CN109233803A - A kind of polymer fluorescent nano grain and its preparation method and application - Google Patents
A kind of polymer fluorescent nano grain and its preparation method and application Download PDFInfo
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- CN109233803A CN109233803A CN201810826967.3A CN201810826967A CN109233803A CN 109233803 A CN109233803 A CN 109233803A CN 201810826967 A CN201810826967 A CN 201810826967A CN 109233803 A CN109233803 A CN 109233803A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 151
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000000975 dye Substances 0.000 claims abstract description 60
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000008187 granular material Substances 0.000 claims abstract description 52
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 31
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 22
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims abstract description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims abstract description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims abstract description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 4
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 238000009792 diffusion process Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000006071 cream Substances 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 230000004313 glare Effects 0.000 abstract description 5
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical class O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 abstract description 2
- 235000013339 cereals Nutrition 0.000 description 66
- 239000010410 layer Substances 0.000 description 18
- 239000011241 protective layer Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- -1 acryl Chemical group 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 208000033748 Device issues Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133504—Diffusing, scattering, diffracting elements
-
- 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
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of polymer fluorescent nano grains, for liquid crystal display device, including polymer nano granules and the dye stuff of rhodamine kinds and hydrophobic balance object that are supported on the polymer nano granules, the dye stuff of rhodamine kinds and the hydrophobic balance object are combined together by electrostatic attraction, and the hydrophobic balance object includes at least one of perchlorate, tetraphenylboron sodium, four (4- fluorophenyl) boronation sodium hydrates and trityl four (pentafluorophenyl group) borate.The polymer fluorescent nano grain can be absorbed yellow orange light and emit feux rouges, can be used in liquid crystal display device, reduce the interference of yellow orange light veiling glare, promote colour gamut, while emitting feux rouges and guaranteeing that brightness is constant；Meanwhile dye stuff of rhodamine kinds is supported on polymer fluorescent nano grain and can reunite to avoid dye stuff of rhodamine kinds, improves absorption efficiency and fluorescence efficiency, the polymer fluorescent nano grain have wide practical use in liquid crystal display device.
Description
Technical field
The present invention relates to field of display technology more particularly to a kind of polymer fluorescent nano grain and preparation method thereof and answer
With.
Background technique
With flourishing for display technology, high colour gamut has become an important developing direction.High colour gamut means
TV can show that more colourful color, and there is stronger color to show ability, can effectively avoid in this way
Occurs the case where distortion and color lump when display.Since the type of color increases, so that the color switching in television image can be with
More naturally, making the level of picture more clearly demarcated, more details can be showed and be more nearly true effect.For
LCD TV promotes colour gamut and mainly passes through three primary colors (red, green, blue) because screen itself does not have spontaneous light attribute
Color fim filter is realized；In addition it is also possible to carry out the promotion of colour gamut by the adjustment of backlight.
Currently, the mode for promoting backlight purity is the backlight using blue led and red green fluorescence material, or use quantum dot
QD backlight technology.However the drawback of both colour gamut method for improving maximums is the red green blue tricolor light finally issued and impure
Only.Because it does not purify red green blue tricolor light in the process for promoting colour gamut, there are yellow orange light, so issuing
Red green blue tricolor light it is impure.Therefore, it is necessary to a kind of methods that can be avoided yellow orange light and improve colour gamut.
Summary of the invention
In view of this, being used for liquid crystal display device, including polymer the present invention provides a kind of polymer fluorescent nano grain
Nano particle and the dye stuff of rhodamine kinds being supported on the polymer nano granules and hydrophobic balance object, the rhodamine dye
Material and the hydrophobic balance object are combined together by electrostatic attraction.It is concurrent that yellow orange light can be absorbed in the polymer fluorescent nano grain
Feux rouges is penetrated, can be used in liquid crystal display device, the interference of yellow orange light veiling glare is reduced, promotes colour gamut, while emitting feux rouges guarantee
Brightness is constant；Meanwhile dye stuff of rhodamine kinds is supported on polymer fluorescent nano grain and group can occur to avoid dye stuff of rhodamine kinds
It is poly-, improve absorption efficiency and fluorescence efficiency.
In a first aspect, the present invention provides a kind of polymer fluorescent nano grain, including polymer nano granules and it is supported on
Dye stuff of rhodamine kinds and hydrophobic balance object on the polymer nano granules, the dye stuff of rhodamine kinds and the hydrophobic balance
Object is combined together by electrostatic attraction, and the hydrophobic balance object includes perchlorate, tetraphenylboron sodium, four (4- fluorophenyl) boronations
At least one of sodium hydrate and trityl four (pentafluorophenyl group) borate.
In the present invention, the uv-visible absorption spectra of the dye stuff of rhodamine kinds and fluorescence emission spectrum can be seen that
Its absorption peak concentrates in yellow orange optical range, and emission peak is in red light region.Therefore, the Luo Dan on the polymer fluorescent nano grain
Bright class dyestuff can be absorbed yellow orange light (570nm-610nm) and launch feux rouges (610nm-700nm).
In the present invention, the polymer nano granules have three-dimensional netted space structure, are approximately spherical, the Luo Dan
It is combined together between bright class dyestuff and the hydrophobic balance object by electrostatic attraction and is located at the polymer nano granules
Inside reticular structure and surface, that is, be supported on the polymer nano granules, can reunite to avoid dye stuff of rhodamine kinds
And fluorescent quenching is caused to influence fluorescence efficiency, be conducive to the dispersion of dye stuff of rhodamine kinds, improve absorption efficiency and fluorescence efficiency, and
And its stability is helped to improve, preferably in the preparation of film.
In the present invention, the dye stuff of rhodamine kinds is basic dye, is that can dissociate generation cation in aqueous solution
Dyestuff, and hydrophobic balance object dissociates generate anion in aqueous solution, the rhodamine and the hydrophobic balance object pass through
Electrostatic attraction is combined together, and is supported on the polymer nano granules, so that polymer fluorescent nano grain is integrally positive and negative
Charge balance guarantees polymer fluorescent nano grain overall stability.
Optionally, the polymer nano granules include poly lactide-glycolide acid, polymethyl methacrylate and
At least one of polycaprolactone.
Optionally, the dye stuff of rhodamine kinds has the structure as shown in formula (I),
Wherein, R1、R2、R3、R4、R5、R6、R7Independently selected from C1-C25Alkyl, C1-C25Halogenated alkyl and C6-C25's
At least one of aromatic radical, the alkyl are straight chain or the chain-like alkyl with branch, and the halogenated alkyl is straight chain or band
There is the halogenated alkyl of branch.
Optionally, the aromatic radical includes at least one of mono-cyclic aromatic base and multiring aromatic.
Optionally, the structure of the aromatic radical isWherein, R8Selected from C1-C25Alkyl, C1-
C25Alkoxy and C1-C25At least one of alkenyl；R9、R10、R11Independently selected from H, C1-C25Alkyl, C1-C25's
Ester group, C1-C25Alkoxy and C1-C25At least one of halogenated alkyl.
It is further alternative, the alkyl be straight chain or the chain-like alkyl with branch, the halogenated alkyl be straight chain or
Halogenated alkyl with branch.
Optionally, the structure of the aromatic radical isWherein, R12Selected from C1-C25Alkane
Base, C1-C25Alkoxy and C1-C25At least one of alkenyl；R13、R14、R15、R16Independently selected from H, C1-C25Alkane
Base, C1-C25Ester group, C1-C25Alkoxy and C1-C25At least one of halogenated alkyl.
It is further alternative, the alkyl be straight chain or the chain-like alkyl with branch, the halogenated alkyl be straight chain or
Halogenated alkyl with branch.
Optionally, the weight average molecular mass of the polymer nano granules is 10000-40000.
Optionally, the partial size of the polymer nano granules is 20nm-80nm.It is further alternative, the polymer nano
The partial size of rice grain is 20nm-70nm, 25nm-55nm or 30nm-50nm.
Optionally, point of polymer nano granules described in the polymer fluorescent nano grain and the dye stuff of rhodamine kinds
Subnumber ratio is 1:(1000-3000).
Optionally, the partial size of the polymer fluorescent nano grain is 20nm-100nm.
Second aspect, the present invention provides a kind of preparation method of polymer fluorescent nano grain as described in relation to the first aspect,
Include:
The solution containing the polymer nano granules, the solution containing the dye stuff of rhodamine kinds is respectively configured and is dredged containing described
The solution of water balance object simultaneously mixes to form mixed solution, and the polymer fluorescent nano is prepared through nanoprecipitation method
Grain.
Optionally, the concentration of the solution containing the polymer nano granules is 1mg/mL-5mg/mL.It is further optional
, the concentration of the solution containing the polymer nano granules is 1.2mg/mL-4.7mg/mL, 1.8mg/mL-4.1mg/mL
Or 2.0mg/mL-3.8mg/mL.
Specifically, can be, but not limited to be dissolved in acetonitrile solvent for the polymer nano granules obtain it is described containing described poly-
Close the solution of object nano particle.
In the present invention, the polymer nanocomposite can be controlled by the concentration of the polymer nano granules solution
The partial size of grain.
Optionally, the partial size of the polymer nano granules is 20nm-80nm.It is further alternative, the polymer nano
The partial size of rice grain is 20nm-70nm, 25nm-55nm or 30nm-50nm.
Optionally, the concentration of dye stuff of rhodamine kinds described in the mixed solution is the polymer nano granules concentration
10%-30%.Further alternative, the concentration of dye stuff of rhodamine kinds described in the mixed solution is the polymer nanocomposite
12%-27%, 15%-25% or 16%-22% of grain concentration.
In the present invention, polymer fluorescent nano can be controlled by the concentration of dye stuff of rhodamine kinds in the mixed solution
The molecular amounts of polymer nano granules and dye stuff of rhodamine kinds ratio in grain.
Optionally, point of polymer nano granules described in the polymer fluorescent nano grain and the dye stuff of rhodamine kinds
Subnumber ratio is 1:(1000-3000).
In the present invention, in the mixed solution hydrophobic balance object concentration according to the concentration of the dye stuff of rhodamine kinds into
Row selection, to guarantee the positive and negative charge balance of polymer fluorescent nano grain.
It is optionally, described that the polymer fluorescent nano grain is prepared through nanoprecipitation method, comprising:
It will be rapidly added in the mixed solution in the buffer of pH 7-8, the polymer fluorescent nano can be obtained
Grain, the volume of the buffer are 3-8 times of the mixed liquor volume.
It is optionally, described that the polymer fluorescent nano grain is prepared through nanoprecipitation method, comprising:
The mixed solution is added dropwise in aqueous solution, the polymer fluorescent nano grain can be obtained.
Optionally, the partial size of the polymer fluorescent nano grain is 20nm-100nm.
The third aspect, the present invention provides a kind of liquid crystal display device, the liquid crystal display device include diffusion sheet and partially
The material of at least one of mating plate, the diffusion sheet and the polaroid includes polymer fluorescent nano described in first aspect
Grain.
Optionally, when the diffusion sheet is single layer structure, the material of the diffusion sheet includes the polymer fluorescent nano
Grain.Specifically, can be, but not limited to be dispersed in acryl resin for the polymer fluorescent nano grain, coated formation
The diffusion sheet.It is further alternative, it further include scattering particles in the diffusion sheet, so that preferably being carried out when light source passes through scattered
It penetrates.Optionally, when the diffusion sheet is multilayered structure, at least one layer of material includes the polymer in the diffusion sheet
Fluorescence nano grain.
Optionally, the polaroid includes polymer fluorescent nano granulosa, the material of the polymer fluorescent nano granulosa
Including the polymer fluorescent nano grain.Specifically, can be, but not limited to, when the polaroid include removing protective film and according to
When the secondary adhesion coating being arranged on the removing protective film, the first protective layer, polarizing layer, the second protective layer and surface protection film,
The polymer fluorescent nano grain can be set between first protective layer and the polarizing layer, the polarizing layer and described
Between second protective layer or between second protective layer and the surface protection film, specifically, being selected according to actual needs
It selects.Optionally, the polymer fluorescent nano granulosa with a thickness of 500nm-1500nm.
Beneficial effects of the present invention: the present invention provides a kind of polymer fluorescent nano grains, are used for liquid crystal display device, packet
The dye stuff of rhodamine kinds and hydrophobic balance object for including polymer nano granules and being supported on the polymer nano granules, sieve
Red bright class dyestuff and the hydrophobic balance object are combined together by electrostatic attraction；The dye stuff of rhodamine kinds and described hydrophobic flat
Weighing apparatus object is supported on the inside and surface of the polymer nano granules, can reunite to avoid dye stuff of rhodamine kinds, improves and inhales
Rate of producing effects and fluorescence efficiency, hydrophobic balance object can guarantee the charge balance of polymer fluorescent nano grain；The polymer fluorescent is received
The preparation process of the grain of rice is simple, is suitble to industrialized production；Polymer fluorescent nano grain obtained can be absorbed yellow orange light and emit
Feux rouges reduces the interference of yellow orange light veiling glare, promotes colour gamut, while emitting feux rouges and guaranteeing that brightness is constant, in liquid crystal display device
It is with a wide range of applications.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.Specific embodiment described herein is only used to explain this
Invention, is not intended to limit the present invention.
Fig. 1 is a kind of LCD device structure schematic diagram that present invention implementation provides；
Fig. 2 is the structural schematic diagram that the present invention implements diffusion sheet in a kind of liquid crystal display device provided；
Fig. 3 is another liquid crystal display device result schematic diagram that present invention implementation provides；
Fig. 4 is the structural schematic diagram that the present invention implements polaroid in another liquid crystal display device provided, wherein in Fig. 4
(a) be the first polaroid structural schematic diagram, (b) is the structural schematic diagram of second of polaroid in Fig. 4, and (c) is the in Fig. 4
The structural schematic diagram of three kinds of polaroids, (d) is the structural schematic diagram of the 4th kind of polaroid in Fig. 4.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The present invention provides a kind of polymer fluorescent nano grain, including polymer nano granules and it is supported on the polymer
Dye stuff of rhodamine kinds and hydrophobic balance object on nano particle, the dye stuff of rhodamine kinds and the hydrophobic balance object pass through electrostatic
Gravitation is combined together, the hydrophobic balance object include perchlorate, tetraphenylboron sodium, four (4- fluorophenyl) boronation sodium hydrates and
At least one of trityl four (pentafluorophenyl group) borate.
In the present invention, the uv-visible absorption spectra of the dye stuff of rhodamine kinds and fluorescence emission spectrum can be seen that
Its absorption peak concentrates in yellow orange optical range, and emission peak is in red light region.Therefore, the Luo Dan on the polymer fluorescent nano grain
Bright class dyestuff can be absorbed yellow orange light (570nm-610nm) and launch feux rouges (610nm-700nm).
In the present invention, the dye stuff of rhodamine kinds can occur in the polymer surfaces to avoid dye stuff of rhodamine kinds
Reunite and fluorescent quenching is caused to influence fluorescence efficiency, be conducive to the dispersion of dye stuff of rhodamine kinds, improves absorption efficiency and fluorescence effect
Rate, and its stability is helped to improve, preferably in the preparation of film.
In the present invention, the polymer nano granules have three-dimensional netted space structure, are approximately spherical, the Luo Dan
It is combined together between bright class dyestuff and the hydrophobic balance object by electrostatic attraction and is located at the polymer nano granules
Inside reticular structure and surface, that is, be supported on the polymer nano granules, can reunite to avoid dye stuff of rhodamine kinds
And fluorescent quenching is caused to influence fluorescence efficiency, be conducive to the dispersion of dye stuff of rhodamine kinds, improve absorption efficiency and fluorescence efficiency, and
And its stability is helped to improve, preferably in the preparation of film.
In the present invention, the dye stuff of rhodamine kinds is basic dye, is that can dissociate generation cation in aqueous solution
Dyestuff, and hydrophobic balance object dissociates generate anion in aqueous solution, the rhodamine and the hydrophobic balance object pass through
Electrostatic attraction is combined together, and is supported on the polymer nano granules, so that polymer fluorescent nano grain is integrally positive and negative
Charge balance guarantees polymer fluorescent nano grain overall stability.
In embodiments of the present invention, the dye stuff of rhodamine kinds has the structure as shown in formula (I),
Wherein, R1、R2、R3、R4、R5、R6、R7Independently selected from C1-C25Alkyl, C1-C25Halogenated alkyl and C6-C25's
At least one of aromatic radical, the alkyl are straight chain or the chain-like alkyl with branch, and the halogenated alkyl is straight chain or band
There is the halogenated alkyl of branch.Optionally, the aromatic radical includes at least one of mono-cyclic aromatic base and multiring aromatic.It is optional
, the structure of the aromatic radical isWherein, R8Selected from C1-C25Alkyl, C1-C25Alkoxy
And C1-C25At least one of alkenyl；R9、R10、R11Independently selected from H, C1-C25Alkyl, C1-C25Ester group, C1-C25's
Alkoxy and C1-C25At least one of halogenated alkyl.Further alternative, the alkyl is straight chain or the chain with branch
Shape alkyl, the halogenated alkyl are straight chain or the halogenated alkyl with branch.Optionally, the structure of the aromatic radical isWherein, R12Selected from C1-C25Alkyl, C1-C25Alkoxy and C1-C25Alkenyl in
It is at least one；R13、R14、R15、R16Independently selected from H, C1-C25Alkyl, C1-C25Ester group, C1-C25Alkoxy and C1-C25
At least one of halogenated alkyl.Further alternative, the alkyl is straight chain or the chain-like alkyl with branch, the halogen
Substituted alkyl is straight chain or the halogenated alkyl with branch.
In embodiments of the present invention, the polymer includes poly lactide-glycolide acid, poly-methyl methacrylate
At least one of ester and polycaprolactone.
In embodiments of the present invention, the weight average molecular mass of the polymer nano granules is 10000-40000.
In embodiments of the present invention, the partial size of the polymer nano granules is 20nm-80nm.It is further alternative,
The partial size of the polymer nano granules is 20nm-70nm, 25nm-55nm or 30nm-50nm.
In embodiments of the present invention, polymer nano granules described in the polymer fluorescent nano grain and the Luo Dan
The molecular number ratio of bright class dyestuff is 1:(1000-3000).
In embodiments of the present invention, the partial size of the polymer fluorescent nano grain is 20nm-100nm.
Polymer fluorescent nano grain provided by the invention includes polymer nano granules and is supported on the polymer nanocomposite
Dye stuff of rhodamine kinds and hydrophobic balance object on particle, the dye stuff of rhodamine kinds and the hydrophobic balance object pass through electrostatic attraction
It is combined together；The dye stuff of rhodamine kinds and the hydrophobic balance object are supported on inside and the table of the polymer nano granules
Face can reunite to avoid dye stuff of rhodamine kinds, and improving absorption efficiency and fluorescence efficiency, hydrophobic balance object can guarantee to polymerize
The charge balance of object fluorescence nano grain；The polymer fluorescent nano grain can be absorbed yellow orange light and emit feux rouges, can be used for liquid
In crystal device, the interference of yellow orange light veiling glare is reduced, promotes colour gamut, while emitting feux rouges and guaranteeing that brightness is constant.
The present invention also provides the preparation methods of above-mentioned polymer fluorescent nano grain, comprising:
The solution containing the polymer nano granules, the solution containing the dye stuff of rhodamine kinds is respectively configured and is dredged containing described
The solution of water balance object simultaneously mixes to form mixed solution, and the polymer fluorescent nano is prepared through nanoprecipitation method
Grain.
In embodiments of the present invention, the concentration of the solution containing the polymer nano granules is 1mg/mL-5mg/
mL.It is further alternative, the concentration of the solution containing the polymer nano granules be 1.2mg/mL-4.7mg/mL,
1.8mg/mL-4.1mg/mL or 2.0mg/mL-3.8mg/mL.Specifically, can be, but not limited to as the polymer nano granules
It is dissolved in and obtains the solution containing the polymer nano granules in acetonitrile solvent.
In the present invention, the polymer nanocomposite can be controlled by the concentration of the polymer nano granules solution
The partial size of grain.Optionally, the partial size of the polymer nano granules is 20nm-80nm.It is further alternative, the polymer nano
The partial size of rice grain is 20nm-70nm, 25nm-55nm or 30nm-50nm.
In embodiments of the present invention, the concentration of dye stuff of rhodamine kinds is the polymer concentration in the composite solution
10%-30%.Further alternative, the concentration of dye stuff of rhodamine kinds is the polymer concentration in the composite solution
12%-27%, 15%-25% or 16%-22%.
In the present invention, polymer fluorescent nano can be controlled by the concentration of dye stuff of rhodamine kinds in the mixed solution
The molecular amounts of polymer nano granules and dye stuff of rhodamine kinds ratio in grain.Optionally, institute in the polymer fluorescent nano grain
The molecular number ratio for stating polymer nano granules and the dye stuff of rhodamine kinds is 1:(1000-3000).
In the present invention, in the mixed solution hydrophobic balance object concentration according to the concentration of the dye stuff of rhodamine kinds into
Row selection, to guarantee the positive and negative charge balance of polymer fluorescent nano grain.
It is in embodiments of the present invention, described that the polymer fluorescent nano grain is prepared through nanoprecipitation method, comprising:
It will be rapidly added in the mixed solution in the buffer of pH 7-8, the polymer fluorescent nano grain can be obtained, it is described slow
The volume of fliud flushing is 3-8 times of the mixed liquor volume.
It is in embodiments of the present invention, described that the polymer fluorescent nano grain is prepared through nanoprecipitation method, comprising:
The mixed solution is added dropwise in aqueous solution, the polymer fluorescent nano grain can be obtained.
In embodiments of the present invention, the partial size of the polymer fluorescent nano grain is 20nm-100nm.
The preparation process of polymer fluorescent nano grain provided by the invention is simple, is suitble to industrialized production.
The present invention also provides a kind of liquid crystal display device, the liquid crystal display device includes in diffusion sheet and polaroid
The material of at least one, the diffusion sheet and the polaroid includes above-mentioned polymer fluorescent nano grain.
A kind of liquid crystal display device is provided in embodiments of the present invention, specifically can be, but not limited to as straight-down negative
LCD, referring to Fig. 1, the directly-down type LCD includes reflecting plate 11, light source led 12, diffuser plate 13, diffusion sheet 14, brightness enhancement film
15, LCD panel 16 and outline border 17.Optionally, the diffusion sheet 14 is single layer structure, the material of the diffusion sheet 14
Matter includes above-mentioned polymer fluorescent nano grain.Specifically, can be, but not limited to uniformly divide for the polymer fluorescent nano grain
It is dispersed in acryl resin, it is coated to form the diffusion sheet 14.It optionally, further include scattering particles in the diffusion sheet 14,
So that being preferably scattered when light source passes through.Optionally, the diffusion sheet 14 is multilayered structure.Specifically, can with but it is unlimited
When being sandwich structure for the diffusion sheet 14, referring to Fig. 2, the diffusion sheet 14 includes upper layer 141,142 and of middle layer
Lower layer 143.The lower layer 143 attaches with the diffuser plate 13.Specifically, can be, but not limited to is described for the upper layer 141
Polymer fluorescent nano grain, scattering particles are evenly distributed on coated formation in acryl resin.Specifically, can be, but not limited to
Material for the middle layer 142 is macromolecule resin.Optionally, the macromolecule resin includes polyethylene terephthalate
At least one of ester, polyether ester, polystyrene and polycarbonate.Specifically, can be, but not limited to as the lower layer 143 be institute
It states polymer fluorescent nano grain and is evenly distributed on coated formation in acryl resin.Optionally, the lower layer 143 with a thickness of
100nm-300nm。
A kind of liquid crystal display device is provided in embodiments of the present invention, specifically can be, but not limited to as straight-down negative
LCD, referring to Fig. 3, the directly-down type LCD includes reflecting plate 21, light source led 22, diffuser plate 23, polaroid 24, liquid crystal display
Control panel 25 and outline border 26.Referring to Fig. 4, polaroid 24 includes removing protective film 241, adhesion coating 242, the first protective layer
243, polarizing layer 244, the second protective layer 245 and surface protection film 246 optionally receive polymer fluorescent provided by the invention
The grain of rice, which is dispersed in acryl resin and is coated with, forms transparent polymer fluorescent nano granulosa 247.Optionally, described poly-
Close object fluorescence nano granulosa 247 with a thickness of 500nm-1500nm.The polymer fluorescent nano granulosa 247 is added to polarisation
Become one layer of structure in polaroid 24 in piece 24.It please refers in Fig. 4 (a), can be, but not limited to receive for the polymer fluorescent
Grain of rice layer 247 is between the adhesion coating 242 and first protective layer 243.It please refers in Fig. 4 (b), can be, but not limited to
It is the polymer fluorescent nano granulosa 247 between first protective layer 243 and the polarizing layer 244.Please refer to Fig. 4
In (c), can be, but not limited to be located at for the polymer fluorescent nano granulosa 247 polarizing layer 244 and second protection
Between layer 245.It please refers in Fig. 4 (a), can be, but not limited to be located at described second for the polymer fluorescent nano granulosa 247
Between protective layer 245 and the surface protection film 246.
In the present invention, the light that the light source led in liquid crystal display device issues is described after the diffusion sheet or polaroid
Polymer fluorescent nano grain in diffusion sheet or polaroid can be absorbed yellow orange light and emit feux rouges, reduce the sending of veiling glare, together
Shi Tigao colour gamut and keep original brightness.Polymer fluorescent nano grain provided by the invention has in liquid crystal display device
Broad application prospect.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of polymer fluorescent nano grain is used for liquid crystal display device, which is characterized in that including polymer nano granules and bear
The dye stuff of rhodamine kinds and hydrophobic balance object being loaded on the polymer nano granules, the dye stuff of rhodamine kinds and described hydrophobic
Counterbalance is combined together by electrostatic attraction, and the hydrophobic balance object includes perchlorate, tetraphenylboron sodium, four (4- fluorophenyls)
At least one of boronation sodium hydrate and trityl four (pentafluorophenyl group) borate.
2. polymer fluorescent nano grain as described in claim 1, which is characterized in that the polymer nano granules include poly- cream
At least one of acid-co-glycolic acid, polymethyl methacrylate and polycaprolactone.
3. polymer fluorescent nano grain as described in claim 1, which is characterized in that the dye stuff of rhodamine kinds has such as formula
(I) structure shown in,
Wherein, R1、R2、R3、R4、R5、R6、R7Independently selected from C1-C25Alkyl, C1-C25Halogenated alkyl and C6-C25Fragrance
At least one of base, the alkyl are straight chain or the chain-like alkyl with branch, and the halogenated alkyl is for straight chain or with branch
The halogenated alkyl of chain.
4. polymer fluorescent nano grain as claimed in claim 3, which is characterized in that the structure of the aromatic radical isWherein, R8Selected from C1-C25Alkyl, C1-C25Alkoxy and C1-C25Alkenyl at least
It is a kind of；R9、R10、R11Independently selected from H, C1-C25Alkyl, C1-C25Ester group, C1-C25Alkoxy and C1-C25Alkyl halide
At least one of base.
5. polymer fluorescent nano grain as described in claim 1 again, which is characterized in that the polymer nano granules are divided equally
Protonatomic mass is 10000-40000.
6. polymer fluorescent nano grain as described in claim 1, which is characterized in that the partial size of the polymer fluorescent nano grain
For 20nm-100nm.
7. polymer fluorescent nano grain as described in claim 1, which is characterized in that described in the polymer fluorescent nano grain
The molecular number ratio of polymer nano granules and the dye stuff of rhodamine kinds is 1:(1000-3000).
8. a kind of preparation method of such as described in any item polymer fluorescent nano grains of claim 1-7, which is characterized in that packet
It includes:
The solution containing the polymer nano granules, the solution containing the dye stuff of rhodamine kinds is respectively configured and containing described hydrophobic flat
The solution of weighing apparatus object simultaneously mixes to form mixed solution, and the polymer fluorescent nano grain is prepared through nanoprecipitation method.
9. the preparation method of polymer fluorescent nano grain as claimed in claim 8, which is characterized in that described to contain the polymer
The concentration of the solution of nano particle is 1mg/mL-5mg/mL, and the concentration of dye stuff of rhodamine kinds described in the mixed solution is institute
State the 10%-30% of polymer nano granules concentration.
10. a kind of liquid crystal display device, which is characterized in that the liquid crystal display device include in diffusion sheet and polaroid at least
The material of one kind, the diffusion sheet and the polaroid includes the described in any item polymer fluorescent nano grains of claim 1-7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407970A (en) * | 2019-07-19 | 2019-11-05 | 深圳市华星光电技术有限公司 | Preparation method, pure color material and the liquid crystal display device of dye stuff of rhodamine kinds monomeric oligomeric conjunction object |
| CN111081749A (en) * | 2019-12-31 | 2020-04-28 | Tcl华星光电技术有限公司 | Display device and manufacturing method thereof |
| CN111077698A (en) * | 2019-12-17 | 2020-04-28 | Tcl华星光电技术有限公司 | Backlight module and liquid crystal display device |
-
2018
- 2018-07-25 CN CN201810826967.3A patent/CN109233803A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407970A (en) * | 2019-07-19 | 2019-11-05 | 深圳市华星光电技术有限公司 | Preparation method, pure color material and the liquid crystal display device of dye stuff of rhodamine kinds monomeric oligomeric conjunction object |
| WO2021012515A1 (en) * | 2019-07-19 | 2021-01-28 | Tcl华星光电技术有限公司 | Method for preparing rhodamine dye monomer low polymer, pure color material, and liquid crystal display device |
| CN111077698A (en) * | 2019-12-17 | 2020-04-28 | Tcl华星光电技术有限公司 | Backlight module and liquid crystal display device |
| CN111081749A (en) * | 2019-12-31 | 2020-04-28 | Tcl华星光电技术有限公司 | Display device and manufacturing method thereof |
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Address after: 9-2 Tangming Avenue, Guangming New District, Shenzhen City, Guangdong Province Applicant after: TCL China Star Optoelectronics Technology Co.,Ltd. Address before: 9-2 Tangming Avenue, Guangming New District, Shenzhen City, Guangdong Province Applicant before: Shenzhen China Star Optoelectronics Technology Co.,Ltd. |
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Application publication date: 20190118 |