CN110016352A - A kind of trans- polymer dispersion liquid crystal material, liquid crystal light valve and its application - Google Patents

A kind of trans- polymer dispersion liquid crystal material, liquid crystal light valve and its application Download PDF

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CN110016352A
CN110016352A CN201810020222.8A CN201810020222A CN110016352A CN 110016352 A CN110016352 A CN 110016352A CN 201810020222 A CN201810020222 A CN 201810020222A CN 110016352 A CN110016352 A CN 110016352A
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liquid crystal
trans
group
polymer dispersion
dispersion liquid
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丁文全
周振婷
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Jiangsu He Cheng Display Technology Co Ltd
Jiangsu Hecheng Display Technology Co Ltd
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Jiangsu He Cheng Display Technology Co Ltd
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Abstract

The present invention provides a kind of trans- polymer dispersion liquid crystal material, liquid crystal light valve and its applications.The trans- polymer dispersion liquid crystal material includes following component: the nematic phase liquid crystal composition of negative dielectric anisotropic；UV curable or heat-setting glue；From alignment materials.The trans- polymers dispersed liquid crystal light valve includes the first base layer from top to bottom set gradually, the first conductive layer, liquid crystal layer, the second conductive layer, the second base layer, contains above-mentioned trans- polymer dispersion liquid crystal material in the liquid crystal layer.When the trans- polymer dispersion liquid crystal material is applied in light shutter device, have the advantages that stability is good, saturating state transmitance is high, mist state mist degree is big and mechanical property is excellent, shock resistance is strong.

Description

A kind of trans- polymer dispersion liquid crystal material, liquid crystal light valve and its application
Technical field
The invention belongs to liquid crystal applications technical fields, and in particular to not powered to one kind is in light transmission state, power-up in mist state Polymer dispersion liquid crystal material and its application in light shutter device are particularly applicable to the neck such as intelligent window, transparence display Domain.
Background technique
Polymer dispersed liquid crystals (polymer dispersed liquid crystal, PDLC) is to fill liquid crystal molecule In the three-dimensional net structure that macromolecule is formed, when no electric field is applied, the director of liquid crystal molecule is in irregular distribution, film In strong light-scattering state；Under electric field action, the long axis of liquid crystal molecule is parallel to electric field alignment, the transparent state of film. The electro-optical properties feature of trans- PDLC film are as follows: the transparent state of film when not applying electric field to film；Apply when to film Film is in light-scattering state when electric field.Since its electro-optical properties feature and formal PDLC film are exactly the opposite, relative to just Formula PDLC film, referred to as trans- PDLC film.Common formal polymer dispersion optoelectronic film needs lasting in light transmission state Power supply supply needs to expend big when to work as this most time of photoelectric device, especially intelligent window be the device work of light transmission state The electric energy of amount.Therefore, design the trans- photoelectric device of light transmission state can be presented under zero electric field in energy shortages today without Doubtful more practical and environmentally friendly, trans- PDLC film also becomes the hot spot studied at present.
Chinese patent CN106154617A discloses a kind of polymer dispersed liquid crystals light modulation device, contains micro- knot in the device Structure layer and polymer dispersed liquid crystal layer, the polymer dispersed liquid crystal layer have voltage driving under light refractive index from n1 to n2 The refractive index of the ability of transformation, the microstructured layers is n1 or n2, and when applying first voltage, the microstructured layers gather with described The refractive index for closing object dispersing liquid crystal layer is identical, shows as light transmission state；When a second voltage is applied, the microstructured layers gather with described The refractive index for closing object dispersing liquid crystal layer is not identical, shows as mist state.The device realizes light transmission state dependent on the characteristic of dual-frequency liquid crystal It with the conversion of mist state, needs that dual-frequency liquid crystal and glue polymerization form a film in the case where low frequency electric field drives, then is changed by high-frequency electric field The refractive index of liquid crystal, polymerizing condition is complicated, and the power consumption of high-frequency drive is also larger.
Chinese patent CN106336875A discloses a kind of preparation method of trans- polymer dispersed liquid-crystal film, part It is saturating that technical solution uses cholesteric liquid crystal (compound 7,8,9 has chirality) step-by-step polymerization to form cholesteric liquid crystal arranged in parallel State, then Focal conic state is formed by electric field driven, mist state effect is formed, disadvantage is polymerizing condition complexity, light transmission state effect Transparency is also poor；There are also portion of techniques schemes to be polymerize under parallel state using negativity nematic liquid crystal, forms light transmission state, then It is powered, acts on forming mist state using the dynamic scattering of liquid crystal molecule, disadvantage is that power consumption is big, and driving can generate heat for a long time.
Chinese patent CN106281361A discloses a kind of polymer network liquid crystal display, and liquid crystal media layer is to utilize What nematic liquid crystal (the preferably nematic liquid crystal of negative dielectric anisotropic) and mixed with polymers were formed, which has better OFF state light transmittance, bigger visual angle.But polymer content (preferably 1-10%) within 1-15% in the liquid crystal media layer, by The polymer network that polymer is formed can not play dynamics supporting role to nematic liquid crystal, it is therefore desirable to carry out PI system in advance Journey, and can be only applied in the Hard base layer (such as glass substrate) of support construction, it can not accomplish Flexible Displays.
For another example Chinese patent CN104597661A, CN106753428A draws to reduce PI processing procedure into liquid crystal media Entering from orientation agent, but the weight percent of its polymerisable monomer in the liquid crystal layer is still lower (10% or less), film forming is poor, and Cohesive force between the polymer network and substrate of formation is insufficient, can not accomplish that large area flexible is shown.
In addition Chinese patent CN106699960A also discloses a kind of step-by-step polymerization preparation method of temperature control light modulation film, is adopted Liquid crystal monomer is a kind of liquid crystal material that transformation can be realized between smectic C and cholesteric phase.Equally exist polymerization The problem of complex process, implements more limited in addition, its liquid crystal material range of choice is narrow.
From the foregoing, it will be observed that trans- PDLC has complex process, less effective mostly in the prior art, people compel to be essential Wanting one kind to be readily able to, production, changing effect is good, saturating state transmitance is high, mist state mist degree is big and mechanical property is excellent, shock resistance Strong trans- PDLC display device.
Summary of the invention
The object of the present invention is to provide one kind can be directly by way of photocuring or heat cure by negative dielectric anisotropic Nematic liquid crystal polymerize the trans- polymer dispersion liquid crystal material to be formed in vertical state, by the trans- polymer dispersed liquid crystals material When material is applied in light shutter device, there is good stability, light transmission state transmitance height, mist state mist degree greatly and mechanical property is excellent, anti- The strong advantage of impact property.
One aspect of the present invention provides a kind of trans- polymer dispersion liquid crystal material, including following component:
The nematic phase liquid crystal composition of negative dielectric anisotropic；
UV curable or heat-setting glue；
From alignment materials.
In some technical solutions of the invention, further, the trans- polymer dispersion liquid crystal material can also be wrapped Include liquid crystal liquid crystal property polymerisable monomer.
In some technical solutions of the invention, at least contain in the nematic phase liquid crystal composition of the negative dielectric anisotropic There is a kind of compound of general formula I:
Wherein,
R1And R2Each independently represent-H ,-F, the alkyl of linear chain or branched chain containing 1-12 carbon atom or alkoxy, The alkenyl or alkenyloxy group of linear chain or branched chain containing 2-12 carbon atom, naphthenic base or-O (CH containing 3-12 carbon atom2)pO(CH2)qCH3, wherein in the alkyl or alkoxy, the alkenyl or alkenyloxy group and the naphthenic base it is one or more- H can be replaced by-F, one or more-CH2It can be substituted by-O-, precondition is that oxygen atom is not connected directly；
Z1And Z2Expression singly-bound independent ,-CO-O- ,-O-CO- ,-CH2O-、-OCH2-、-CH2CH2,-CH=CH- Or-C ≡ C-；
L1And L2Expression-F ,-Cl ,-CN or-NCS independent；
RingAnd ringIt each independently representsWherein,In one or more-CH2It can be substituted by-O-,In one or more-H can be by halogen Replace；
N1 indicates 1,2 or 3, and when n1 is 2 or 3, ringCan be identical or different, Z1It can be identical or not Together；
N2 indicates 0 or 1；
P indicates 1~12 integer；
Q indicates 0~12 integer.
In some embodiments of the present invention, the compound of the general formula I accounts for the nematic of the negative dielectric anisotropic 1% or more of phase liquid crystal total weight；Preferably, the compound of the general formula I accounts for the nematic phase liquid of the negative dielectric anisotropic 20% or more of brilliant total weight；It is highly preferred that the compound of the general formula I accounts for the nematic liquid crystal of the negative dielectric anisotropic 50% or more of total weight.
In some technical solutions of the invention, further, the compound of the general formula I is formed selected from following compound Group:
Wherein,
R1And R2Expression-H independent ,-F, the linear or branched alkyl group containing 1-7 carbon atom or alkoxy contain The linear chain or branched chain alkenyl or alkenyloxy group of 2-7 carbon atom,Or-O (CH2)pO(CH2)qCH3, wherein one or more-H in the alkyl or alkoxy, the alkenyl or alkenyloxy group can be replaced by-F, one Or more-CH2It can be substituted by-O-, precondition is that oxygen atom is not connected directly；
P indicates 1~12 integer；
Q indicates 0~12 integer.
In some embodiments of the present invention, further, in the nematic liquid crystal of the negative dielectric anisotropic also It may include and account for compound of the one or more of its total weight 0-60% selected from formula M:
Wherein,
RiAnd RiiIt each independently represents-H, the linear or branched alkyl group containing 1-12 carbon atom or alkoxy, contain The linear chain or branched chain alkenyl or alkenyloxy group of 2-12 carbon atom；
RingAnd ringIt is identical or different, it each independently represents
ZiIndicate singly-bound ,-CH2CH2,-CH=CH- ,-C ≡ C- ,-CH2O-、-OCH2,-CO-O- or-O-CO-；
A indicates 1,2 or 3, and when a is 2 or 3, ringIt can be identical or different.
In some technical solutions of the invention, it is further preferred that the compound of the general formula II accounts for the negative dielectric The 0-40% of anisotropic nematic liquid crystal total weight；Still further preferably, the compound of the general formula II accounts for described negative The 0-20% of the nematic liquid crystal total weight of dielectric anisotropy.Still further preferably, the compound of the general formula II accounts for institute State the 1-20% of the nematic liquid crystal total weight of negative dielectric anisotropic.
In some technical solutions of the invention, it is further preferred that the compound of the formula M is selected from by following chemical combination The group of object composition:
In some technical solutions of the invention, it is further preferred that RiAnd RiiEach independently representing carbon atom number is The linear or branched alkyl group or alkoxy of 1-7, the linear chain or branched chain alkenyl or alkenyloxy group that carbon atom number is 2-7.
In some technical solutions of the invention, further, in the nematic liquid crystal of the negative dielectric anisotropic also It may include and account for compound of the one or more of its total weight 0-20% selected from general formula N:
Wherein,
RiiiAnd RivIt each independently represents linear or branched alkyl group or alkoxy containing 1-12 carbon atom, contain 2- The linear chain or branched chain alkenyl or alkenyloxy group ,-O (CH of 12 carbon atoms2)pO(CH2)qCH3、Its Described in one or more-H in linear or branched alkyl group or alkoxy and the linear chain or branched chain alkenyl or alkenyloxy group can To be replaced by-F.
In some technical solutions of the invention, further, the UV curable or heat-setting glue are at least Be made of non-liquid crystal property polymerisable monomer, initiator and prepolymer, the prepolymer be selected from acrylatcs systems, epoxy systems or Vinyl ethers system, wherein the acrylatcs systems can be selected from polyurethane acrylic resin system, epoxy acrylate body System, polyester acrylate system, polyether acrylate system or pure acrylate system.It certainly, as needed, can also be to glue The various auxiliary agents such as plasticizer, stabilizer, defoaming agent and coupling agent are added in water.
It is further, described to be selected from following general formula II from alignment materials in some technical solutions of the invention Compound:
Wherein,
A11Indicate aryl, heteroaryl, the heterocycle that can be optionally replaced by one or more identical or different group L Or alicyclic group,
The group L indicates halogen ,-CN ,-NO independently of one another in all cases2、-NCO、-NCS、-OCN、-SCN、 Linear or branched alkyl group or alkoxy with 1-5 carbon atom, in addition, one or more non-end-in these groups CH2Group can be independently of one another by-C ≡ C- ,-CF2O- ,-CH=CH-,-O-、-CO- O- ,-O-CO- are substituted in such a way that oxygen atom is not directly connected to each other, and one of them or more H can be substituted by halogen；
Z11Expression-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-S-CO- ,-CO- independently of one another in all cases S-、-O-CO-O-、-CO-NR0-、-NR0-CO-、-NR0-CO-NR00、-NR0-CO-O-、-O-CO-NR0-、-OCH2-、-CH2O-、- SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-CH2CH2-、-(CH2)4-、-CF2CH2-、-CH2CF2,-CH= N- ,-N=CH- ,-N=N- ,-CH=CR0-、-CY01=CY02,-C ≡ C- ,-CH=CH-CO-O- ,-O-CO-CH=CH- or list Key；
Y01And Y02Each independently represent-F ,-Cl or-CN；
R0And R00Each independently represent-H or the linear or branched alkyl group containing 1-12 carbon atom；
R11Respectively linear or branched alkyl group or alkoxy containing 1-15 carbon atom are indicated independently of one another, in addition, this One or more non-end-CH in a little groups2Group can be independently of one another by-C ≡ C- ,-CF2O- ,-CH=CH-,- O- ,-CO-O- ,-O-CO- are substituted in such a way that oxygen atom is not directly connected to each other, and One of them or more H can be substituted by halogen；
AG expression-Sp-X11；
SpIndicate the linear chain or branched chain alkylidene containing 1-15 carbon atom, the linear chain or branched chain containing 2-15 carbon atom Alkenylene, one or more-CH in the alkylidene or alkenylene2Group can independently of one another by-O- ,-CO-O- ,- O-CO- ,-S- ,-NH- are substituted in such a way that hetero atom is not directly connected to each other；
X11Expression-NH2,-SH ,-OH ,-COOH or following formula group:
A indicates 0~5 integer.
It is further, described to be also selected from polyvinyl alcohol from alignment materials in some technical solutions of the invention (PVA) or silylating reagent, such as: DMOAP (molecular formula are as follows: CH3-(CH2)17(CH3)2N+(CH2)3Si(OCH3)3Cl-)。
In some technical solutions of the invention, it is further preferred that the compound of the general formula II is selected from following chemical combination The group of object composition:
And
R11-(CH2)mOH II -6,
Wherein,
R11Indicate the linear or branched alkyl group containing 1-5 carbon atom；
R0Expression-H or linear or branched alkyl group containing 1-5 carbon atom；
L1To L12Each independently represent-H ,-F ,-Cl ,-CF3、CHF2Or the linear chain or branched chain alkane containing 1-5 carbon atom Base；
T, u, v, w, x, y and z each independently represent 0 or 1；
The integer of m expression 0-12；
RingIt indicates
And above-mentioned each compound-(CH2)mIn structure, one or more-CH2Group can independently of one another by- CH=CH- ,-C ≡ C- ,-O- ,-CO-O- ,-O-CO- ,-S- ,-NH- are substituted in such a way that hetero atom is not directly connected to each other, and one A or more-H can be independently of one another by linear or branched alkyl group or alkoxy substitution containing 1-5 carbon atom.
In some technical solutions of the invention, further, the liquid crystal liquid crystal property polymerisable monomer is selected from following general formula III Compound:
Wherein,
P1It indicates Or-SH；
Sp1Indicate the alkylidene of singly-bound or the linear chain or branched chain containing 1-20 carbon atom, wherein in the alkylidene One or more non-conterminous-CH2Group can be independently of one another by-O- ,-S- ,-COO- ,-OCO- ,-OCO-O- ,-S- CO- ,-CO-S- ,-CH=CH- or-C ≡ C- are substituted, and the H in the alkylidene can be taken by one or more halogen or CN Generation；
Qp1Indicate singly-bound ,-O- ,-S- ,-NH- ,-NHCOO- ,-OCONH- ,-CF2O-、-OCF2-、-CF2S-、-SCF2-、- CH2CH2-、-CF2CH2-、-CH2CF2-、-CF2CF2,-CF=CH- ,-CH=CF- ,-CF=CF- ,-CO- ,-COO- ,-OCO- ,- OCOO-、-CH2-、-OCH2-、-SCH2-、-CH2S- ,-CH=CH- ,-C ≡ C- ,-CH=CH-COO- or-OCO-CH=CH-；
R1 and r2 each independently represents 1,2 or 3；
MGpIndicate that mesomorphic group or mesomorphism support group；
Rp1Indicate the alkyl of halogen ,-CN or the linear chain or branched chain containing 1-20 carbon atom, one in the alkyl or More non-conterminous-CH2Group can be independently of one another by-O- ,-S- ,-NH- ,-NCH3-、-CO-、-COO-、- OCO- ,-OCO-O- ,-S-CO- ,-CO-S- ,-CH=CH- or-C ≡ C- substitution, alternatively, Rp1It can be P2-Sp2-Qp2, wherein P2、Sp2、Qp2Definition respectively with P1、Sp1、Qp1It is identical.
In some technical solutions of the invention, further, the MGpIt indicates
Wherein, A1、A2And A3Each independently represent 1,4- cyclohexyl, 1,4- cyclohexenyl group, piperidines -1,4- diyl, 1,4- It is sub- two rings [2,2,2] octyl, 1,4- phenyl, pyridine -2,5- diyl, pyrimidine -2,5- diyl, naphthalene -2,6- diyl, trans- decahydronaphthalene Naphthalene -2,6- diyl, tetrahydronaphthalene -2,6- diyl and 1,2- dihydroindene, wherein one or two of described Isosorbide-5-Nitrae-cyclohexyl - the CH not being directly connected to2It can be substituted independently of one another by-O- or-S-, one or more-H in the Isosorbide-5-Nitrae-phenyl It can be replaced independently of one another by halogen, the alkyl of-CN or the linear chain or branched chain containing 1-4 carbon atom or alkoxy；
Zp1And Zp2It is identical or different, be independently selected from by singly-bound ,-O- ,-S- ,-NH- ,-NHCOO- ,-OCONH- ,- CF2O-、-OCF2-、-CF2S-、-SCF2-、-CH2CH2-、-CF2CH2-、-CH2CF2-、-CF2CF2,-CF=CH- ,-CH= CF- ,-CF=CF- ,-CO- ,-COO- ,-OCO- ,-OCOO- ,-CH2-、-OCH2-、-SCH2-、-CH2S- ,-CH=CH- ,-C ≡ The group of C- ,-CH=CH-COO- and-OCO-CH=CH- composition；
R3 indicates 0,1 or 2.
In some technical solutions of the invention, it is further preferred that the compound of the general formula III is selected from following chemical combination The group of object composition:
Wherein,
R4 and r5 each independently represents 0,1,2,3 or 4.
In some technical solutions of the invention, it is further preferred that the compound of the general formula III be selected from general formula III c, The group of III d, III g and III h composition.
In some technical solutions of the invention, still further preferably, the compound of the general formula III c is selected from followingization Close the group of object composition:
The compound of the general formula III d is selected from the group of following compound composition:
The compound of the general formula III g is selected from the group of following compound composition:
The compound of the general formula III h is selected from the group of following compound composition:
Wherein,
LNIndicate halogenated containing 1-5 carbon atom or not by halogenated linear or branched alkyl group or alkoxy ,- COOCH3、-CF2COOC2H5；
The q1And q2Each independently represent the positive integer of 1-12.
In some embodiments of the present invention, the nematic liquid crystal of the negative dielectric anisotropic accounts for the trans- polymerization The 50-85% of object dispersed liquid crystal material total weight；The UV curable or heat-setting glue account for the trans- polymer The 10-40% of dispersed liquid crystal material total weight；It is described to account for the trans- polymer dispersion liquid crystal material total weight from alignment materials 1-10%；The liquid crystal liquid crystal property polymerisable monomer accounts for the 3-10% of the trans- polymer dispersion liquid crystal material total weight.
In some embodiments of the present invention, it is further preferred that the nematic liquid crystal of the negative dielectric anisotropic Account for the 60-85% of the trans- polymer dispersion liquid crystal material total weight；The UV curable or heat-setting glue account for The 30-40% of the trans- polymer dispersion liquid crystal material total weight；It is described to account for the trans- polymer dispersion from alignment materials The 1-5% of liquid crystal material total weight；The liquid crystal liquid crystal property polymerisable monomer accounts for the trans- polymer dispersion liquid crystal material total weight 5-10%.
In some embodiments of the present invention, the compound of the general formula I preferably is selected from following compound: I-1, I-3, I- 4, the group of I-5, I-6, I-9, I-18, I-19, I-20, I-24 composition.
In some embodiments of the present invention, the compound of the formula M preferably is selected from following compound: M-5, M-16, With the group of M-18 composition.
In some embodiments of the present invention, the compound of the general formula II preferably is selected from following compound: II -1 (R11 =-C3H7, L1=L2=L3=-H, t=m=0, u=v=1),The group of composition.
In some embodiments of the present invention, the compound of the general formula III preferably is selected from following compound: III g-1 (LN =-CH3, q1=q2=4), III h-1 (LN=-CO-OCH3, q1=q2=4) composition group.
It can also be mixed in order to realize different display effects, in trans- polymer dispersion liquid crystal material of the invention The dyestuff of 0.01-10wt%.
In some embodiments of the present invention, the dye molecule is dichroic dye.
In some embodiments of the present invention, the dichroic dye molecules be selected from by azo, Anthraquinones, phthalocyanine, One of cyanines class, group of indigoids, fragrant methane, nitro and nitroso composition or more dyestuff.
In some embodiments of the present invention, the preferably described dichroic dye is selected from by azo, Anthraquinones and its group One of group of conjunction or more dyestuff.
In some embodiments of the present invention, the two colors dyestuff is selected from by one of following compound or more Kind:
Maximum absorption wavelength 574nm；
Maximum absorption wavelength 610nm；
Maximum absorption wavelength 570nm；
Maximum absorption wavelength 595nm；
Maximum absorption wavelength 507nm；
Maximum absorption wavelength 526-533nm；
Maximum absorption wavelength 573nm；
Maximum absorption wavelength 574nm；
Maximum absorption wavelength 533-542nm；
Maximum absorption wavelength 390-398nm；
Maximum absorption wavelength 402nm；
Maximum absorption wavelength 439-446nm；
Maximum absorption wavelength 443-450nm；
Maximum absorption wavelength 511nm；
Maximum absorption wavelength 447nm；
Maximum absorption wavelength 450nm；
Maximum absorption wavelength 563-573nm；
Maximum absorption wavelength 580-589nm；
Maximum absorption wavelength 591-599nm；
Maximum absorption wavelength 592-600nm；
Maximum absorption wavelength 621-660nm；
Maximum absorption wavelength 572nm；
Maximum absorption wavelength 591-606nm；
Maximum absorption wavelength 634-643nm；
Maximum absorption wavelength 674nm；
Maximum absorption wavelength 555nm；
Maximum absorption wavelength 640nm；
Maximum absorption wavelength 645nm；
Maximum absorption wavelength 680nm；
Maximum absorption wavelength 760nm；
Maximum absorption wavelength 670nm；
Maximum absorption wavelength 760nm；
Maximum absorption wavelength 595nm；
Maximum absorption wavelength 630nm；
Maximum absorption wavelength 595nm；
Maximum absorption wavelength 535nm；
Maximum absorption wavelength 595nm.
Selection one of which or more homogencous dyes is configured to dye composite as needed, take heating, ultrasonic wave, The modes such as suspension make it mix, dissolve in proportion with liquid crystal molecule, glue, from alignment materials, obtain liquid crystal material.
In order to adjust the polymerization speed of glue and liquid crystal liquid crystal property polymerisable monomer, trans- polymer dispersed liquid crystals material of the invention The photoinitiator of 0.01-5wt% can also be additionally incorporated in material.
In some embodiments of the present invention, the photoinitiator is selected from 184,907, TPO or 173 photoinitiators.
In some embodiments of the present invention, it is highly preferred that the photoinitiator is 184 photoinitiators.
Another aspect of the present invention also provides a kind of trans- polymers dispersed liquid crystal light valve, including what is from top to bottom set gradually First base layer, the first conductive layer, liquid crystal layer, the second conductive layer, the second base layer, wherein containing above-mentioned in the liquid crystal layer Trans- polymer dispersion liquid crystal material.
In some embodiments, first base layer, the second matrix layer material can independently be glass or transparent Plastics, preferably glass, the transparent plastic can in flexible or non-flexible, the transparent plastic can be used polyester (PET or PEN), polycarbonate (PC), cellulose triacetate (TAC), polypropylene (PP), polyethylene (PE), nylon (Nylon), polychlorostyrene second Alkene (PVC), NC Nitroncellulose (NC), polytetrafluoroethylene (PTFE) (PTFE), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), the transparent material such as polyurethane (Pu), polystyrene (PS).
In some embodiments, first conductive layer, the second conductive layer are transparency conducting layer, and oxidation can be used Indium tin (ITO), conducting polymer (Conductive Polymer), nano silver, carbon nanotube (CNT), graphene (Graphene) transparent materials such as.Conductive coating can pass through machinery coating, chemical vapor deposition (CVD), sputter coating, electrification The methods of plated film is learned to be uniformly distributed to form film on base layer.First conductive layer and the second conductive layer can be according to displays Or the demand of erasing pattern is divided into different shape and several units.
First base layer, the second base layer and conductive layer of the invention may be incorporated in together, such as commercially available polyester film- Tin indium oxide (PET-ITO) is merged as commodity selling；First base layer, the second base layer and conductive layer can also To be individually present, different film ground and conductive coating are used respectively, but the two must be transparent material.
Trans- polymers dispersed liquid crystal light valve provided by the invention can be applied particularly to vehicle glass, intelligent window, electricity The photoswitches such as sub- curtain field may be implemented to be transparent under normality (being not powered on), operating conditions (energization) effect fog-like.
It should be understood that term used in the present invention " mesomorphic group " or " mesomorphism support group " are this field skills Art personnel are known and are described in the literature, and will be understood to refer to due to the interaction that attracts and repel Anisotropic group essentially contributes to generate liquid crystalline phase in low molecular weight or polymeric material, includes mesomorphic group Compound (mesomorphic compound) not necessarily itself have liquid crystalline phase.For mesomorphic compound, only with other chemical combination After object mixing and/or after polymerisation, it is also possible to show Mesomorphic behavior.Typical mesomorphic group is for example rigid small Rodlike or patelliform unit.Pure AppI.Chem.73 (5), 888 (2001) and C.Tschierske, G.PeIzI, S.DieIe., Angew.Chem.2004 gives art used in related mesomorphic or liquid-crystal compounds in 116,6340-6368 The summary of language and definition.
Term as used herein " halogen " will be understood to refer to F, Cl, Br or I.
The utility model has the advantages that
Trans- polymer dispersion liquid crystal material provided by the invention has the advantages that polymerization technique and driving method are simple, Compared with traditional polymer polymerizing object network Liquid Crystal material, material of the invention is in the island structure mutually separated, has heat steady Qualitative advantage high, mechanical impact force is strong.
Detailed description of the invention
Fig. 1 is the effect picture under trans- polymers dispersed liquid crystal light valve made from embodiment 1 is not powered on；
Fig. 2 is the effect picture under trans- polymers dispersed liquid crystal light valve made from embodiment 1 is powered；
Fig. 3 is the structure chart of trans- polymer dispersion liquid crystal material under microscopic visualization made from embodiment 1；
Fig. 4 is the structure chart of existing polymer network liquid crystal material under microscopic visualization.
Specific embodiment
Illustrate the present invention below with reference to specific embodiment.It should be noted that the following examples are the present invention Example, be only used to illustrate the present invention, and be not limited to the present invention.Without departing from the spirit or scope of the invention, It can carry out other combinations and the various improvement in present inventive concept.
For convenient for expressing, in following embodiment, unit structure code listed by table 1 of liquid-crystal composition is indicated:
The group structure code of 1 liquid-crystal compounds of table
By taking the compound of following structural formula as an example:
The structural formula such as indicates by code listed in Table 1, then can be expressed as: nCPWOm, and the n in code indicates left end alkyl C atomicity, such as n are " 3 ", that is, indicate that the alkyl is-C3H7；C in code represents cyclohexyl；P represents 1,4- phenylene；W Represent the fluoro- 1,4- phenylene of 2,3- bis-；O represents oxygen substituent group；M indicates the C atom number of right end alkyl, such as m is " 2 ", i.e., Indicate that the alkyl is-C2H5。
Hereafter " mist degree " is tested using WGT-S light transmittance/mist degree analyzer.
Reference literature " In-situ photopolymerization of oriented liquid-crystalline Acrylates:oriented polymer networks from a mesogenic diacrylate, Makromol.Chem., the 1989,190,2255-2268 (photopolymerization in situ of directional crystal acrylate: from the double propylene of mesomorphic The oriented polymer network of acid esters, polymer chemistry, 1989,190,2255-2268) " and patent US6136225, Method disclosed in JPH083111A synthesizes polymerizable liquid crystal compound according to the present invention.
Embodiment 1
Liquid-crystal composition LC-1 is configured to by each compound and weight percent listed in table 2:
2 liquid-crystal composition LC-1 of table formula
Component codes Weight percent
3PTWO1 15
3PTWO2 14
5PTWO2 14
3CPTWO1 11
3CPTWO2 11
5CPTWO2 10
3PWO2 6
3C1OWWO2 4
4C1OWWO2 4
5C1OWWO2 4
3C1OWO2 7
It amounts to 100
From alignment materials: II -1 (R11=-C3H7, L1=L2=L3=-H, t=m=0, u=v=1)；
Liquid crystal liquid crystal property polymerisable monomer: III g-1 (LN=-CH3, q1=q2=4)；
Glue: model SEPDLC-2005 (offer of Taiwan Xi Ng special material company)；
By above-mentioned LC-1, from alignment materials, liquid crystal liquid crystal property polymerisable monomer, glue 82:3:5:10 in mass ratio in yellow light item It is uniformly mixed under part, obtains the trans- polymer dispersion liquid crystal material, which is filled Infuse into 13 μm of the liquid crystal cell without orientation, stand 10min, will be filled with mixture liquid crystal cell be placed in key light wavelength be 365nm, Light intensity 5mW/cm2UV lamp under, irradiate 10min, be made print, the as described trans- polymers dispersed liquid crystal light valve, in nothing Under conditions of electric field action, mist degree 6, as shown in Figure 1, through print, the text being clear that in background is applied to print Add the voltage of 60Hz, 30V, mist degree 85, as shown in Fig. 2, can not find out background content.
Print obtained is carried out to tear piece open, liquid crystal layer therein dries after acetone cleans, and is formed by micro- sem observation Polymer architecture, it can be seen that typical island phase separation structure as shown in Figure 3, this kind of structure have thermal stability and The strong feature of mechanical impact force.
As a comparison, Fig. 4 illustrates the microstructure that common polymer network liquid crystal material is presented under the microscope, can To find out, this kind of structure is Filamentous in network, and thermal stability and mechanical impact force are poor.
Embodiment 2
Liquid-crystal composition LC-2 is configured to by each compound and weight percent listed in table 3:
3 liquid-crystal composition LC-2 of table formula
From alignment materials: with embodiment 1；
Liquid crystal liquid crystal property polymerisable monomer: III h-1 (LN=-CO-OCH3, q1=q2=4)；
Glue: model OP-10 (offer of this Jiao Ye Co., Ltd of Shenzhen sadie)；
By above-mentioned LC-2, from alignment materials, liquid crystal liquid crystal property polymerisable monomer, glue 65:3:7:25 in mass ratio in yellow light item It is uniformly mixed under part, the trans- polymer dispersion liquid crystal material is obtained, by the trans- polymer dispersion liquid crystal material again 35 It is mixed into appropriate 15 μm of introns under conditions of DEG C, mixture obtained is filled in PET-ITO film by way of roll-in, 20-30min is stood, so that mixture is formed from orientation in film.The PET-ITO film for accompanying mixture, which is placed in key light wavelength, is 365nm, light intensity 5mW/cm2UV lamp under, irradiate 10min, be made print, the as described trans- polymers dispersed liquid crystal light valve, It is under conditions of no electric field action, mist degree 20, applies the voltage of 60Hz, 40V, mist degree 80 to print.
Embodiment 3
Liquid-crystal composition LC-3 is configured to by each compound and weight percent listed in table 4:
4 liquid-crystal composition LC-3 of table formula
From alignment materials:
Liquid crystal liquid crystal property polymerisable monomer: with embodiment 2；
Glue: model UV-200 (offer of Ku Er industry (Shanghai) Co., Ltd.)；
By above-mentioned LC-3, from alignment materials, liquid crystal liquid crystal property polymerisable monomer, glue 60:5:5:30 in mass ratio in yellow light item Under part be uniformly mixed, then into mixture be added 2% dichroic dye (by above-mentioned number be 1,6,12 dichroic dye by It is mixed according to mass ratio 3:2:8), stirring and dissolving is uniform, obtains the trans- polymer dispersion liquid crystal material, this is trans- poly- It closes object dispersed liquid crystal material and is mixed into appropriate 10 μm of introns under conditions of 35 DEG C again, it will be obtained mixed by way of roll-in It closes object to be filled in PET-ITO film, stands 30min, so that mixture is formed from orientation in film.The PET- of mixture will be accompanied It is 365nm, light intensity 5mW/cm that ito film, which is placed in key light wavelength,2UV lamp under, irradiate 15min, be made print, it is as described trans- Polymers dispersed liquid crystal light valve, under no electric field, mist degree 15 is in slightly dark state, applies the electricity of 60Hz, 30V to print Pressure, mist degree 60 are in dark brown mist state.
Trans- polymer dispersion liquid crystal material provided by the invention has the advantages that polymerization technique and driving method are simple, Compared with traditional polymer network liquid crystal material, material of the invention is in the island structure mutually separated, high with thermal stability, The strong advantage of mechanical impact force.
The present invention can also be familiar with by other various embodiments, without deviating from the spirit and substance of the present invention Those skilled in the art makes various corresponding changes and modifications, but these corresponding changes and modifications in accordance with the present invention All it should fall within the scope of protection of the appended claims of the present invention.

Claims (14)

1. a kind of trans- polymer dispersion liquid crystal material, which is characterized in that including following component:
The nematic phase liquid crystal composition of negative dielectric anisotropic；
UV curable or heat-setting glue；
From alignment materials.
2. trans- polymer dispersion liquid crystal material according to claim 1, which is characterized in that can also include liquid crystal liquid crystal property can Polymerized monomer.
3. trans- polymer dispersion liquid crystal material according to claim 1, which is characterized in that the negative dielectric anisotropic Nematic phase liquid crystal composition at least contain a kind of general formula I compound:
Wherein,
R1And R2It each independently represents-H ,-F, the alkyl of linear chain or branched chain containing 1-12 carbon atom or alkoxy, contain Alkenyl or alkenyloxy group, the naphthenic base containing 3-12 carbon atom, the-O (CH of the linear chain or branched chain of 2-12 carbon atom2)pO (CH2)qCH3, wherein one or more-H in the alkyl or alkoxy, the alkenyl or alkenyloxy group and the naphthenic base It can be replaced by-F, one or more-CH2It can be substituted by-O-, precondition is that oxygen atom is not connected directly；
Z1And Z2Expression singly-bound independent ,-CO-O- ,-O-CO- ,-CH2O-、-OCH2-、-CH2CH2,-CH=CH- or-C ≡C-；
L1And L2Expression-F ,-Cl ,-CN or-NCS independent；RingAnd ringEach independently It indicatesWherein,In one or more-CH2It can be substituted by-O-,In one or more H can be optionally substituted by halogen；
N1 indicates 1,2 or 3, and when n1 is 2 or 3, ringCan be identical or different, Z1It can be identical or different；
N2 indicates 0 or 1；
P indicates 1~12 integer；
Q indicates 0~12 integer.
4. trans- polymer dispersion liquid crystal material according to claim 1, which is characterized in that the UV curable can The glue of heat cure is at least made of non-liquid crystal property polymerisable monomer, initiator and prepolymer, and the prepolymer is selected from acrylic acid Ester system, epoxy systems or vinyl ethers system, wherein the acrylatcs systems can be selected from polyurethane acrylic resin body System, epoxy acrylate system, polyester acrylate system, polyether acrylate system or pure acrylate system.
5. trans- polymer dispersion liquid crystal material according to claim 1, which is characterized in that it is described can be with from alignment materials Compound selected from following general formula II:
Wherein,
A11Indicate aryl, heteroaryl, heterocycle or the rouge that can be optionally replaced by one or more identical or different group L Ring race group,
The group L indicates halogen ,-CN ,-NO independently of one another in all cases2,-NCO ,-NCS ,-OCN ,-SCN, have The linear or branched alkyl group or alkoxy of 1-5 carbon atom, in addition, one or more non-end-CH in these groups2- Group can be independently of one another by-C ≡ C- ,-CF2O- ,-CH=CH-,-O-、-CO-O-、- O-CO- is substituted in such a way that oxygen atom is not directly connected to each other, and one of them or more H can be substituted by halogen；
Z11Expression-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-S-CO- ,-CO-S- ,-O- independently of one another in all cases CO-O-、-CO-NR0-、-NR0-CO-、-NR0-CO-NR00、-NR0-CO-O-、-O-CO-NR0-、-OCH2-、-CH2O-、- SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-CH2CH2-、-(CH2)4-、-CF2CH2-、-CH2CF2,-CH= N- ,-N=CH- ,-N=N- ,-CH=CR0-、-CY01=CY02,-C ≡ C- ,-CH=CH-CO-O- ,-O-CO-CH=CH- or list Key；
Y01And Y02Each independently represent-F ,-Cl or-CN；
R0And R00Each independently represent-H or the linear or branched alkyl group containing 1-12 carbon atom；
R11Linear or branched alkyl group or alkoxy containing 1-15 carbon atom are respectively indicated independently of one another, in addition, these bases One or more non-end-CH in group2Group can be independently of one another by-C ≡ C- ,-CF2O- ,-CH=CH-,- O- ,-CO-O- ,-O-CO- are substituted in such a way that oxygen atom is not directly connected to each other, and One of them or more H can be substituted by halogen；
AG expression-Sp-X11；
Sp indicates the linear chain or branched chain alkylidene containing 1-15 carbon atom, the linear chain or branched chain Asia alkene containing 2-15 carbon atom Base, one or more-CH in the alkylidene or alkenylene2Group can be independently of one another by-O- ,-CO-O- ,-O- CO- ,-S- ,-NH- are substituted in such a way that hetero atom is not directly connected to each other；
X11Expression-NH2,-SH ,-OH ,-COOH or following formula group:
A indicates 0~5 integer.
6. trans- polymer dispersion liquid crystal material according to claim 5, which is characterized in that the compound of the general formula II Group selected from following compound composition:
And
R11-(CH2)mOH II -6,
Wherein,
R11Indicate the linear or branched alkyl group containing 1-5 carbon atom；
R0Expression-H or linear or branched alkyl group containing 1-5 carbon atom；
L1To L12Each independently represent-H ,-F ,-Cl ,-CF3、-CHF2Or the linear or branched alkyl group containing 1-5 carbon atom；
T, u, v, w, x, y and z each independently represent 0 or 1；
The integer of m expression 0-12；
RingIt indicates
And above-mentioned each compound-(CH2)mIn structure, one or more-CH2Group can be independently of one another by-CH= CH- ,-C ≡ C- ,-O- ,-CO-O- ,-O-CO- ,-S- ,-NH- are substituted in such a way that hetero atom is not directly connected to each other, one or More-H can be independently of one another by linear or branched alkyl group or alkoxy substitution containing 1-5 carbon atom.
7. trans- polymer dispersion liquid crystal material according to claim 1, which is characterized in that described also from alignment materials To be selected from polyvinyl alcohol or silylating reagent.
8. trans- polymer dispersion liquid crystal material according to claim 2, which is characterized in that the polymerizable list of liquid crystal liquid crystal property Body is selected from the compound of following general formula III:
Wherein,
P1It indicates Or-SH；
Sp1Indicate the alkylidene of singly-bound or the linear chain or branched chain containing 1-20 carbon atom, wherein one in the alkylidene Or more non-conterminous-CH2Group can independently of one another by-O- ,-S- ,-COO- ,-OCO- ,-OCO-O- ,-S-CO- ,- CO-S- ,-CH=CH- or-C ≡ C- are substituted, and the H in the alkylidene can be replaced by one or more halogen or CN；
Qp1Indicate singly-bound ,-O- ,-S- ,-NH- ,-NHCOO- ,-OCONH- ,-CF2O-、-OCF2-、-CF2S-、-SCF2-、- CH2CH2-、-CF2CH2-、-CH2CF2-、-CF2CF2,-CF=CH- ,-CH=CF- ,-CF=CF- ,-CO- ,-COO- ,-OCO- ,- OCOO-、-CH2-、-OCH2-、-SCH2-、-CH2S- ,-CH=CH- ,-C ≡ C- ,-CH=CH-COO- or-OCO-CH=CH-；
R1 and r2 each independently represents 1,2 or 3；
MGpIndicate that mesomorphic group or mesomorphism support group；
Rp1Indicate the alkyl of halogen ,-CN or the linear chain or branched chain containing 1-20 carbon atom, it is one or more in the alkyl A non-conterminous-CH2Group can be independently of one another by-O- ,-S- ,-NH- ,-NCH3-、-CO-、-COO-、-OCO-、- OCO-O- ,-S-CO- ,-CO-S- ,-CH=CH- or-C ≡ C- substitution, alternatively, Rp1It can be P2-Sp2-Qp2, wherein P2、Sp2、 Qp2Definition respectively with P1、Sp1、Qp1It is identical.
9. trans- polymer dispersion liquid crystal material according to claim 2, which is characterized in that the negative dielectric anisotropic Nematic liquid crystal account for the 50-85% of the trans- polymer dispersion liquid crystal material total weight；The UV curable can warm Cured glue accounts for the 10-40% of the trans- polymer dispersion liquid crystal material total weight；It is described accounted for from alignment materials it is described anti- The 1-10% of formula polymer dispersion liquid crystal material total weight；The liquid crystal liquid crystal property polymerisable monomer accounts for the trans- polymer dispersion liquid The 3-10% of brilliant material total weight.
10. trans- polymer dispersion liquid crystal material according to claim 1, which is characterized in that can also be mixed with 0.01- The dyestuff of 10wt%.
11. a kind of trans- polymers dispersed liquid crystal light valve, including the first base layer, first conductive from top to bottom set gradually Layer, liquid crystal layer, the second conductive layer, the second base layer, which is characterized in that contain any one of claim 1-10 in the liquid crystal layer The trans- polymer dispersion liquid crystal material.
12. trans- polymers dispersed liquid crystal light valve according to claim 11, which is characterized in that first base layer, Second matrix layer material can independently be glass or transparent plastic.
13. trans- polymers dispersed liquid crystal light valve according to claim 11, which is characterized in that first conductive layer, Second conductive layer is transparency conducting layer, and first conductive layer and the second conductive layer can be according to showing or erasing pattern Demand is divided into different shape and several units.
14. the described in any item trans- polymers dispersed liquid crystal light valves of claim 11-13 are in the application in photoswitch field.
CN201810020222.8A 2018-01-09 2018-01-09 A kind of trans- polymer dispersion liquid crystal material, liquid crystal light valve and its application Pending CN110016352A (en)

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