CN106353848B - Circular polarizer and preparation method thereof - Google Patents
Circular polarizer and preparation method thereof Download PDFInfo
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- CN106353848B CN106353848B CN201611024937.8A CN201611024937A CN106353848B CN 106353848 B CN106353848 B CN 106353848B CN 201611024937 A CN201611024937 A CN 201611024937A CN 106353848 B CN106353848 B CN 106353848B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
- G02B5/3091—Birefringent or phase retarding elements for use in the UV
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
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- Spectroscopy & Molecular Physics (AREA)
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a circular polarizer and a preparation method thereof. According to the invention, the surface of a base material is coated with a first orientation layer and a second orientation layer respectively, a phase difference layer is formed on the surface of the second orientation layer, the surface of the first orientation layer is coated with a polarization layer mixture, the polarization layer mixture comprises a plurality of polymerizable liquid crystal monomers, dichroic pigments and ultraviolet light absorbers, under the irradiation of ultraviolet light, the polymerizable liquid crystal monomers with more polymerizable groups on one side close to an ultraviolet light source are enriched, the polymerizable liquid crystal monomers with less polymerizable groups on one side far away from the ultraviolet light source are enriched, the polymerizable liquid crystal monomers with more polymerizable groups are in a nematic phase, the viscosity of the nematic phase is lower, and a continuous and perfect curing film is formed; the polymerizable liquid crystal monomer with less polymerizable groups presents a smectic phase, and the smectic phase is an ideal two-dimensional ordered structure and plays a role in polarizing to form a polarizing layer; has the advantages of thin thickness and good flexibility; has good anti-reflection property in the whole visible light range.
Description
Technical field
The present invention relates to display fields, and in particular to a kind of rotatory polarization piece and preparation method thereof.
Background technique
ORGANIC ELECTROLUMINESCENCE DISPLAYS technology have self-luminous, wide viewing angle, almost infinite high contrast, compared with low power consumption, pole
High reaction speed and can flexibility the advantages that, it is considered to be substitute the next-generation mainstream display technology of LCD technology.But,
Display of organic electroluminescence used at present exists anti-indoors or under outdoor strong light but because there are metal electrode structures
Light causes the interference read, causes dark-state not dark enough.General solution be outside along with can environment resistant light reflect
Rotatory polarization piece.Extraneous natural light is passed through by the circularly polarized light for only having a certain rotation direction after rotatory polarization piece, and the circle of another rotation direction is inclined
Vibration light be then absorbed, by circularly polarized light opposite rotation direction is changed into after metal electrode reflects again, this opposite rotation direction
Reflected light is absorbed when through the rotatory polarization piece in outside, can be eliminated the interference of external environmental light in this way, be obtained real dark-state.
The line polarisation piece of institute's large-scale use is mainly by intermediate polyvinyl alcohol and the Triafol T of two sides at present
It constitutes, further includes release film and protective film.Wherein polyvinyl alcohol dyes under stretching condition through iodine or dichroic dye, plays production
The effect of raw polarised light.The polaroid complex process of this traditional handicraft preparation, with high costs and thickness are partially thick, and general thickness is all
Between 150~250 μm.To this polaroid to be applied in display of organic electroluminescence as rotatory polarization piece, then need
Compound at least one layer of phase difference film on online polaroid is wanted, causes thickness thicker, flexural property is poor, also will increase corresponding
The weight of display of organic electroluminescence.
Summary of the invention
For the above problems of the prior art, the invention proposes a kind of rotatory polarization piece and preparation method thereof, circles
Polaroid can coated technique be made, and have slimming and good flexural property.
An object of the present invention is to provide a kind of rotatory polarization pieces.
Rotatory polarization piece of the invention includes: substrate, first alignment layer, polarizing layer, second orientation layer and phase separation layer；Its
In, substrate is isotropism, is coated with first alignment layer on a surface of substrate；Polarizing layer is coated on the surface of first alignment layer
Mixture, polarizing layer mixture include a variety of polymerisable liquid crystal monomers, dichroism pigment and UV absorbers, a variety of polymerizable
The number for the polymerizable groups that liquid crystal monomer has has differences, under the ultraviolet light of fixed temperature, UV absorbers
With ultraviolet absorption characteristic, there are ultraviolet ray intensity gradients on the direction of propagation of ultraviolet light, and the strong region of ultraviolet ray intensity can
The polymerization speed of polymerizable liquid crystal monomer is very fast, on the contrary then relatively slow；Meanwhile the polymerisable liquid crystal monomer polymerization that polymerizable groups are more
Speed is also very fast, and the polymerization speed of polymerisable liquid crystal monomer gradually weakens along the direction of propagation of ultraviolet light, far from ultraviolet source
The more polymerisable liquid crystal monomer of the unpolymerized polymerizable groups number of side will be against ultraviolet optical propagation direction and to close to purple
Outer smooth side diffusion, after completed polymerisation, the concentration of polymerisable liquid crystal monomer is fixed, and can gather close to ultraviolet source side
Close group numbers it is more polymerisable liquid crystal monomer enrichment, and far from ultraviolet source side polymerizable groups it is small numbers of can
Polymerizable liquid crystal monomer enrichment；Phase transformation existing for the different polymerisable liquid crystal monomer of the number of polymerizable groups is different, poly-
It closes temperature to be higher than at a temperature of the opposite smectic phase transition point of nematic, the more polymerisable liquid crystal monomer of polymerizable groups number is presented
Nematic phase, nematic viscosity is lower, forms continuous and perfect cured film；The small numbers of polymerisable liquid crystal of polymerizable groups
Smectic phase is presented in monomer, and smectic phase is ideal two dimensional structure, plays the role of being polarized, and forms polarizing layer；In the another of substrate
One surface is coated with second orientation layer；Phase separation layer mixture, phase separation layer mixture packet are coated on the surface of second orientation layer
Nematic phase polymerisable liquid crystal, initiator and solvent are included, solvent is removed through volatilization after coating, is formed after polymerizing curable in nematic phase
Phase separation layer.
In order to guarantee that the emergent light after dichroism pigment absorbs is linearly polarized light, it is desirable that the long axis of dichroism pigment is orientated
Direction is consistent, therefore by liquid crystal, the orientation of dichroism pigment is driven with the orientation of liquid crystal.In order to guarantee dichroism pigment to entering
Fully absorbing for light is penetrated, then requires dichroism pigment to have in the two-dimensional direction and more preferably arranges, if making dichroism pigment molecule
It is then excellent selection in smectic liquid crystal.But in general, the temperature range of smectic liquid crystal will be lower than nematic
Phase, and viscosity is significantly larger than nematic phase.In planar orientation, during being changed by the opposite smectic phase of the nematic of liquid crystal,
Liquid crystal coatings will appear cracking phenomena, and transition process wants long enough, influence production efficiency.
Polarizing layer mixture of the invention uses the different a variety of polymerisable liquid crystals of number for the polymerizable groups having
Monomer, there are smectic phases and nematic phase two-phase coexistent structure for the liquid crystal film after leading to polymerization.In polarizing layer mixture further
Including initiator and solvent.Polymerization temperature is higher than the temperature of the opposite smectic phase transformation of nematic within 5 DEG C.
The mass percentage content of UV absorbers is 0.1~10%；The mass percentage content of dichroism pigment is
0.1~15%.Further include solvent except polymerisable liquid crystal, dichroism pigment and UV absorbers, mass percent 5~
Between 90%；Further, initiator of the mass percent of component between 0~10wt% is added, accelerates polymerization speed；It is added
Moistening flatting agent of the mass percent of component between 0.0001~5wt%, change composition and substrate binding ability and
Film forming.
It is pre-formed the first and second oriented layer respectively in substrate surface, to realize liquid in polarizing layer and phase separation layer
Brilliant orientation.
The material of first alignment layer or second orientation layer, which uses, has coating polarizing layer mixture or phase separation layer mixture
The substance of good heat resistance will not be dissolved and had afterwards.It is preferred that high molecular material, such as polyvinyl alcohol, polyimides, alkyl change
Property polyvinyl alcohol, polyacrylamide, polyethyleneimine, polystyrene, polyvinyl pyrrolidone, polyacrylic acid or polyacrylic acid
Esters high molecular material.Layer material is orientated can also individually be used in mixed way.
With upper oriented layer material, the method realization through flannelette friction is mixed to polarizing layer mixture and phase separation layer after the drying
Close the orientation of liquid crystal and dichroism pigment in object.
Alternatively, first alignment layer or second orientation layer use the Photoinduced alignment material for orientation anchorage force occur by illumination.
Oriented layer is prepared by Photoinduced alignment material shape irradiation polarised light (preferably polarized ultraviolet).Its advantage is can to pass through selection
The direction of the polarised light of irradiation can freely control the method for alignment of polymerizability liquid-crystal compounds.Photoinduced alignment material is logical
It crosses photoreactive group and issues raw molecularly oriented induction or isomerization reaction, dimerization reaction, photo-crosslinking, light in the irradiation of light
Decomposition reaction and obtain orientation anchorage force.
Photoinduced alignment material is preferably to have carbon-to-carbon double bond, carbon-to-nitrogen double bond, nitrogen-with unsaturated bond, especially double bond
The material of at least one photoreactive group in nitrogen double bond and carbon-oxygen double bond.Photoreactive group lifts to contain vinyl, more
Alkenyl, Stilbene base, stibazole base, chalcone base and cinnamoyl, aromatic series schiff bases, aromatic series hydrazone, azobenzene, idol
Quinoline, heteroaromatic azo group, bisazo base, azoxybenzene, diphenylmethyl ketone group, cumarin base, anthraquinonyl and horse
Carry out one of imide or a variety of.Wherein, preferably with the photoreactive group for being able to carry out light dimerization reaction, such as cortex cinnamomi
The light orientation material of acyl group or chalcone base.
Substrate is polyester resin, polycarbonate resin, polystyrene resin, polyacrylate resin, polymethylacrylic acid
One of ester resin, polyurethane resin, polycyclic alkene resin, polyvinyl resin and Corvic or a variety of mixing
Object, preferably poly cyclene resin COP；The thickness of substrate is at 5~300 μm, and preferably 20~200 μm, in order to guarantee obtained circle
Polaroid is frivolous and flexible, and further preferably 20~100 μm.
The phase difference of phase separation layer is λ/4.The thickness of phase separation layer is true by the birefringence institute of nematic phase polymerisable liquid crystal
Fixed, i.e., the product of birefringence and thickness is phase-delay value, and on the basis of wavelength 550nm, 550nm is in visible light wave range
Between be worth, phase separation layer realizes the phase difference of λ/4 with the median of visible light.
Polymerisable liquid crystal monomer refers to polymerizable compound under ultraviolet light, has one or more polymerizable groups
Group.Polymerizable groups are acryloyl group, methylacryloyl, fluoropropene base, Chloroallyl, trifluoromethyl acrylic, oxa- ring
Butane group, vinyl ether, vinyl ketone base, dimaleoyl imino, phenyl maleimide base, vinyl, styryl, two
One of acetyl group and epoxy group are a variety of.
Polymerization methods use uv-light polymerization.
UV absorbers are benzophenone, alkenes, azo or phosphonium salt.
Dichroism pigment refers to the pigment different from the absorbance of short-axis direction of the absorbance with molecular long axis direction.Such as
Fruit has above-mentioned property, and dichroism pigment can be dyestuff, be also possible to pigment, is also possible to the mixture of multiple compounds.
Dichroism pigment has maximum absorption wavelength within the scope of 300~700nm, using acridine pigment, anthocyanin pigments, naphthalene
One of pigment, azopigment and anthraquinone pigment are a variety of.It is preferred that azopigment using monoazo pigment, bisazo pigment,
One of trisazo- pigment, four azopigments and Stilbene azopigment are a variety of, further preferred bisazo pigment and trisazo-
Pigment.
Initiator is using benzoin compound, benzophenone cpd, alkyl phenones compound, acylphosphine oxidation
Object, triaizine compounds, salt compounded of iodine with one of sulfonium salt or a variety of.Such as: Benzoyl Oxide, azodiisobutyronitrile, benzoin
Ethers, benzophenone, acetophenones, benzil ketals class, diaryl iodonium salt, triarylsulfonium salt, diphenyl iodine four
Borofluoride, diphenyl iodine hexafluorophosphonate, diphenyl iodine arsenate, diphenyl iodine four (pentafluorophenyl group) borate,
4- methoxyphenyl phenyl-iodide tetrafluoroborate, 4- methoxyphenyl phenyl-iodide hexafluorophosphonate, 4- methoxyphenyl benzene
Base iodine hexafluoro arsenate, bis- (4- tert-butyl-phenyl) iodine diphenyl iodine tetrafluoroborates, bis- (4- tert-butyl-phenyl) iodine
Diphenyl iodine hexafluorophosphonate, bis- (4- tert-butyl-phenyl) iodine diphenyl iodine trifluoro-methanyl sulfonates, triphenylsulfonium
Hexafluorophosphonate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium four (pentafluorophenyl group) borate, 4- methoxyphenyl two
Phenyl sulfonium tetraphydro-borate, 4- methoxyphenyl diphenyl sulfonium tetrahydro phosphonate, 4- methoxyphenyl diphenyl sulfonium four
Hydrogen arsenate, 4- methoxyphenyl diphenyl sulfonium trifluoromethayl sulfonic acid ester, 4- methoxyphenyl diphenyl sulfonium triphenylsulfonium
Four (pentafluorophenyl group) borates, 4- phenyl thiophenyl diphenyl sulfonium hexafluoro arsenate, benzil dimethyl ketal and it is bis- (2,
4,6- trimethylbenzoyls) one of-phenylphosphine oxide or a variety of.Photoinitiator and the not stringent area of thermal initiator
Point, above initiator is determined by polymerization methods either photoinitiator is also possible to thermal initiator.
Solvent be benzene,toluene,xylene, mesitylene, n-butylbenzene, diethylbenzene, tetrahydronaphthalene, methoxybenzene, 1,
2- dimethoxy benzene, glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, hexamethylene
Ketone, ethyl acetate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol list
Ethyl ether acetate ester, 2-Pyrrolidone, n-methyl-2-pyrrolidone, dimethylformamide, chloroform, methylene chloride, first chlorination carbon,
Dichloroethanes, trichloro ethylene, tetrachloro-ethylene, chlorobenzene, the tert-butyl alcohol, diacetone alcohol, glycerine, acetin, ethylene glycol, three
One of ethylene glycol, hexylene glycol, glycol monoethyl ether, ethyl cellosolve and butyl cellosolve are a variety of.It is preferred that polymerizable
Monomer have excellent dissolution performance and boiling point be greater than 60 DEG C and lower than 200 DEG C, non-toxic or low-toxic, low-corrosiveness, Yi Huishou
Solvent.
Further, polarizing layer mixture of the invention and phase separation layer mixture can also according to selected ingredient, technique and
Actual demand decides whether to add polymerization inhibitor, defoaming agent, diluent, ultraviolet absorbing agent, alignment agent, surfactant, ultraviolet
One of solidification glue and heat-curable glue are a variety of.
It is another object of the present invention to provide a kind of preparation methods of rotatory polarization piece.
The preparation method of rotatory polarization piece of the invention, comprising the following steps:
1) isotropic substrate is provided；
2) first alignment layer is coated on a surface of substrate；
3) it is coated with polarizing layer mixture on the surface of first alignment layer, polarizing layer mixture includes a variety of polymerisable liquid crystal lists
The number of body, dichroism pigment and UV absorbers, the polymerizable groups that a variety of polymerisable liquid crystal monomers have has differences；
4) under the ultraviolet light of fixed temperature, UV absorbers have ultraviolet absorption characteristic, in the biography of ultraviolet light
Broadcast on direction that there are ultraviolet ray intensity gradients, the polymerization speed of the strong region polymerisable liquid crystal monomer of ultraviolet ray intensity is very fast, instead
It is then relatively slow；Meanwhile polymerizable groups it is more polymerisable liquid crystal monomer polymerization speed it is also very fast, along the direction of propagation of ultraviolet light
The polymerization speed of upper polymerisable liquid crystal monomer gradually weakens, far from ultraviolet source side unpolymerized polymerizable groups number compared with
More polymerisable liquid crystal monomers after completed polymerisation, will can gather against ultraviolet optical propagation direction and to spreading by black light side
The concentration for closing liquid crystal monomer is fixed, close to the more polymerisable liquid crystal monomer of ultraviolet source side polymerizable groups number
Enrichment, and the small numbers of polymerisable liquid crystal monomer enrichment of polymerizable groups far from ultraviolet source side；Polymerizable groups
Phase transformation existing for the different polymerisable liquid crystal monomer of number is different, is higher than the opposite smectic phase transformation of nematic in polymerization temperature
At a temperature of, nematic phase is presented in the more polymerisable liquid crystal monomer of polymerizable groups number, and nematic viscosity is lower, is formed continuous
And perfect cured film；Smectic phase is presented in the small numbers of polymerisable liquid crystal monomer of polymerizable groups, and smectic phase is ideal two
Ordered structure is tieed up, plays the role of being polarized, forms polarizing layer；
5) second orientation layer is coated on another surface of substrate；
6) it is coated with phase separation layer mixture on the surface of second orientation layer, phase separation layer mixture includes that nematic phase is polymerizable
Liquid crystal, initiator and solvent remove solvent through volatilization after coating, form phase separation layer after polymerizing curable in nematic phase, obtain
Circular polarizing disk of the polarizing layer in conjunction with phase separation layer.
Wherein, in step 1), to guarantee the bonding force between coating and substrate, it is however generally that, substrate surface need to do electricity
Dizzy processing.
In step 2) or step 5), in order to assign oriented layer orientation anchorage force, rub as needed.Oriented layer is adopted
Be coated on the surface of substrate with blade coating, bar coating, rotary coating or the method for roller coating, preferably coating efficiency it is high and
Low-cost bar rubbing method.
In step 4) or step 6), polarizing layer or phase separation layer are applied by coating method using blade coating, bar
One of cloth, rotary coating and roller coating mode is coated on first or second oriented layer.It is preferred that coating efficiency it is high, at
This cheap bar rubbing method.
Advantages of the present invention:
The present invention uses the substrate of isotropic, and surface is respectively coated first alignment layer and second orientation layer, takes second
Phase separation layer is formed to the surface of layer, is coated with polarizing layer mixture on the surface of first alignment layer, polarizing layer mixture includes more
Kind polymerisable liquid crystal monomer, dichroism pigment and UV absorbers, the polymerizable groups that a variety of polymerisable liquid crystal monomers have
Number have differences, under the ultraviolet light of fixed temperature, close to ultraviolet source side polymerizable groups number it is more
The enrichment of polymerisable liquid crystal monomer, and the small numbers of polymerisable liquid crystal monomer of polymerizable groups far from ultraviolet source side is rich
Nematic phase is presented in collection, the more polymerisable liquid crystal monomer of polymerizable groups number, and nematic viscosity is lower, is formed continuous and complete
The cured film of beauty；Smectic phase is presented in the small numbers of polymerisable liquid crystal monomer of polymerizable groups, and smectic phase is that ideal two dimension has
Sequence structure plays the role of being polarized, and forms polarizing layer；With slimming and good flexural property；In entire visible-range,
With good preventing reflection characteristic.
Detailed description of the invention
Fig. 1 is the sectional view of one embodiment of rotatory polarization piece of the invention；
Fig. 2 is polymerizability liquid crystal monomer, dichroism pigment and the purple in one embodiment of rotatory polarization piece of the invention
The structural formula of outer light absorber, wherein (a) is the structural formula of the first polymerisable liquid crystal monomer；It (b) is second of polymerizable liquid
The structural formula of brilliant monomer；It (c) is the structural formula of ultraviolet absorber；It (d) is the structural formula of the first dichroism pigment；It (e) is the
The structural formula of two kinds of dichroism pigments；It (f) is the structural formula of the third dichroism pigment.
Specific embodiment
With reference to the accompanying drawing, by specific embodiment, the present invention is further explained.
In the present embodiment, " % " refers both to mass percent if being not particularly illustrated.
As shown in Figure 1, the rotatory polarization piece of the present embodiment includes: substrate 1, first alignment layer 2, polarizing layer 3, second orientation layer
4 and phase separation layer 5.
In the present embodiment, the polymerisable liquid crystal monomer in the polymerisable liquid crystal in polarizing layer includes double polymerizable groups monomers
With single polymerizable groups monomer；Double polymerizable groups monomer temperatures are successively presented from low to high to the same sex, nematic phase and crystalline phase,
Isotropism, nematic phase, smectic phase and crystalline phase is successively presented in single polymerizable groups monomer temperature from low to high, when temperature is slightly lower
When single polymerizable groups monomer nematic phase is to smectic phase transition point, nematic phase is presented in mixed liquid crystal.In addition UV Absorption
Under conditions of agent, along with double polymerizable groups monomer moving towards ultraviolet source side in the polymerization process of fixed temperature
It moves, it is rich far from ultraviolet source side list polymerizable groups monomer close to the double polymerizable groups monomer enrichments in ultraviolet source side
Collect, the liquid crystal film obtained after polymerizing curable has the Phase stracture of nematic phase, transition state and smectic phase.Due to leaning near ultraviolet
Light side liquid film is nematic phase, and nematic viscosity is lower, is easily formed continuous, perfect cured film, can effectively prevent
The only cracking during film-forming；Smectic phase is being presented far from ultraviolet source side, having benefited from the ideal two dimension of smectic phase has
The dichroism pigment of sequence structure, minute quantity addition can play the role of being polarized well.
The preparation method of the rotatory polarization piece of the present embodiment, comprising the following steps:
1) isotropic substrate is provided:
Using poly cyclene resin COP film, 20~100 μm of thickness.
2) first alignment layer is coated on a surface of substrate:
It with wet-film thickness is that 8 microns of bar is coated on that (power is through sided corona treatment by 2% polyvinyl alcohol water solution
500 watts) 25 microns thick of COP film on, dried 2 minutes at 80 DEG C, apply 2kg/cm on flannelette2Power rub poly- second
Enol coating, obtains first alignment layer.
3) it is coated with polarizing layer mixture on the surface of first alignment layer, polarizing layer mixture includes a variety of polymerisable liquid crystal lists
The number of body, dichroism pigment and UV absorbers, the polymerizable groups that a variety of polymerisable liquid crystal monomers have has differences:
A) preparation of polarizing layer mixture:
Structural formula is as shown in Fig. 2, by 20% the first polymerisable liquid crystal monomer, second 71.1% of polymerisable liquid crystal
Monomer, 3% dichroism pigment (wherein the first dichroism pigment, second of dichroism pigment and the third dichroism pigment
Content be respectively 55%, 30%, 15%), the UV absorbing dyes of 4.7% initiator Irgacure 369,1%, 0.2%
Levelling agent BYK361N be dissolved in toluene, be configured to the solution of solid content 35%, with G4 sand core funnel filter, polarisation is prepared
Layer mixture；
B) polarizing layer mixture is coated on the first alignment layer prepared with bar.
4) it is transferred to baking 2 minutes in 60 DEG C of baking oven and is passed through nitrogen into baking oven to remove solvent, is using radiation wavelength
(ultraviolet ray intensity at film is 0.4mW/cm to the ultraviolet lamp of 365nm2) irradiation polymerize polymerisable liquid crystal in 10 minutes, consolidate
The polarizing layer of change.
5) second orientation layer is coated on another surface of substrate:
In the other side for the COP film for having been coated with cholesteric liquid crystal through corona, painting polyethylene alcoholic solution, drying, friction
And etc. preparation second orientation layer.
6) phase separation layer mixture is coated on the oriented layer 2 prepared with the bar that wet-film thickness is 6 microns, in
2 minutes are dried at 70 DEG C to remove solvent, nitrogen is passed through into baking oven, using the ultraviolet lamp that radiation wavelength is 365nm (at film
Ultraviolet ray intensity be 1.8mW/cm2) irradiation polymerize nematic phase polymerisable liquid crystal, cured phase separation layer is obtained,
Phase difference is about 140nm.
The above prepared rotatory polarization piece is fitted on reflecting plate, reflectivity is measured.In 400~700nm wave-length coverage
Interior light, any wavelength is 1~15%.As it can be seen that rotatory polarization piece of the invention has good in entire visible-range
Preventing reflection characteristic.
It is finally noted that the purpose for publicizing and implementing example is to help to further understand the present invention, but this field
Technical staff be understood that without departing from the spirit and scope of the invention and the appended claims, it is various replacement and repair
It is all possible for changing.Therefore, the present invention should not be limited to embodiment disclosure of that, and the scope of protection of present invention is to weigh
Subject to the range that sharp claim defines.
Claims (10)
1. a kind of rotatory polarization piece, which is characterized in that the rotatory polarization piece includes: substrate, first alignment layer, polarizing layer, second takes
To layer and phase separation layer；Wherein, the substrate is isotropism, is coated with first alignment layer on a surface of substrate；First
The surface of oriented layer is coated with polarizing layer mixture, and the polarizing layer mixture includes a variety of polymerisable liquid crystal monomers, dichroism color
Element and UV absorbers, the number for the polymerizable groups that a variety of polymerisable liquid crystal monomers have has differences, in fixation
Under the ultraviolet light of temperature, UV absorbers have ultraviolet absorption characteristic, and there are ultraviolet on the direction of propagation of ultraviolet light
The polymerization speed of light intensity gradient, the strong region polymerisable liquid crystal monomer of ultraviolet ray intensity is very fast, on the contrary then relatively slow；Meanwhile it can
The more polymerisable liquid crystal monomer polymerization speed of polymer-based group is also very fast, the polymerisable liquid crystal monomer along the direction of propagation of ultraviolet light
Polymerization speed gradually weaken, the more polymerisable liquid crystal list of unpolymerized polymerizable groups number far from ultraviolet source side
Body will be against ultraviolet optical propagation direction and to spreading, after completed polymerisation by black light side, the concentration of polymerisable liquid crystal monomer
It is fixed, the polymerisable liquid crystal monomer enrichment more close to ultraviolet source side polymerizable groups number, and far from ultraviolet
The small numbers of polymerisable liquid crystal monomer enrichment of the polymerizable groups of light source side；The number of polymerizable groups is different to gather
Phase transformation existing for conjunction liquid crystal monomer is different, polymerizable at a temperature of polymerization temperature is higher than the opposite smectic phase transition point of nematic
Nematic phase is presented in the more polymerisable liquid crystal of group numbers, and nematic viscosity is lower, forms continuous and perfect cured film；It can
Smectic phase is presented in the small numbers of polymerisable liquid crystal of polymer-based group, and smectic phase is ideal two dimensional structure, plays and is polarized work
With formation polarizing layer；Second orientation layer is coated on another surface of substrate；Phase separation layer is coated on the surface of second orientation layer
Mixture, the phase separation layer mixture include nematic phase polymerisable liquid crystal, initiator and solvent, and removal of being volatilized after coating is molten
Agent forms phase separation layer after polymerizing curable in nematic phase.
2. rotatory polarization piece as described in claim 1, which is characterized in that the phase difference of the phase separation layer is λ/4.
3. rotatory polarization piece as described in claim 1, which is characterized in that polymerization temperature is higher than the opposite smectic phase transition point of nematic
Temperature is within 5 DEG C.
4. rotatory polarization piece as described in claim 1, which is characterized in that the mass percentage content of the UV absorbers is
0.1~10%；The mass percentage content of the dichroism pigment is 0.1~15%.
5. rotatory polarization piece as described in claim 1, which is characterized in that the material of the first alignment layer or second orientation layer is adopted
With the substance with that will not be dissolved after coating polarizing layer mixture or phase separation layer mixture and with good heat resistance；Or institute
It states first alignment layer or second orientation layer uses the Photoinduced alignment material for orientation anchorage force occur by illumination.
6. rotatory polarization piece as described in claim 1, which is characterized in that the substrate is polyester resin, polycarbonate resin, gathers
Styrene resin, polyacrylate resin, polymethacrylate resin, polyurethane resin, polycyclic alkene resin, polyethylene tree
One of rouge and Corvic or a variety of mixtures.
7. rotatory polarization piece as described in claim 1, which is characterized in that the polymerisable liquid crystal monomer refers in ultraviolet light
Under polymerizable compound, there are one or more polymerizable groups；Polymerizable groups be acryloyl group, methylacryloyl,
Fluoropropene base, Chloroallyl, trifluoromethyl acrylic, oxetanyl, vinyl ether, vinyl ketone base, maleimide
One of amido, phenyl maleimide base, vinyl, styryl, diacetyl and epoxy group are a variety of.
8. rotatory polarization piece as described in claim 1, which is characterized in that the UV absorbers be benzophenone, alkenes,
Azo or phosphonium salt.
9. rotatory polarization piece as described in claim 1, which is characterized in that the dichroism pigment has within the scope of 300~700nm
Maximum absorption wavelength, using one of acridine pigment, anthocyanin pigments, naphthalene pigment, azopigment and anthraquinone pigment or a variety of.
10. a kind of preparation method of rotatory polarization piece, which is characterized in that the preparation method comprises the following steps:
1) isotropic substrate is provided；
2) first alignment layer is coated on a surface of substrate；
3) first alignment layer surface be coated with polarizing layer mixture, polarizing layer mixture include a variety of polymerisable liquid crystal monomers,
The number of dichroism pigment and UV absorbers, the polymerizable groups that a variety of polymerisable liquid crystal monomers have has differences；
4) under the ultraviolet light of fixed temperature, UV absorbers have ultraviolet absorption characteristic, in the propagation side of ultraviolet light
Upwards there are ultraviolet ray intensity gradients, the polymerization speed of the strong region polymerisable liquid crystal monomer of ultraviolet ray intensity is very fast, it is on the contrary then
It is relatively slow；Meanwhile polymerizable groups it is more polymerisable liquid crystal monomer polymerization speed it is also very fast, can along the direction of propagation of ultraviolet light
The polymerization speed of polymerizable liquid crystal monomer gradually weakens, and the unpolymerized polymerizable groups number far from ultraviolet source side is more
Polymerisable liquid crystal monomer will be against ultraviolet optical propagation direction and to spreading, after completed polymerisation by black light side, polymerizable liquid
The concentration of brilliant monomer is fixed, and the polymerisable liquid crystal monomer more close to ultraviolet source side polymerizable groups number is rich
Collection, and the small numbers of polymerisable liquid crystal monomer enrichment of polymerizable groups far from ultraviolet source side；The number of polymerizable groups
Phase transformation existing for the different polymerisable liquid crystal monomer of mesh is different, is higher than the opposite smectic phase transition point of nematic in polymerization temperature
At a temperature of, nematic phase is presented in the more polymerisable liquid crystal of polymerizable groups number, and nematic viscosity is lower, is formed continuous and complete
The cured film of beauty；Smectic phase is presented in the small numbers of polymerisable liquid crystal of polymerizable groups, and smectic phase is ideal sequential 2 D knot
Structure plays the role of being polarized, and forms polarizing layer；
5) second orientation layer is coated on another surface of substrate；
6) it is coated with phase separation layer mixture on the surface of second orientation layer, phase separation layer mixture includes the polymerizable liquid of nematic phase
Brilliant, initiator and solvent remove solvent through volatilization after coating, form phase separation layer after polymerizing curable in nematic phase, obtain partially
Circular polarizing disk of the photosphere in conjunction with phase separation layer.
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| JP7281953B2 (en) * | 2018-07-25 | 2023-05-26 | 住友化学株式会社 | laminate |
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