito thin film, by separation pad or
Glass microballoon controls the thickness of liquid crystal device；
3) as shown in Figure 1, applying an electric field to liquid crystal film, the burnt cone for making liquid crystal molecule be in non-reflective state is knitted
Structure, and light irradiation polymerization is carried out in its cholesteric phase temperature range；Electric field, the liquid crystal after polymerization are closed after light irradiation polymerization
It will form polymer network inside film.
In the preparation method of the above-mentioned reflective film with light erasing function, chiral helicene class described in step 1
The helical twisting power for closing object has the characteristic to change under exciting light (300-460nm) irradiation, preferably, chiral helicene
Class compound is selected from the one or more of following compound:
Formula (1) described R1–R9Selected from for H atom, phenyl ring, CnH2n+1Alkyl chain, OCnH2n+1Oxyalkyl chain or R1–R9It is selected from
One or more of following group, it is 1-12 that n, which is selected from,；
In the preparation method of the above-mentioned reflective film with light erasing function, chipal compounds described in step 1) are
One or more kinds of chipal compounds, it is preferable that the following are the chipal compounds that can be used in the present invention, but are not limited to these
Material:
In the preparation method of the above-mentioned reflective film with light erasing function, main body small molecule liquid described in step 1)
Crystalline substance is the mixture of nematic liquid crystal or cholesteric liquid crystal or nematic liquid crystal and cholesteric liquid crystal.Preferably, the main body
Small molecule liquid crystal material is nematic liquid crystal SLC1717 or nematic liquid crystal E7.
In the preparation method of the above-mentioned reflective film with light erasing function, non-liquid crystal property described in step 1) can gather
It is optional but be not limited to following one or more to close monomer, as unsaturated polyester (UP), epoxy acrylate, urethane acrylate,
Polyester acrylate, epoxy acrylate, polyenoid thiol, polyether acrylate, water-and acrylate, vinyl ethers
Deng.
In the preparation method of the above-mentioned reflective film with light erasing function, liquid crystal liquid crystal property used in step 1) is polymerizable
Monomer is one or more kinds of chiral or achiral liquid crystal monomers, and the following are the polymerizable lists of the liquid crystal liquid crystal property that can be used in the present invention
Body, but it is not limited to these materials:
In the preparation method of the above-mentioned reflective film with light erasing function, photoinitiator used in step 1),
For benzoin isopropyl ether (Irgacure 651), the fluoro- 3- pyrroles's phenyl titanocenes (Irgacure 784) of double 2,6- bis- and hexichol
One of ketone is a variety of, but is not limited to these materials.
In the preparation method of the above-mentioned reflective film with light erasing function, preferably, the light irradiation is poly-
The irradiation optical wavelength of conjunction is any wave band within the scope of 300-500nm, and light irradiation time is -1 hour 5 minutes, irradiates luminous intensity
For 1 μ W/cm2-500mW/cm2。
In the preparation method of the above-mentioned reflective film with light erasing function, preferably, the liquid crystal film
With a thickness of 2 μm -50 μm.
As shown in Fig. 2, the liquid crystal film that the present invention is prepared has high brightness and the pressure of high contrast writes reflection
The light of display function, large area electrically erasable function and small area selection area wipes function:
1) cholesteric liquid crystal of liquid crystal film is presented non-reflective burnt cone in original state and is knitted due to the effect of polymer network
Structure (a)；
2) pressure is applied to the region for needing to be written information above liquid crystal film, since the boundary effect of film substrate is compeled
Cholesteric liquid crystal is set to form planar texture, and reflected wavelength lambda=n × p0Visible light, wherein n is that cholesteric liquid crystal being averaged
Refractive index, p0For the initial screw pitch of cholesteric liquid crystal, this state can keep stablizing constant for a long time, that is, realize pressure book
Write reflection display function (b)；
3) electric field is applied to liquid crystal film, all liquid crystal molecules form the burnt cone of random arrangement under the action of electric field
Texture, and the information that the cholesteric liquid crystal for erasing planar orientation before this is saved realize full frame large area electrically erasable function
Energy (c)；
4) to erasure information region is needed in liquid crystal film, i.e. the cholesteric liquid crystal in planar texture carries out exciting light spoke
According to changed in the screw pitch of cholesteric liquid crystal simultaneously as the disturbance of liquid crystal molecule and the effect of polymer network, cholesteric
Phase liquid crystal molecule is changed into conical texture, erases the information that the cholesteric liquid crystal of planar orientation before this is saved, realizes small
The accurate light of surface area wipes function (d)；
5) after closing electric field or exciting light, cholesteric liquid crystal molecule still keeps burnt under the action of polymer network
Bore the non-reflective state (a) of texture.
It can realize that the pressure of liquid crystal film writes reflection display, full frame electrically erasable and accurate area by above-mentioned mode
Domain light wipes function.
Preferably, the exciting light radiation parameter in light erase process: appointing within the scope of a length of 300-460nm of excitation light wave
Meaning wave band, exciting light irradiation time are -1 hour 1 second, and excitating light strength is 1.0 μ W/cm2–300.0W/cm2。
Further, when adding up-conversion luminescence nanomaterial in photoresponse cholesteric liquid crystal compound system, due to
Long-wave band exciting light can be converted into short-wave band transmitting light in situ by up-conversion luminescence nanomaterial, and excitation wavelength range can
To widen to 300-1500nm, wherein the matrix of up-conversion luminescence nanomaterial is NaYF4、NaGdF4And NaYbF4It is a kind of at
Point simple substance or the compound core-shell structure of Multiple components, the doping with rare-earth ions element in mesostroma include Yb, Tm, Er, Ho, Nd and
The one or more of Mn.
In conclusion compared with prior art, the present invention having the advantage that
1. the preparation method of the reflective film with light erasing function of the invention, material therefor is from a wealth of sources, synthesis letter
Single, low in cost, simple processing is conducive to large area production.
2. the preparation method of the reflective film with light erasing function of the invention, by selecting different nematic phase liquid
The type of brilliant, chiral spiral shell vinyl compound, chipal compounds, polymer monomer, photoinitiator and upper transformation Illuminant nanometer material
And ratio, adjust the wavelength of exciting light and the intensity of irradiation, environment temperature, liquid crystal device substrate and thickness, it is available pre-
The reflective film with different regulation and control models, different regulation speed and different display modes first set.
3. the reflective film with light erasing function of the invention, using photoresponse cholesteric liquid crystal in pressure, electric field, light
Responsiveness variation under the conditions of irradiation etc., can be transformed into different optical textures, and corresponding light is presented in polymer network
Learn performance, i.e. reflective condition and non-reflective state.Wherein exciting light control technique has contactless remote operation, light source can replace
It changes, regulate and control the features such as accurate, realize the accurate light erasing function of small area selection area.
Detailed description of the invention
Fig. 1 is the preparation process with the reflective film of light erasing function；
Fig. 2 is that the pressure of reflective film writes the principle signal of display, full frame electrically erasable and accurate area light erase process
Figure；
Fig. 3 is pictorial diagram of the reflective film in pressure writing, light erasing and electrically erasable process of the preparation of embodiment 1；
Fig. 4 is the reflective film of the preparation of embodiment 1 in information display area and without the reflectance spectrum of information display area；
Fig. 5 is the interior polymer network structure of reflective film prepared by embodiment 1.
Specific embodiment
With the drawings and specific embodiments, the present invention is described in further detail below, but the present invention is not limited to this
A little embodiments.
Embodiment 1:
By chiral spiral shell vinyl compound (left-handed)/R5011 (dextrorotation)/polymerizable list of nematic liquid crystal SLC1717/ liquid crystal liquid crystal property
Proportionally 3.00/4.30/87.20/5.00/0.50 (wt%) is blended body/photoinitiator Irgacure 651, modulates light and rings
Answer cholesteric liquid crystal compound system.The glass microballoon (5 μm) that mass fraction is 0.50wt% is added to photoresponse cholesteric first
In phase crystal compound system and it is uniformly mixed；Then obtained compound system is placed in two panels ito thin film, is squeezed and is made by roller
At liquid crystal film；AC field (5V, 100Hz) is applied to liquid crystal film by ITO conductive layer, so that liquid crystal molecule is formed burnt cone and knits
Structure then irradiates (365nm, 2.0mW/cm using light2) 30min photopolymerization processing is carried out to liquid crystal film, finally it is prepared
Liquid crystal handwriting pad.
As shown in figure 3, carrying out pressure writing, the information of available " PKU " printed words on liquid crystal handwriting pad；Use excitation
Light (410nm, 10.0mW/cm2) irradiation 5s is carried out to " K " printed words therein after, can be carried out light erasing, and " P " on side
" U " printed words remain unchanged；AC field (5V, 100Hz) is applied to liquid crystal board, all display information can be carried out to electric wiping
It removes.
Reflectance spectrum test is carried out to reflective film using fiber spectrometer, as shown in figure 4, the display information area can be learnt
The visible light of domain reflection is in 520nm or so, and non-display information area will not reflect any visible light.
Reflective film is immersed in cyclohexane solution 5 days, the small molecule liquid crystal in film is washed away, utilizes scanning electron microscope pair
Polymer network structure inside film is characterized, as shown in Figure 5.
The structural formula of liquid crystal liquid crystal property polymerisable monomer described in the present embodiment is as follows:
The structural formula of chiral spiral shell vinyl compound described in the present embodiment is as follows:
Embodiment 2:
By chiral spiral shell vinyl compound (left-handed)/non-liquid crystal property polymerisable monomer of R1011 (dextrorotation)/nematic liquid crystal E7//
Liquid crystal liquid crystal property polymerisable monomer/photoinitiator Irgacure 784 proportionally 4.50/11.90/79.7/1.00/2.40/0.50
(wt%) it is blended, modulates photoresponse cholesteric liquid crystal compound system.The glass microballoon for being first 0.50wt% by mass fraction
(10 μm) are added in photoresponse cholesteric liquid crystal compound system and are uniformly mixed；Then obtained compound system is placed in two panels
In ito thin film, liquid crystal film is crushed to by roller；By ITO conductive layer to liquid crystal film apply AC field (5V,
100Hz), so that liquid crystal molecule is formed conical texture, then, irradiate (480nm, 20.0mW/cm using light2) liquid crystal film is carried out
30min photopolymerization processing, is finally prepared liquid crystal handwriting pad.
Pressure writing, the display information of available reflection visible light (480nm) are carried out on liquid crystal handwriting pad；Using sharp
Shine (380nm, 20.0mW/cm2) irradiation 2s is carried out to part display information after, can be carried out light erasing, and other displays
Information remains unchanged；AC field (5V, 100Hz) is applied to liquid crystal board, all display information can be subjected to electrically erasable.
The structural formula of non-liquid crystal property polymerisable monomer described in the present embodiment is as follows:
The structural formula of liquid crystal liquid crystal property polymerisable monomer described in the present embodiment is as follows:
The structural formula of chiral spiral shell vinyl compound described in the present embodiment is as follows:
Embodiment 3:
By chiral spiral shell vinyl compound (dextrorotation)/S5011 (left-handed)/nanoparticle NaGdF4:Mn@NaYF4: Er, Nd/ to
The non-liquid crystal property polymerisable monomer of column phase liquid crystal SLC1717//liquid crystal liquid crystal property polymerisable monomer/photoinitiator benzophenone is proportionally
6.30/5.60/1.50/81.20/1.20/3.80/0.40 (wt%) is blended, photoresponse cholesteric liquid crystal compound system is modulated.
The glass microballoon (7.5 μm) that mass fraction is 0.50wt% is added in photoresponse cholesteric liquid crystal compound system and is mixed first
It closes uniform；Then obtained compound system is placed in two panels ito thin film, liquid crystal film is crushed to by roller；It is led by ITO
Electric layer applies AC field (5V, 100Hz) to liquid crystal film, so that liquid crystal molecule is formed conical texture and is then irradiated using light
(350nm, 5.0mW/cm2) 60min photopolymerization processing is carried out to liquid crystal film, liquid crystal handwriting pad is finally prepared.
Pressure writing, the display information of available reflection visible light (600nm) are carried out on liquid crystal handwriting pad；Using sharp
Shine (850nm, 40.0mW/cm2) irradiation 3s is carried out to part display information after, can be carried out light erasing, and other displays
Information remains unchanged；AC field (5V, 100Hz) is applied to liquid crystal board, all display information can be subjected to electrically erasable.
The structural formula of non-liquid crystal property polymerisable monomer described in the present embodiment is as follows:
The structural formula of liquid crystal liquid crystal property polymerisable monomer described in the present embodiment is as follows:
The structural formula of chiral spiral shell vinyl compound described in the present embodiment is as follows:
Embodiment 4:
Chiral spiral shell vinyl compound (dextrorotation)/non-liquid crystal property of S1011 (left-handed)/nematic liquid crystal SLC1717/ is polymerizable
Proportionally 2.50/12.50/78.6/5.7/0.70 (wt%) is blended monomer/photoinitiator Irgacure 651, modulates light
Respond cholesteric liquid crystal compound system.The glass microballoon (3 μm) that mass fraction is 0.30wt% is added to photoresponse gallbladder first
In steroid phase crystal compound system and it is uniformly mixed；Then obtained compound system is placed in two panels ito thin film, is squeezed by roller
Liquid crystal film is made；AC field (5V, 100Hz) is applied to liquid crystal film by ITO conductive layer, liquid crystal molecule is made to form burnt cone
Texture then irradiates (365nm, 2.0mW/cm using light2) 60min photopolymerization processing is carried out to liquid crystal film, finally it is prepared into
To liquid crystal handwriting pad.
Pressure writing, the display information of available reflection visible light (580nm) are carried out on liquid crystal handwriting pad；Using sharp
Shine (425nm, 90.0mW/cm2) irradiation 3s is carried out to part display information after, can be carried out light erasing, and other displays
Information remains unchanged；AC field (5V, 100Hz) is applied to liquid crystal board, all display information can be subjected to electrically erasable.
The structural formula of non-liquid crystal property polymerisable monomer and ratio described in the present embodiment are as follows:
For 80wt%；
For 20wt%；
The structural formula of chiral spiral shell vinyl compound described in the present embodiment is as follows:
Embodiment 5:
By chiral spiral shell vinyl compound (dextrorotation)/S5011 (left-handed)/nanoparticle NaGdF4:Mn@NaYF4: Er, Nd/ to
The non-liquid crystal property polymerisable monomer/photoinitiator Irgacure 784 of column phase liquid crystal SLC1717/ proportionally 4.80/3.40/
1.00/82.60/7.20/1.00 (wt%) is blended, and modulates photoresponse cholesteric liquid crystal compound system.First by mass fraction
Glass microballoon (12.5 μm) for 0.30wt% is added in photoresponse cholesteric liquid crystal compound system and is uniformly mixed；Then will
Obtained compound system is placed in two panels ito thin film, is crushed to liquid crystal film by roller；It is thin to liquid crystal by ITO conductive layer
Film applies AC field (5V, 100Hz), and liquid crystal molecule is made to form conical texture, then, irradiates (500nm, 50.0mW/ using light
cm2) 60min photopolymerization processing is carried out to liquid crystal film, liquid crystal handwriting pad is finally prepared.
Pressure writing, the display information of available reflection visible light (510nm) are carried out on liquid crystal handwriting pad；Using sharp
Shine (920nm, 60.0mW/cm2) irradiation 2s is carried out to part display information after, can be carried out light erasing, and other displays
Information remains unchanged；AC field (5V, 100Hz) is applied to liquid crystal board, all display information can be subjected to electrically erasable.
The structural formula of non-liquid crystal property polymerisable monomer and ratio described in the present embodiment are as follows:
For 75wt%；
For 25wt%；
The structural formula of chiral spiral shell vinyl compound described in the present embodiment is as follows:
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Although ginseng
It is described the invention in detail according to embodiment, it will be apparent to an ordinarily skilled person in the art that technical side of the invention
Case is modified or replaced equivalently, and without departure from the spirit and scope of technical solution of the present invention, should all be covered in the present invention
Scope of the claims in.
Claims (9)
1. a kind of reflective film with light erasing function, which is characterized in that the film includes:
Photoresponse cholesteric liquid crystal compound system is perfused among ito thin film, compacting forms thin with a thickness of 2 μm -50 μm of liquid crystal
Film；
The photoresponse cholesteric liquid crystal compound system includes the main body small molecule that mass fraction is 60.0wt%-95.0wt%
Chiral spiral shell vinyl compound, the mass fraction 0.2wt%- that liquid crystal material, mass fraction are 0.1wt%-15.0wt%
The chipal compounds of 30.0wt%, the liquid crystal liquid crystal property polymerisable monomer of 0.0wt%-20.0wt%, 0.0wt%-20.0wt% it is non-
The photoinitiator of liquid crystal liquid crystal property polymerisable monomer and 0.1wt%-5.0wt%.
2. the reflective film according to claim 1 with light erasing function, which is characterized in that the main body small molecule liquid
Brilliant material is nematic liquid crystal SLC1717 or nematic liquid crystal E7.
3. the reflective film according to claim 1 with light erasing function, which is characterized in that the chirality helicene class
Close the one or more that object is selected from compound shown in following formula:
In formula, R1–R9Selected from H atom, phenyl ring, CnH2n+1Alkyl chain, OCnH2n+1One or more of oxyalkyl chain, n, which is selected from, is
1-12；
Or R1–R9Selected from one or more of following group, it is 1-12 that n, which is selected from,；
4. the reflective film according to claim 1 with light erasing function, which is characterized in that the chipal compounds
Selected from one or more of S811, R811, S1011, R1011, S5011 and R5011.
5. the reflective film according to claim 1 with light erasing function, which is characterized in that the photoresponse cholesteric phase
Crystal compound system further includes up-conversion luminescence nanomaterial, and the matrix of the up-conversion luminescence nanomaterial includes NaYF4、
NaGdF4And NaYbF4One of ingredient simple substance or the compound core-shell structure of Multiple components, the doping with rare-earth ions in mesostroma
Element includes one or more of Yb, Tm, Er, Ho, Nd and Mn.
6. the reflective film according to claim 1 with light erasing function, which is characterized in that the reflective film has height
The pressure of brightness and high contrast writes the light erasing of reflection display function, large area electrically erasable function and small area selection area
Function, specifically:
1) non-reflective conical texture is presented in original state due to the effect of polymer network for the cholesteric liquid crystal of liquid crystal film；
2) pressure is applied to the region for needing to be written information above liquid crystal film, since the boundary effect of film substrate forces gallbladder
Steroid phase Formation of liquid crystals planar texture, and reflection wavelengthVisible light, whereinFor being averaged for cholesteric liquid crystal
Refractive index, p0For the initial screw pitch of cholesteric liquid crystal, this state can keep stablizing constant for a long time, that is, realize pressure book
Write reflection display function；
3) electric field is applied to liquid crystal film, the burnt cone that all liquid crystal molecules form random arrangement under the action of electric field is knitted
Structure, and the information that the cholesteric liquid crystal for erasing planar orientation before this is saved realize full frame large area electrically erasable function；
4) to erasure information region is needed in liquid crystal film, i.e. the cholesteric liquid crystal in planar texture carries out exciting light irradiation,
It is changed in the screw pitch of cholesteric liquid crystal simultaneously as the disturbance of liquid crystal molecule and the effect of polymer network, cholesteric phase
Liquid crystal molecule is changed into conical texture, erases the information that the cholesteric liquid crystal of planar orientation before this is saved, realizes facet
The accurate light in product region wipes function；
5) after closing electric field or exciting light, cholesteric liquid crystal molecule still keeps burnt cone to knit under the action of polymer network
The non-reflective state of structure.
7. the reflective film according to claim 1 with light erasing function, which is characterized in that swashing in light erase process
Luminescence irradiation condition are as follows: any wave band within the scope of a length of 300-460nm of excitation light wave, exciting light irradiation time are 1 second -1 small
When, excitating light strength is 1.0 μ W/cm2–300.0W/cm2。
8. the reflective film according to claim 7 with light erasing function, which is characterized in that when in photoresponse cholesteric phase
When adding up-conversion luminescence nanomaterial in crystal compound system, excitation wavelength range is widened to 300-1500nm.
9. the preparation method of the reflective film with light erasing function described in claim any one of 1-8, the preparation method packet
Include following steps:
1) by mass fraction be 60.0wt%-95.0wt% main body small molecule liquid crystal material, mass fraction 0.1wt%-
The chiral spiral shell vinyl compound of 15.0wt%, chipal compounds, the 0.0wt%- that mass fraction is 0.2wt%-30.0wt%
The liquid crystal liquid crystal property polymerisable monomer of 20.0wt%, the non-liquid crystal property polymerisable monomer of 0.0wt%-20.0wt% and 0.1wt%-
The photoinitiator mixture of 5.0wt% is uniform and obtains the mixed crystal compound system with very wide cholesteric phase temperature range；
2) photoresponse cholesteric liquid crystal compound system is pressed into liquid crystal film with plastics ito thin film, by separation pad or glass
Microballon controls the thickness of liquid crystal device；
3) electric field is applied to liquid crystal film, so that liquid crystal molecule is in the conical texture of non-reflective state, and in its cholesteric phase
Light irradiation polymerization is carried out in temperature range；Electric field is closed after light irradiation polymerization, will form inside the liquid crystal film after polymerization
Polymer network.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110286511A (en) * | 2019-06-20 | 2019-09-27 | 湖南皓志纳米技术有限公司 | A kind of liquid crystal handwriting pad film and preparation method thereof containing big HTP value chiral agent |
| CN111454736A (en) * | 2020-04-27 | 2020-07-28 | Tcl华星光电技术有限公司 | Circular polarization modulation device and preparation method thereof |
| WO2021116139A1 (en) * | 2019-12-12 | 2021-06-17 | Merck Patent Gmbh | Composition |
| CN113759585A (en) * | 2021-08-24 | 2021-12-07 | 山东蓝贝思特教装集团股份有限公司 | Optical erasing element and optical erasing element erasing light wavelength determination method |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090152772A1 (en) * | 2004-01-28 | 2009-06-18 | Kent State University And Lachezar Komitov | Method of fabricating electro-optical devices with polymer-stabilized liquid crystal molecules |
| CN101706625A (en) * | 2009-11-13 | 2010-05-12 | 北京科技大学 | Method for preparing wide wave reflective film by using polymer stabilized cholesteric phase liquid crystal material |
| CN102778718A (en) * | 2012-07-05 | 2012-11-14 | 北京科技大学 | Method for preparing broadband reflection liquid crystal polarizing film with high performance |
| CN103246096A (en) * | 2012-02-13 | 2013-08-14 | 江苏和成显示科技股份有限公司 | Bistable liquid crystal handwriting device |
| CN104297836A (en) * | 2014-10-17 | 2015-01-21 | 京东方科技集团股份有限公司 | Preparation method for liquid crystal thin film, liquid crystal thin film prepared through preparation method and circular polarizer prepared through preparation method |
| CN105467708A (en) * | 2016-02-03 | 2016-04-06 | 京东方科技集团股份有限公司 | Writing board, electronic writing equipment and manufacturing method |
| CN106405916A (en) * | 2016-12-16 | 2017-02-15 | 北京大学 | Reverse type electric-control liquid-crystal light adjusting film and preparation method thereof |
| CN107092110A (en) * | 2017-06-06 | 2017-08-25 | 深圳市厚璞科技有限公司 | A kind of display device and its display methods for being integrated with bistable liquid crystal film |
| CN107315270A (en) * | 2017-06-28 | 2017-11-03 | 北京大学 | Write with light or light wipes bistable liquid crystal devices of function and preparation method thereof |
-
2017
- 2017-11-14 CN CN201711120169.0A patent/CN109782505A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090152772A1 (en) * | 2004-01-28 | 2009-06-18 | Kent State University And Lachezar Komitov | Method of fabricating electro-optical devices with polymer-stabilized liquid crystal molecules |
| CN101706625A (en) * | 2009-11-13 | 2010-05-12 | 北京科技大学 | Method for preparing wide wave reflective film by using polymer stabilized cholesteric phase liquid crystal material |
| CN103246096A (en) * | 2012-02-13 | 2013-08-14 | 江苏和成显示科技股份有限公司 | Bistable liquid crystal handwriting device |
| CN102778718A (en) * | 2012-07-05 | 2012-11-14 | 北京科技大学 | Method for preparing broadband reflection liquid crystal polarizing film with high performance |
| CN104297836A (en) * | 2014-10-17 | 2015-01-21 | 京东方科技集团股份有限公司 | Preparation method for liquid crystal thin film, liquid crystal thin film prepared through preparation method and circular polarizer prepared through preparation method |
| CN105467708A (en) * | 2016-02-03 | 2016-04-06 | 京东方科技集团股份有限公司 | Writing board, electronic writing equipment and manufacturing method |
| CN106405916A (en) * | 2016-12-16 | 2017-02-15 | 北京大学 | Reverse type electric-control liquid-crystal light adjusting film and preparation method thereof |
| CN107092110A (en) * | 2017-06-06 | 2017-08-25 | 深圳市厚璞科技有限公司 | A kind of display device and its display methods for being integrated with bistable liquid crystal film |
| CN107315270A (en) * | 2017-06-28 | 2017-11-03 | 北京大学 | Write with light or light wipes bistable liquid crystal devices of function and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 石海兵: "柔性双稳态胆甾相液晶显示单元的研究", 《中国优秀硕士学位论文全文数据库-信息科技辑》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110286511A (en) * | 2019-06-20 | 2019-09-27 | 湖南皓志纳米技术有限公司 | A kind of liquid crystal handwriting pad film and preparation method thereof containing big HTP value chiral agent |
| 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 |
| WO2021116139A1 (en) * | 2019-12-12 | 2021-06-17 | Merck Patent Gmbh | Composition |
| CN114787075A (en) * | 2019-12-12 | 2022-07-22 | 默克专利股份有限公司 | Composition comprising a fatty acid ester and a fatty acid ester |
| JP2023505715A (en) * | 2019-12-12 | 2023-02-10 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Composition |
| CN111454736A (en) * | 2020-04-27 | 2020-07-28 | Tcl华星光电技术有限公司 | Circular polarization modulation device and preparation method thereof |
| CN111454736B (en) * | 2020-04-27 | 2022-02-22 | Tcl华星光电技术有限公司 | Circular polarization modulation device and preparation method thereof |
| CN115356870B (en) * | 2021-05-17 | 2024-05-28 | 肯特显示器公司 | Liquid crystal device erased by bending |
| CN115356870A (en) * | 2021-05-17 | 2022-11-18 | 肯特显示器公司 | Liquid crystal devices erased by bending |
| CN113759585A (en) * | 2021-08-24 | 2021-12-07 | 山东蓝贝思特教装集团股份有限公司 | Optical erasing element and optical erasing element erasing light wavelength determination method |
| CN113759585B (en) * | 2021-08-24 | 2023-06-13 | 山东蓝贝思特教装集团股份有限公司 | Optical erasing member and optical erasing wavelength determining method thereof |
| CN116515340A (en) * | 2023-03-06 | 2023-08-01 | 北京印刷学院 | A kind of cholesteric phase liquid crystal/polymer composite system microcapsule and preparation method thereof |
| CN116515340B (en) * | 2023-03-06 | 2024-05-03 | 北京印刷学院 | A cholesteric liquid crystal/polymer composite system microcapsule and its preparation method |
| CN116606189A (en) * | 2023-05-06 | 2023-08-18 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal molecular motor with photo-thermal dual responsiveness and preparation method and application thereof |
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