CN106338854B - The method that heating-ultraviolet light step-by-step polymerization prepares cholesteric liquid crystal function film - Google Patents
The method that heating-ultraviolet light step-by-step polymerization prepares cholesteric liquid crystal function film Download PDFInfo
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Abstract
The invention discloses the methods that a kind of heating-ultraviolet light step-by-step polymerization prepares cholesteric liquid crystal function film, cholesteric liquid crystal mixture, liquid crystal liquid crystal property ultraviolet light polymerisable monomer, photoinitiator, thermal polymerization monomer and glass microballoon are clipped in two panels after mixing to be coated among the transparent conductive film of tin indium oxide, it is even with roll-in, first heat cure, after its thermal polymerization monomer is complete.Keep cholesteric liquid crystal parallel-oriented by the effect of electric field again, while carrying out ultraviolet light, is solidified into trans- or bistable state pdlc film.Prepared by the present invention trans- or bistable state PDLC thin-film material can control polymeric network structure by the allotment of uv photopolymerization monomer and thermal polymerization monomer, improve the electro-optical properties of PDLC film, enhance cohesive force between liquid crystal/polymer composite and two layers of ITO plastic film, and improves trans- and bistable state PDLC film thermal stability.
Description
Technical field
The invention belongs to field of functional materials, and specifically, the present invention is more particularly directed to a kind of heating-ultraviolet light step-by-step polymerization systems
The method of standby cholesteric liquid crystal function film.
Background technique
Intelligent glass is that the optical properties such as a kind of transmitance, reflectivity or color can be adjusted by electric field, temperature, magnetic field etc.
The glass of section.The polymer dispersed liquid crystals (Polymer dispersed liquidcrystals, PDLC) that the present invention uses is thin
Film is a kind of compound electrooptical material of Liquid Crystal/Polymer.PDLC is applied in electric-controlled intelligent glass art, is made by adjusting extra electric field
Glass is converted between transparent and opaque two states.Electric-controlled intelligent glass have energy-saving and environmental protection, protection privacy, safety, every
The advantages that sound and regulation facilitate, can be widely used for the car sunroofs such as benz, BMW, top-grade building, bank, insurance company, doctor
The fields such as the partitions such as institute, hotel, dining room, Jin Dian, exhibition of cultural relics room, museum, church, command centre, the construction of door, window, ceiling
Institute.
Current PDLC film majority uses nematic liquid crystal, it is necessary to work under lasting electric field, with energy-efficient big
Power is advocated, we have invested sight the cholesteric liquid crystal of particular molecule arrangement.Cholesteric liquid crystal under different conditions this
Body has several different TEXTURE STATEs, and wherein planar texture (p) and conical texture (fc) are two kinds of stable texture, they are all
Voltage is not needed to maintain, can remain stable in the state of null field.The adjustable salt ion of electric field is doped with negativity Jie
Conversion between the cholesteric liquid crystal Focal conic state and parallel state of electric constant.When applying direct current or low frequency electric field, in liquid crystal molecule
The unstability of hydromechanics dynamic occurs for portion, but when voltage reaches certain threshold value, and dynamic scattering occurs for liquid crystal molecule, and light is presented
Scattering states.When applying high-frequency electric field, liquid crystal molecule can obtain planar orientation, and transparent state is presented.
In trans- and bistable state PDLC membrane-film preparation process, it also often will appear Liquid Crystal/Polymer composite material and two
Cohesive force defective tightness between layer tin indium oxide (ITO) plastic film and the case where cause ITO plastic film to be detached from, this is to big rule
The technique production of mould brings very big difficulty, not only reduces the performance quality of product, has also seriously affected the economic effect of product
Benefit.
Summary of the invention
The object of the present invention is to provide the sides that a kind of heating-ultraviolet light step-by-step polymerization prepares cholesteric liquid crystal function film
The trans- or bistable state PDLC thin-film material of method, this method preparation can pass through the allotment of uv photopolymerization monomer and thermal polymerization monomer
To control polymeric network structure, the electro-optical properties of improvement PDLC film, enhancing liquid crystal/polymer composite and two
Cohesive force between layer ITO plastic film, and trans- or bistable state PDLC film thermal stability is improved, in very good solution production
Practical problem.
In order to achieve the above objectives, present invention employs the following technical solutions:
A kind of heating-ultraviolet light step polymerization prepares trans- and bistable state PDLC film method, by cholesteric liquid crystal
Mixture, liquid crystal liquid crystal property ultraviolet light polymerisable monomer, photoinitiator, thermal polymerization monomer and glass microballoon are clipped in two panels after mixing
It is coated among the transparent conductive film of tin indium oxide (ITO), first heat cure even with roll-in, after its thermal polymerization monomer is complete.Lead to again
The effect for crossing electric field keeps cholesteric liquid crystal parallel-oriented, while carrying out ultraviolet light, is solidified into trans- or bistable state pdlc film.
Specific making step are as follows:
1) the liquid crystal liquid crystal property ultraviolet light polymerisable monomer that weight percent is 1wt%~20wt% cholesteric liquid crystal is introduced to mix
It closes in object and photoinitiator mixture is ultraviolet polymerisable monomer crystal compound system, the additive amount of photoinitiator is that liquid crystal liquid crystal property is ultraviolet
0.01wt%~10wt% of photopolymerizable monomer and cholesteric liquid crystal mixture gross mass；
2) the polysulfide alcohol type curing agent that weight percent is 20wt%~80wt% is introduced into mixture in thermal polymerization monomer is
Thermal polymerization compound system；
3) by weight percent be 10wt%~60wt% thermal polymerization compound system introduce weight percent be 40wt%~
90wt% mixture after ultraviolet polymerisable monomer liquid crystal complex system, uniformly mixed at a temperature of 0 DEG C~70 DEG C, formed it is each to
Same sex liquid；
4) into isotropic liquid be added thermosetting accelerator formed mixed system, thermosetting accelerator content be it is each to
The 1.0~5.0% of same sex liquid gross mass；
5) glass microballoon is added to mixed system, controls the thickness of pdlc film, the content of glass microballoon is that mixed system is total
The 0.5~1.0% of quality；
6) it is poured into after mixing the mixed system that glass microballoon is added with the glass substrate system for being coated with conductive indium-tin oxide layer
In the liquid crystal cell of work, or with the plastic film for being coated with conductive indium-tin oxide layer the mixed system that glass microballoon is added is pressed into
Liquid crystal film, the thermal polymerization at 0~55 DEG C, thermal polymerization time are 3~30 days；Cholesteric liquid crystal is then made by the effect of electric field
It is parallel-oriented, while being irradiated with ultraviolet light, finally it is solidified into cholesteric liquid crystal function film；
The cholesteric liquid crystal function film is trans- or bistable state PDLC film.
Method of the invention is suitable for all cholesteric liquid crystals, especially following cholesteric liquid crystal mixtures, the gallbladder
Steroid phase liquid crystal compound includes chiral additives and nematic liquid crystal mixture.
Preferably, the chiral additives are selected from one of S811, R811, R1011, CB15 and ZLI-4572 or more
Kind.
Preferably, the nematic liquid crystal mixture contains I, II, III, IV, V, VI and VII class compound, all kinds of chemical combination
It is 35~50%, II class compound is 10~30% that object is respectively as follows: compound I by weight percentage, and Group III compound is 5
It is 1~3%, VI class compound is 10~20%, VII class compound that~10%, IV class compound, which are 10~15%, V compound,
It is 0.05~0.1%；The general structure of classes of compounds is respectively as follows:
Wherein, R1~R11Respectively alkyl-CnH2n+1Or alkoxy-OCnH2n+1In one, wherein n be integer 1~5；Z
For one or more of singly-bound ,-COO- or-C ≡ C- group；L1~L2One in respectively-H atom ,-F atom or cyano
It is a；L3~L4One in respectively-H atom or cyano；m1~m4Value be respectively 0 or 1, and not simultaneously be 0 or 1.
In addition, nematic liquid crystal mixture in the present invention can also use (the Jiangsu and at display section HNG726200-100
The production of skill limited liability company, Tc=101 DEG C).
Preferably, the liquid crystal liquid crystal property ultraviolet light polymerisable monomer is selected from one of following structural compounds or a variety of, but
It is not limited to these compounds:
Compound 1:
Compound 2:
Compound 3:
Compound 4:
Compound 5:
Compound 6:
Compound 7:
Compound 8:
Compound 9:
Compound 10:
Above-mentioned liquid crystal liquid crystal property ultraviolet light polymerisable monomer is monofunctional monomer or bifunctionality or polyfunctional monomer
Preferably, the thermal polymerization monomer is epoxy resin, is specifically as follows glycidol ethers compound, glycidol
One of ester type compound, glycidol amine compound and aliphatic epoxy compound are a variety of.But it is not limited to these
Material.More specifically, one of following structural compounds or a variety of can be selected from:
Compound a:
Compound b:
Compound c:
Compound d:
Compound e:
Compound f:
Compound g:
Compound h:
Compound i:
Compound j:
Preferably, in step 6), the condition of ultraviolet light are as follows: wavelength 365nm, ultraviolet ray intensity are 1 μ W/cm2~
3mW/cm2, light application time 1min~60min.
Photoinitiator used in the present invention be benzil ketals (such as benzil dimethyl ketal, i.e. benzoin dimethylether,
Product name is Irgacure 651) or fragrant ketone (such as benzophenone, thio anthrone)
Curing agent polysulfide alcohol type curing agent used in the present invention is (such as: Poly [oxy (methyl-1,2-
ethanediyl)],a-hydro-w-(2-hydroxy-3-mercaptopropoxy)-,a,a',a”-ether with 2-
(hydroxymethyl) -2-methyl-1,3-propanediol (3:1), product name Capcure3-800)
Thermosetting accelerator used in the present invention be tertiary amine compounds (such as: adjacent (dimethylamino methyl) phenol, trade name
Referred to as DMP-10)；2,4,6- tri- (dimethylamino methyl) phenol, product name are DMP-30 etc.).
Nematic liquid crystal is small molecule liquid crystal material in the present invention, can be negative dielectric anisotropic small molecule liquid crystal material
(big negative dielectric anisotropic substance substitution can be added with positive dielectric anisotropy small molecule liquid crystal), may finally be had
There is the crystal compound system of negative dielectric anisotropic, so that the molecule in crystal compound system can be made under AC field effect
It is parallel-oriented.
The present invention causes the preparation of Polymerizing phase splitting method with trans- or bi-stable effect using heating-ultraviolet light irradiation substep
Polymer dispersed liquid crystals (PDLC) film, and by it be applied to electric-controlled intelligent glass.
The present invention produces a kind of trans- or bistable state PDLC film according to the distinctive bistable characteristic of cholesteric liquid crystal,
Replace nematic liquid crystal with cholesteric liquid crystal, can work under null field, and can transparent and opaque two states
Between convert.
The present invention acts on the anchoring of liquid crystal molecule by the content of allotment liquid crystal liquid crystal property photo polymerization monomer, to realize trans-
Or the effect of bistable state PDLC film.
The present invention has the advantages that by selection thermal polymerization monomer and liquid crystal liquid crystal property ultraviolet light polymerisable monomer, through heat and purple
Outer light irradiation causes the step-by-step polymerization cross-linking reaction of above-mentioned polymerization system, and being formed has trans- or bi-stable effect PDLC film material
Material, while enhancing polymer network intensity and improving the interfacial adhesion (peel strength) between macromolecule network and ito film.
Detailed description of the invention
Fig. 1 is the electro-optical properties curve of 1 gained PDLC film of embodiment in the present invention.
Fig. 2 is the polarized light microscopy figure of 1 gained PDLC film of embodiment in the present invention.
Fig. 3 is the polarized light microscopy figure of 2 gained PDLC film of embodiment in the present invention.
Fig. 4 is the polarized light microscopy figure of 3 gained PDLC film of embodiment in the present invention.
Fig. 5 is the electro-optical properties curve of 4 gained PDLC film of embodiment in the present invention.
Specific embodiment
With the drawings and specific embodiments, the present invention is described in further detail below.
Embodiment 1
It is with weight percent by the liquid crystal liquid crystal property uv photopolymerization monomer (compound 1) that weight percent is 3wt%
(the cholesteric liquid crystal mixture selected in the present invention is containing weight percent 14% to the cholesteric liquid crystal mixture of 97wt%
The composition of chiral additives S811 and nematic liquid crystal mixture, nematic liquid crystal mixture is as shown in table 1) and photoinitiator
Irgacure651 is uniformly mixed, and as ultraviolet polymerisable monomer crystal compound system, the additive amount of photoinitiator is that liquid crystal liquid crystal property is purple
The 5% of outer photopolymerizable monomer and cholesteric liquid crystal mixture gross mass；The polysulfide alcohol type that weight percent is 50% is solidified
E51 epoxy resin/glycidol the esters for the epoxy group containing conjugation that agent Capcure 3-800 and weight percent are 50%
ERL-4221 epoxy resin is uniformly mixed, as thermal polymerization compound system；By thermal polymerization compound system and ultraviolet polymerisable monomer
Crystal compound system in mass ratio 2: 8 is uniformly mixed, forms isotropic liquid at a temperature of 55 DEG C.Into isotropic liquid
Thermosetting accelerator is added and forms mixed system, thermosetting accelerator DMP-30 content is isotropic liquid gross mass
5.0%.The glass microballoon that partial size is 20 μm is added into mixed system, controls the thickness of pdlc film, the content of glass microballoon is about
It is the 0.5% of mixed system gross mass.
The mixed system that glass microballoon is added is clipped in two panels to be coated among the transparent conductive film of ITO after evenly mixing, is used
Roll-in is even, forms the film layer of 20 μ m-thicks, is protected from light heat cure 7 days under room temperature (20 DEG C), the ultraviolet light for being later 365nm with wavelength
It is irradiated (while applying high-frequency electric field).Ultraviolet ray intensity is 1 μ W/m2, light application time be 60 minutes to get arrive bistable state
PDLC film.The electro-optical curve of the PDLC film of above-mentioned preparation is measured as shown in Figure 1, from Fig. 1 with liquid crystal comprehensive parameter tester
As can be seen that in zero electric field, film transmitance with higher, when applying low frequency (frequency < 1000Hz) electric field to it, with
The increase film of voltage be changed into scattering states from transparent state, after removing electric field, this scattering states is settled out；When to scattering states
Film when applying high frequency (frequency > 1000Hz) electric field, film is changed into transparent state by scattering states, and after removing electric field, this is transparent
State is settled out.In embodiment 1 PDLC film microscopic appearance using petrographic microscope (POM) measure, as a result as shown in Fig. 2,
Figure it is seen that foring more uniform mesh-structured.Function film obtained by the present embodiment after tested, peel strength
For 1.3N/cm.
Nematic liquid crystal mixture employed in 1 embodiment 1-6 of table
Embodiment 2
It is with weight percent by the liquid crystal liquid crystal property uv photopolymerization monomer (compound 2) that weight percent is 1wt%
(the cholesteric liquid crystal mixture selected in the present invention is containing weight percent 14% to the cholesteric liquid crystal mixture of 99wt%
The composition of chiral additives R811 and nematic liquid crystal mixture, nematic liquid crystal mixture is as shown in table 1) and photoinitiator
Irgacure651 is uniformly mixed, and as ultraviolet polymerisable monomer crystal compound system, the additive amount of photoinitiator is that liquid crystal liquid crystal property is purple
The 0.01% of outer photopolymerizable monomer and cholesteric liquid crystal mixture gross mass；The polysulfide alcohol type that weight percent is 20% is consolidated
E51 epoxy resin/glycidol the esters for the epoxy group containing conjugation that agent Capcure 3-800 and weight percent are 80%
ERL-4221 epoxy resin is uniformly mixed, as thermal polymerization compound system；By thermal polymerization compound system and ultraviolet polymerisable monomer
Crystal compound system in mass ratio 6: 4 is uniformly mixed, forms isotropic liquid at a temperature of 60 DEG C.Into isotropic liquid
Thermosetting accelerator is added and forms mixed system, thermosetting accelerator DMP-30 content is isotropic liquid gross mass
5.0%.The glass microballoon that partial size is 20 μm is added into mixed system, controls the thickness of pdlc film, the content of glass microballoon is about
It is the 0.5% of mixed system gross mass.
The mixed system that glass microballoon is added is clipped in two panels to be coated among the transparent conductive film of ITO after evenly mixing, is used
Roll-in is even, forms the film layer of 20 μ m-thicks, heat cure is protected from light at 30 DEG C 5 days, is shone later with the ultraviolet light that wavelength is 365nm
It penetrates.Ultraviolet ray intensity is 0.4mW/m2, light application time be 50 minutes to get arrive bistable state PDLC film.PDLC is thin in embodiment 2
Film low-light pattern is measured using petrographic microscope (POM), as a result as shown in figure 3, foring long and narrow intercommunicating pore.The present embodiment institute
Obtain function film after tested, peel strength 1.4N/cm.
Embodiment 3
It is with weight percent by the liquid crystal liquid crystal property uv photopolymerization monomer (compound 3) that weight percent is 6wt%
(the cholesteric liquid crystal mixture selected in the present invention is containing weight percent 14% to the cholesteric liquid crystal mixture of 94wt%
The composition of chiral additives R1011 and nematic liquid crystal mixture, nematic liquid crystal mixture is as shown in table 1) and it is light-initiated
Agent Irgacure651 is uniformly mixed, and as ultraviolet polymerisable monomer crystal compound system, the additive amount of photoinitiator is liquid crystal liquid crystal property
The 6% of ultraviolet light polymerisable monomer and cholesteric liquid crystal mixture gross mass；The polysulfide alcohol type that weight percent is 40% is consolidated
E51 epoxy resin/glycidol the esters for the epoxy group containing conjugation that agent Capcure 3-800 and weight percent are 60%
ERL-4221 epoxy resin is uniformly mixed, as thermal polymerization compound system；By thermal polymerization compound system and ultraviolet polymerisable monomer
Crystal compound system in mass ratio 5: 5 is uniformly mixed, forms isotropic liquid at a temperature of 70 DEG C.Into isotropic liquid
Thermosetting accelerator is added and forms mixed system, thermosetting accelerator DMP-30 content is isotropic liquid gross mass
4.0%.The glass microballoon that partial size is 20 μm is added into mixed system, controls the thickness of pdlc film, the content of glass microballoon is about
It is the 0.5% of mixed system gross mass.
The mixed system that glass microballoon is added is clipped in two panels to be coated among the transparent conductive film of ITO after evenly mixing, is used
Roll-in is even, forms the film layer of 20 μ m-thicks, heat cure is protected from light at 40 DEG C 4 days, is shone later with the ultraviolet light that wavelength is 365nm
It penetrates.Ultraviolet ray intensity is 1mW/m2, light application time be 30 minutes to get arrive bistable state PDLC film.PDLC film in embodiment 3
Microscopic appearance is measured using petrographic microscope (POM), as a result as shown in figure 4, foring approximate circle mesh, but size
It is unevenly distributed.Function film obtained by the present embodiment after tested, peel strength 1.6N/cm.
Embodiment 4
It is with weight percent by the liquid crystal liquid crystal property uv photopolymerization monomer (compound 4/5/6) that weight percent is 10wt%
(the cholesteric liquid crystal mixture selected in the present invention is containing weight percent 14% to the cholesteric liquid crystal mixture of 90wt%
The composition of chiral additives CB15 and nematic liquid crystal mixture, nematic liquid crystal mixture is as shown in table 1) and photoinitiator
Irgacure651 is uniformly mixed, and as ultraviolet polymerisable monomer crystal compound system, the additive amount of photoinitiator is that liquid crystal liquid crystal property is purple
The 7% of outer photopolymerizable monomer and cholesteric liquid crystal mixture gross mass；The polysulfide alcohol type that weight percent is 60% is solidified
E51 epoxy resin/glycidol the esters for the epoxy group containing conjugation that agent Capcure 3-800 and weight percent are 40%
ERL-4221 epoxy resin is uniformly mixed, as thermal polymerization compound system；By thermal polymerization compound system and ultraviolet polymerisable monomer
Crystal compound system in mass ratio 4: 6 is uniformly mixed, forms isotropic liquid at a temperature of 40 DEG C.Into isotropic liquid
Thermosetting accelerator is added and forms mixed system, thermosetting accelerator DMP-30 content is isotropic liquid gross mass
3.0%.The glass microballoon that partial size is 20 μm is added into mixed system, controls the thickness of pdlc film, the content of glass microballoon is about
It is the 0.5% of mixed system gross mass.
The mixed system that glass microballoon is added is clipped in two panels to be coated among the transparent conductive film of ITO after evenly mixing, is used
Roll-in is even, forms the film layer of 20 μ m-thicks, heat cure is protected from light at 50 DEG C 4 days, is shone later with the ultraviolet light that wavelength is 365nm
It penetrates.Ultraviolet ray intensity is 2mW/m2, light application time be 20 minutes to get arrive trans- PDLC film.With liquid crystal testing synthesis parameter
Instrument measure the electro-optical curve of the PDLC film of above-mentioned preparation as shown in figure 5, preparation trans- PDLC presented in zero electric field it is transparent
State, when applying low frequency (frequency < 1000Hz) electric field to it, as the increase film of voltage is changed into scattering states from transparent state,
After removing electric field, this scattering states is promptly restored to transparent state.After tested, peel strength is function film obtained by the present embodiment
1.7N/cm。
Embodiment 5
It is with weight percent by the liquid crystal liquid crystal property uv photopolymerization monomer (compound 6/7/8) that weight percent is 15wt%
(the cholesteric liquid crystal mixture selected in the present invention is containing weight percent 14% to the cholesteric liquid crystal mixture of 85wt%
The composition of chiral additives ZLI4572 and nematic liquid crystal mixture, nematic liquid crystal mixture is as shown in table 1) and light draw
Hair agent benzophenone uniformly mixes, and as ultraviolet polymerisable monomer crystal compound system, the additive amount of photoinitiator is liquid crystal liquid crystal property
The 9% of ultraviolet light polymerisable monomer and cholesteric liquid crystal mixture gross mass；The polysulfide alcohol type that weight percent is 70% is consolidated
E51 epoxy resin/glycidol the esters for the epoxy group containing conjugation that agent Capcure 3-800 and weight percent are 30%
ERL-4221 epoxy resin is uniformly mixed, as thermal polymerization compound system；By thermal polymerization compound system and ultraviolet polymerisable monomer
Crystal compound system in mass ratio 3: 7 is uniformly mixed, forms isotropic liquid at a temperature of 30 DEG C.Into isotropic liquid
Thermosetting accelerator is added and forms mixed system, thermosetting accelerator DMP-10 content is isotropic liquid gross mass
2.0%.The glass microballoon that partial size is 20 μm is added into mixed system, controls the thickness of pdlc film, the content of glass microballoon is about
It is the 1% of mixed system gross mass.
The mixed system that glass microballoon is added is clipped in two panels to be coated among the transparent conductive film of ITO after evenly mixing, is used
Roll-in is even, forms the film layer of 20 μ m-thicks, heat cure is protected from light at 55 DEG C 3 days, is shone later with the ultraviolet light that wavelength is 365nm
It penetrates.Ultraviolet ray intensity is 2.5mW/m2, light application time be 10 minutes to get arrive trans- PDLC film.Function obtained by the present embodiment
Film after tested, peel strength 1.4N/cm.
Embodiment 6
It is with weight percent by the liquid crystal liquid crystal property uv photopolymerization monomer (compound 9/10) that weight percent is 20wt%
(the cholesteric liquid crystal mixture selected in the present invention is containing weight percent 14% to the cholesteric liquid crystal mixture of 80wt%
The composition of chiral additives S811 and ZLI4572 and nematic liquid crystal mixture, nematic liquid crystal mixture is as shown in table 1) with
And the thio anthrone of photoinitiator uniformly mixes, as ultraviolet polymerisable monomer crystal compound system, the additive amount of photoinitiator is
The 10% of liquid crystal liquid crystal property ultraviolet light polymerisable monomer and cholesteric liquid crystal mixture gross mass；The polysulfide for being 80% by weight percent
Alcohol type curing agent Capcure 3-800 and the E51 epoxy resin/shrink for the epoxy group containing conjugation that weight percent is 20% are sweet
Grease class ERL-4221 epoxy resin is uniformly mixed, as thermal polymerization compound system；Thermal polymerization compound system is gathered with ultraviolet
The uniformly mixture of monomer liquid crystal compound system in mass ratio 1: 9 is closed, forms isotropic liquid at a temperature of 0 DEG C.To isotropism
Thermosetting accelerator is added in liquid and forms mixed system, thermosetting accelerator DMP-30 content is isotropic liquid gross mass
1%.The glass microballoon that partial size is 20 μm is added into mixed system, controls the thickness of pdlc film, the content of glass microballoon is about
It is the 0.5% of mixed system gross mass.
The mixed system that glass microballoon is added is clipped in two panels to be coated among the transparent conductive film of ITO after evenly mixing, is used
Roll-in is even, forms the film layer of 20 μ m-thicks, heat cure is protected from light at 0 DEG C 30 days, is shone later with the ultraviolet light that wavelength is 365nm
It penetrates.Ultraviolet ray intensity is 3mW/m2, light application time be 1 minute to get arrive trans- PDLC film.Function film obtained by the present embodiment
After tested, peel strength 1.3N/cm.
The experimental results showed that prepared in the electro-optical properties of the bistable state PDLC film in embodiment 1 and embodiment 2~3
The electro-optical properties of bistable state PDLC film are excellent.Driving voltage is low, the response time is short, contrast is high.By double in embodiment 1
Stable state PDLC film is compared with the trans- PDLC film prepared in embodiment 4 it is found that by adjusting liquid crystal liquid crystal property ultraviolet polymerization list
The content of body adjusts polymer network and acts on the anchoring of liquid crystal, realizes the system of bistable state PDLC film or trans- PDLC film
It is standby.(the preferable bistable state PDLC film of electro-optical properties is formed as 1%≤liquid crystal liquid crystal property uv photopolymerization content of monomer < 10%；
The preferably trans- PDLC film of electro-optical properties is formed when 10%≤liquid crystal liquid crystal property uv photopolymerization content of monomer≤20%.)
In conclusion the present invention passes through selection thermal polymerization monomer and ultraviolet light polymerisable monomer, through heat and ultraviolet light irradiation
The step-by-step polymerization cross-linking reaction for causing above-mentioned polymerization system enhances polymer network intensity and improves macromolecule network and ITO
Interfacial adhesion between film forms the trans- and bistable state PDLC thin-film material with excellent electro-optical properties.
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 (6)
1. the method that a kind of heating-ultraviolet light step-by-step polymerization prepares cholesteric liquid crystal function film, the method includes following steps
It is rapid:
1) the liquid crystal liquid crystal property ultraviolet light polymerisable monomer that weight percent is 1wt%~20wt% is introduced into cholesteric liquid crystal mixture
Neutralization photoinitiator mixture is ultraviolet polymerisable monomer crystal compound system, and the additive amount of photoinitiator is that liquid crystal liquid crystal property ultraviolet light can
0.01wt%~10wt% of polymerized monomer and cholesteric liquid crystal mixture gross mass；
2) the polysulfide alcohol type curing agent that weight percent is 20wt%~80wt% is introduced into mixture in thermal polymerization monomer is hot polymerization
Close compound system；
3) by weight percent be 10wt%~60wt% thermal polymerization compound system introduce weight percent be 40wt%~
90wt% mixture after ultraviolet polymerisable monomer liquid crystal complex system, uniformly mixed at a temperature of 0 DEG C~70 DEG C, formed it is each to
Same sex liquid；
4) thermosetting accelerator is added into isotropic liquid and forms mixed system, thermosetting accelerator content is isotropism
The 1.0~5.0% of liquid gross mass；
5) glass microballoon is added to mixed system, controls the thickness of pdlc film, the content of glass microballoon is mixed system gross mass
0.5~1.0%；
6) it is poured into after mixing the mixed system that glass microballoon is added with the glass substrate production for being coated with conductive indium-tin oxide layer
In liquid crystal cell, or with the plastic film for being coated with conductive indium-tin oxide layer the mixed system that glass microballoon is added is pressed into liquid crystal
Film, the thermal polymerization at 0~55 DEG C, thermal polymerization time are 3~30 days；Then keep cholesteric liquid crystal parallel by the effect of electric field
Orientation, while being irradiated with ultraviolet light, finally it is solidified into cholesteric liquid crystal function film；
The cholesteric liquid crystal function film is trans- or bistable state PDLC film；
The cholesteric liquid crystal mixture includes chiral additives and nematic liquid crystal mixture；
The nematic liquid crystal mixture contains I, II, III, IV, V, VI and VII class compound, classes of compounds by weight hundred
It point is 10~30% than to be respectively as follows: compound I be 35~50%, II class compound, Group III compound is 5~10%, IV class
Compound be 10~15%, V compound be 1~3%, VI class compound be 10~20%, VII class compound be 0.05~
0.1%；The general structure of classes of compounds is respectively as follows:
Wherein, R1~R11Respectively alkyl-CnH2n+1Or alkoxy-OCnH2n+1In one, wherein n be integer 1~5；Z is single
One or more of key ,-COO- or-C ≡ C- group；L1~L2One in respectively-H atom ,-F atom or cyano；L3
~L4One in respectively-H atom or cyano；m1~m4Value be respectively 0 or 1, and not simultaneously be 0 or 1；
The liquid crystal liquid crystal property ultraviolet light polymerisable monomer is selected from one of following structural compounds or a variety of:
The thermal polymerization monomer is selected from one of following structural compounds or a variety of:
2. the method according to claim 1, wherein the chiral additives be selected from S811, R811, R1011,
One of CB15 and ZLI-4572 or a variety of.
3. the method according to claim 1, wherein the photoinitiator is benzil ketals class compound or virtue
Fragrant ketone compounds.
4. according to the method described in claim 3, it is characterized in that, the benzil ketals class compound is benzil dimethyl
Ketal, the aromatic ketone compounds are benzophenone or thio anthrone.
5. the method according to claim 1, wherein the thermosetting accelerator is tertiary amine compounds.
6. the method according to claim 1, wherein in step 6), the condition of ultraviolet light are as follows: wavelength is
365nm, ultraviolet ray intensity are 1 μ W/cm2~3mW/cm2, light application time 1min~60min.
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