CN102540608B - A kind of preparation method of flexible light modulation duplexer and flexible light modulation duplexer - Google Patents
A kind of preparation method of flexible light modulation duplexer and flexible light modulation duplexer Download PDFInfo
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- CN102540608B CN102540608B CN201010587229.1A CN201010587229A CN102540608B CN 102540608 B CN102540608 B CN 102540608B CN 201010587229 A CN201010587229 A CN 201010587229A CN 102540608 B CN102540608 B CN 102540608B
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Abstract
The invention provides a kind of preparation method of flexible light modulation duplexer and the obtained flexible light modulation duplexer of the method, recess is formed by being directly printed onto by etching paste on the first transparent electrode layer, coated polymeric dispersed LCD mixed liquor on the first transparent electrode layer that this is formed with recess again, through solidifying to form the polymer dispersed liquid crystal layer with ad hoc structure, obtain the flexible light modulation duplexer that can show special pattern.Preparation method of the present invention overcomes flexible light modulation duplexer because of size-constrained, can not adopt traditional LCD Graphic transitions, the defect of etch process, and can prepare simply, continuously can the flexible light modulation duplexer of display graphics.
Description
Technical field
The present invention relates to field of photoelectric technology, particularly, the preparation method relating to a kind of flexible light modulation duplexer and the flexible light modulation duplexer prepared by the method.
Background technology
Polymer Dispersed Liquid Crystal (Polymerdispersedliquidcrystals, PDLC) film is a kind of photoelectricity composite material, and liquid crystal droplet is dispersed in polymeric matrix, by extra electric field, PDLC film is changed to transparent by opaque.Polymer dispersed liquid crystal film slewing rate is fast, response time is generally Millisecond, more superior is the making that can realize large area light modulation film, and can be useful in the privacy places such as meeting room, bedroom, bathroom, polymer dispersed liquid crystal film also can be applied to display aspect in addition.
CN101017304A discloses a kind of flexible electrochromic thin film preparation method, the uniform mix of its surface in flexible conductive film coating one layer of polymeric performed polymer, nematic liquid crystal and light trigger, then in described potpourri surface coverage one deck flexible conductive film, between flexible conductive film, polymer dispersed liquid crystal layer is formed finally by ultraviolet light fast solidification.But, flexible electrochomeric films prepared by the method can only show transparent and milky white two states, the field needing display graphics can not be applied in, and because of size-constrained, traditional liquid crystal display (LiquidCrystalDisplay can not be adopted, LCD) Graphic transitions, etch process, and complex process, cannot continuous seepage.
Summary of the invention
The object of the invention is to solve the problem, provide a kind of simple to operate, can continuous production can the method for flexible light modulation duplexer of display graphics.
Another object of the present invention is also to provide a kind of flexible light modulation duplexer prepared by method of the present invention.
In order to realize above-mentioned first object, the invention provides a kind of preparation method of flexible light modulation duplexer, the method comprises:
(1) on the first flexible and transparent base material, form the first transparent electrode layer, the second flexible and transparent base material forms the second transparent electrode layer;
(2) recess is formed by directly printing etching paste etching on described first transparent electrode layer;
(3) coated polymeric dispersed LCD mixed liquor on the first transparent electrode layer after forming recess, makes described Polymer Dispersed Liquid Crystal mixed liquor be full of described recess and covers described first transparent electrode layer;
(4) the second transparent electrode layer formed on the second flexible and transparent base material is laminated to is coated with on the first transparent electrode layer of Polymer Dispersed Liquid Crystal mixed liquor, forming polymer dispersed liquid crystal layer by being solidificated between the first transparent electrode layer and the second transparent electrode layer.
In order to realize another object above-mentioned, present invention also offers the flexible light modulation duplexer that a kind of preparation method of the present invention obtains, this duplexer is sequentially laminated with the first flexible and transparent base material, the first transparent electrode layer, polymer dispersed liquid crystal layer, the second transparent electrode layer and the second flexible and transparent base material, wherein, described first transparent electrode layer and polymer dispersed liquid crystal layer are formed with mutually chimeric recess and protuberance respectively.
Pass through technique scheme, etching paste is directly printed onto on the first transparent electrode layer and forms recess, coated polymeric dispersed LCD mixed liquor on the first transparent electrode layer that this is formed with recess again, through solidifying to form the polymer dispersed liquid crystal layer with ad hoc structure, obtain the flexible light modulation duplexer that can show special pattern.Preparation method of the present invention overcomes flexible light modulation duplexer because of size-constrained, can not adopt traditional LCD Graphic transitions, the defect of etch process, and can prepare simply, continuously can the flexible light modulation duplexer of display graphics.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for instructions, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the process flow diagram of the embodiment representing preparation method of the present invention;
Fig. 2 is the structural representation of flexible light modulation duplexer of the present invention.
Description of reference numerals
1 with the first transparent electrode layer of the first flexible transparent substrate
2 gravure anilox roll
3 drying tunnels
4 with the second transparent electrode layer of the second flexible transparent substrate
5 rinse baths
6 nozzles
7 air knives
8 applicator rolls
9 composite rolls
10UV solidifies case
11 flexible light modulation duplexers
12 first flexible and transparent base materials
13 first transparent electrode layers
14 polymer dispersed liquid crystal layers
15 second transparent electrode layers
16 second flexible and transparent base materials
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to the preparation method of flexible light modulation duplexer of the present invention, the method comprises:
(1) on the first flexible and transparent base material, form the first transparent electrode layer, the second flexible and transparent base material forms the second transparent electrode layer;
(2) recess is formed by directly printing etching paste etching on described first transparent electrode layer;
(3) coated polymeric dispersed LCD mixed liquor on the first transparent electrode layer after forming recess, makes described Polymer Dispersed Liquid Crystal mixed liquor be full of described recess and covers described first transparent electrode layer;
(4) the second transparent electrode layer formed on the second flexible and transparent base material is laminated to is coated with on the first transparent electrode layer of Polymer Dispersed Liquid Crystal mixed liquor, forming polymer dispersed liquid crystal layer by being solidificated between the first transparent electrode layer and the second transparent electrode layer.
Preparation in accordance with the present invention, in step (1), first flexible and transparent base material being formed the first transparent electrode layer and/or on the second flexible and transparent base material, forms the second transparent electrode layer to adopt the various film build methods of this area routine to be formed, such as in step (1), described first transparent electrode layer and/or described second transparent electrode layer can be formed by least one in vacuum splashing and plating method, sputtering method, ion plating method and cladding process.
As long as the material of described first flexible and transparent base material and/or described second flexible and transparent base material can form film or the thin slice of flexible and transparent, just there is no particular limitation, it can be various resin material, as vibrin, acetate resins, polyethersulfone resin, polycarbonate resin, polyamide, polyimide resin, polyolefin resin, Corvic, polystyrene resin, polyvinyl alcohol resin, poly-allylat resin, polyphenylene sulfide, poly-inclined vinylidene chloride resin and (methyl) acryl resin etc.Wherein, at least one in vibrin, polycarbonate resin and polyolefin resin is preferably.There is no particular limitation for the thickness of described first flexible and transparent base material and/or described second flexible and transparent base material, and in the preferred case, the thickness of described first flexible and transparent base material and/or described second flexible and transparent base material can be 50-200 μm.
Described first transparent electrode layer and/or described second transparent electrode layer can be conventional in this area various conductive film layers, in the preferred case, described first transparent electrode layer and/or described second transparent electrode layer are preferably formed to tin indium oxide (ITO) conductive film layer, Al-Doped ZnO (AZO) conductive film layer or indium zinc oxide (IZO) conductive film layer, and the thickness of described first transparent electrode layer and/or described second transparent electrode layer can be 15-40nm.
Preparation in accordance with the present invention, forms recess by directly printing etching paste etching on described first transparent electrode layer.In the preferred case, the method for described printing etching paste is woodburytype.By intaglio printing, etching paste is printed onto on the first transparent electrode layer according to special pattern, etches, form the recess of special pattern.In the preferred case, by the etching paste be printed onto on the first transparent electrode layer is heating and curing the first transparent electrode layer etched.The condition of described etching can comprise: etch temperature is 60-120 DEG C, and etching period is 5-20min.Can be formed well on the first transparent electrode layer by adopting the mode of woodburytype printing etching paste and have the recess of special pattern, overcome traditional LCD Graphic transitions, etch process by the defect of flexible light modulation duplexer size restriction.Described etching paste for etching the various paste etchants of transparent electrode layer in this area, can be able to be commercially available, such as the HiperEtch09SType40 of MERCK company.
Preparation in accordance with the present invention, the method can also comprise after the etching, removed by etching paste before coated polymeric dispersed LCD mixed liquor.Particularly, the recess forming special pattern can be etched on the first transparent electrode layer after, by the etching paste cleaning removing after solidification, then by air-dry for the first transparent electrode layer after cleaning.
Preparation in accordance with the present invention, in step (3), by coated polymeric dispersed LCD mixed liquor on the first transparent electrode layer of the drying after forming recess, make described Polymer Dispersed Liquid Crystal mixed liquor be full of described recess and cover described first transparent electrode layer.The method of described coated polymeric dispersed LCD mixed liquor can be rolling method.The coating weight of described Polymer Dispersed Liquid Crystal mixed liquor can be selected in a big way, and in the preferred case, the coating thickness of described Polymer Dispersed Liquid Crystal mixed liquor is 10-30 μm.
Preparation in accordance with the present invention, described Polymer Dispersed Liquid Crystal mixed liquor can for the mixed liquor containing acrylic ester monomer, Photoepolymerizationinitiater initiater and nematic liquid crystal.In described Polymer Dispersed Liquid Crystal mixed liquor, the weight ratio of described acrylic ester monomer, Photoepolymerizationinitiater initiater and nematic liquid crystal can be selected in the larger context, in order to improve the display performance of flexible light modulation duplexer, the weight ratio of described acrylic ester monomer and nematic liquid crystal can be 0.3-1.5: 1, be preferably 0.5-1.2: 1, the content of Photoepolymerizationinitiater initiater can be 0.5-3 % by weight, is preferably 1-3 % by weight.
Described acrylic monomer can be at least one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, hydroxyethyl methylacrylate, propyl methacrylate, hydroxy propyl methacrylate, Diacrylate, propylene glycol diacrylate, 1,6-hexanediyl ester, Tetraethylene glycol diacrylate, tri (propylene glycol) diacrylate, bisphenol a diacrylate and trimethylolpropane triacrylate.
Described Photoepolymerizationinitiater initiater can be at least one in benzoin ethyl ether, benzoin isobutyl ether, 1-hydroxy-cyclohexyl-phenyl ketone, phenyl two (2,4,6-trimethylbenzoyl) phosphine oxide, trisbromomethyl phenyl sulfone and benzophenone.
Described nematic liquid crystal can be at least one in biphenyls liquid crystal, second alkyne type liquid crystal, dicyclic hexane liquid crystal, cyclohexylbenzene class and phenol ester liquid crystal.
Preparation in accordance with the present invention, being laminated to by the second transparent electrode layer formed on the second flexible and transparent base material in step (4) is coated with on the first transparent electrode layer of Polymer Dispersed Liquid Crystal mixed liquor, forms polymer dispersed liquid crystal layer by being solidificated between the first transparent electrode layer and the second transparent electrode layer.After on the first electrode layer, coated polymeric dispersed LCD mixed liquor forms Polymer Dispersed Liquid Crystal mixed liquor coating layer, the second transparent electrode layer formed on the second flexible and transparent base material is in advance layered in by extruding on Polymer Dispersed Liquid Crystal mixed liquor coating layer, then Polymer Dispersed Liquid Crystal mixed liquor is made to solidify to form polymer dispersed liquid crystal layer, the method of described solidification can be the curing of various routine in this area, as long as Polymer Dispersed Liquid Crystal mixed liquor can be made to solidify to form polymer dispersed liquid crystal layer, just there is no special restriction.In the preferred case, in order to improve the display effect of the polymer dispersed liquid crystal layer solidify to form, the method for described solidification is preferably ultraviolet curing method.The condition of described ultraviolet curing method comprises: uitraviolet intensity is 10-40mW/cm
2, set time is 1-5min.
As the preparation method of flexible light modulation duplexer of the present invention, below in conjunction with accompanying drawing 1, method of the present invention is further illustrated.
Fig. 1 is the process flow diagram of the embodiment representing preparation method of the present invention.As shown in Figure 1, the first transparent electrode layer 1 with the first flexible transparent substrate is unreeled, this first transparent electrode layer 1 prints etching paste through gravure anilox roll 2, then etching paste is made to solidify and etch the first transparent electrode layer 1 through drying tunnel 3, form recess, etching paste after the first nesa coating 1 after drying tunnel 3 utilizes the nozzle 6 cleaning showers liquid of cleaning device to wash solidification, waste liquid enters rinse bath 5, the first nesa coating 1 after cleaning is air-dry by air knife 7, the first nesa coating 1 after air-dry is by applicator roll 8 coated polymeric dispersed LCD mixed liquor, then be formed with the second nesa coating 4 of the second transparent electrode layer in the second flexible transparent substrate by composite roll 9 compound, solidifying case 10 by UV makes Polymer Dispersed Liquid Crystal mixed liquor curability form polymer dispersed liquid crystal layer, form flexible light modulation duplexer 11 thus.
In addition, present invention also offers the flexible light modulation duplexer that a kind of preparation method of the present invention obtains, this duplexer is sequentially laminated with the first flexible and transparent base material, the first transparent electrode layer, polymer dispersed liquid crystal layer, the second transparent electrode layer and the second flexible and transparent base material, wherein, described first transparent electrode layer and polymer dispersed liquid crystal layer are formed with mutually chimeric recess and protuberance respectively.Fig. 2 is the structural representation of flexible light modulation duplexer of the present invention, as shown in Figure 2, flexible light modulation duplexer is sequentially laminated with the first flexible and transparent base material 12, first transparent electrode layer 13, polymer dispersed liquid crystal layer 14, second transparent electrode layer 15 and the second flexible and transparent base material 16.
According to flexible light modulation duplexer of the present invention, be formed with mutually chimeric recess and protuberance respectively by the first transparent electrode layer and polymer dispersed liquid crystal layer, the performance of flexible light modulation duplexer display graphics can be realized.Described mutually chimeric recess and protuberance form recess by etching on the first transparent electrode layer and realize, described polymer dispersed liquid crystal layer is formed on the first transparent electrode layer of recess by being applied to by Polymer Dispersed Liquid Crystal mixed liquor, make described Polymer Dispersed Liquid Crystal mixed liquor be full of described recess and cover described first transparent electrode layer, then solidification can form the polymer dispersed liquid crystal layer being formed with the protuberance chimeric with described recess.
Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
By the following examples the present invention is further described.
Embodiment 1
The present embodiment is for illustration of the preparation method of flexible light modulation duplexer of the present invention and flexible light modulation duplexer.
The ITO electrode layer of the first flexible transparent conducting film (being that the ITO electrode layer that the polyester resin film of 18 μm sputters 35nm thick is made at thickness) use gravure anilox roll be the etching paste (HiperEtch09SType40 of 10 μm with linear velocity 2.5m/min print thickness, purchased from MERCK company), and be heat 5min in the drying tunnel of 80 DEG C to be cured etching in temperature, with the etching paste removing that pure water cleaning will the first conductive film after etching be solidified after solidification etching, and dry.Then by rolling method ITO electrode layer is after the drying coated with by 1,6-hexanediyl ester (HDDA), trimethylolpropane triacrylate (TMPTA), benzophenone and pentylbiphenyl cyanogen mix Polymer Dispersed Liquid Crystal mixed liquor with the ratio that weight ratio is 20: 32: 3: 45, and coating thickness is 20 μm.Then by the ITO electrode layer side of the second flexible transparent conducting film (being that the ITO electrode layer that the polyester resin film of 188 μm sputters 35nm thick is made at thickness) be coated with the first nesa coating side of Polymer Dispersed Liquid Crystal mixed liquor by pressure roller compound, and at light intensity 10mW/cm
2365nm UV-irradiation under solidify 2min, form flexible light modulation duplexer A1.
Embodiment 2
The present embodiment is for illustration of the preparation method of flexible light modulation duplexer of the present invention and flexible light modulation duplexer.
The ITO electrode layer of the first flexible transparent conducting film (being that the ITO electrode layer that the polystyrene resin film of 188 μm sputters 15nm thick is made at thickness) use gravure anilox roll be the etching paste (HiperEtch09SType40 of 10 μm with linear velocity 2.5m/min print thickness, purchased from MERCK company), and be heat 20min in the drying tunnel of 60 DEG C to be cured etching in temperature, with the etching paste removing that pure water cleaning will the first conductive film after etching be solidified after solidification etching, and dry.Then mix Polymer Dispersed Liquid Crystal mixed liquor by trimethylolpropane triacrylate (TMPTA), benzophenone and pentylbiphenyl cyanogen with the ratio that weight ratio is 59: 2: 39 by rolling method ITO electrode layer is after the drying coated with, coating thickness is 10 μm.Then by the ITO electrode layer side of the second flexible transparent conducting film (being that the ITO electrode layer that the polystyrene resin film of 18 μm sputters 15nm thick is made at thickness) be coated with the first nesa coating side of Polymer Dispersed Liquid Crystal mixed liquor by pressure roller compound, and at light intensity 20mW/cm
2365nm UV-irradiation under solidify 3min, form flexible light modulation duplexer A2.
Embodiment 3
The present embodiment is for illustration of the preparation method of flexible light modulation duplexer of the present invention and flexible light modulation duplexer.
The ITO electrode layer of the first flexible transparent conducting film (being that the ITO electrode layer that the polystyrene resin film of 188 μm sputters 35nm thick is made at thickness) use gravure anilox roll be the etching paste (HiperEtch09SType40 of 10 μm with linear velocity 2.5m/min print thickness, purchased from MERCK company), and be heat 10min in the drying tunnel of 120 DEG C to be cured etching in temperature, with the etching paste removing that pure water cleaning will the first conductive film after etching be solidified after solidification etching, and dry.Then mix Polymer Dispersed Liquid Crystal mixed liquor by propylene glycol diacrylate, benzophenone and pentylbiphenyl cyanogen with the ratio that weight ratio is 23: 2: 75 by rolling method ITO electrode layer is after the drying coated with, coating thickness is 30 μm.Then by the ITO electrode layer side of the second flexible transparent conducting film (being that the ITO electrode layer that the polyester resin film of 188 μm sputters 35nm thick is made at thickness) be coated with the first nesa coating side of Polymer Dispersed Liquid Crystal mixed liquor by pressure roller compound, and at light intensity 40mW/cm
2365nm UV-irradiation under solidify 3min, form flexible light modulation duplexer A3.
Claims (9)
1. a preparation method for flexible light modulation duplexer, the method comprises:
(1) etch by adopting woodburytype directly to print etching paste etching on the first transparent electrode layer with the first flexible and transparent base material, to form recess at the first transparent electrode layer, the thickness of described first transparent electrode layer is 15-40nm;
(2) coated polymeric dispersed LCD mixed liquor on the first transparent electrode layer after forming recess, makes described Polymer Dispersed Liquid Crystal mixed liquor be full of described recess and covers described first transparent electrode layer;
(3) being coated with on the first transparent electrode layer of Polymer Dispersed Liquid Crystal mixed liquor by being laminated at the second transparent electrode layer with the second flexible and transparent base material, forming polymer dispersed liquid crystal layer by being solidificated between the first transparent electrode layer and the second transparent electrode layer;
Wherein, the liquid crystal contained in described Polymer Dispersed Liquid Crystal mixed liquor is nematic liquid crystal.
2. preparation method according to claim 1, wherein, the condition of described etching comprises: etch temperature is 60-120 DEG C, and etching period is 5-20min.
3. preparation method according to claim 1, wherein, this preparation method also comprises after the etching, removed by etching paste before coated polymeric dispersed LCD mixed liquor.
4. preparation method according to claim 1, wherein, in step (2), the method for described coated polymeric dispersed LCD mixed liquor is rolling method.
5. the preparation method according to claim 1 or 4, wherein, described Polymer Dispersed Liquid Crystal mixed liquor is the mixed liquor containing acrylic ester monomer, Photoepolymerizationinitiater initiater and nematic liquid crystal.
6. preparation method according to claim 5, wherein, in described Polymer Dispersed Liquid Crystal mixed liquor, the weight ratio of described acrylic ester monomer and nematic liquid crystal is 0.3-1.5: 1, and the content of Photoepolymerizationinitiater initiater is 0.5-3 % by weight.
7. preparation method according to claim 6, wherein, described acrylic monomer is at least one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, hydroxyethyl methylacrylate, propyl methacrylate, hydroxy propyl methacrylate, Diacrylate, propylene glycol diacrylate, 1,6-hexanediyl ester, Tetraethylene glycol diacrylate, tri (propylene glycol) diacrylate, bisphenol a diacrylate and trimethylolpropane triacrylate; Described Photoepolymerizationinitiater initiater is at least one in benzoin ethyl ether, benzoin isobutyl ether, 1-hydroxy-cyclohexyl-phenyl ketone, phenyl two (2,4,6-trimethylbenzoyl) phosphine oxide, trisbromomethyl phenyl sulfone and benzophenone; Described nematic liquid crystal is at least one in biphenyls liquid crystal, second alkyne type liquid crystal, dicyclic hexane liquid crystal, cyclohexylbenzene class and phenol ester liquid crystal.
8. preparation method according to claim 1, wherein, described first flexible and transparent base material and/or the second flexible and transparent base material are formed by least one be selected from vibrin, acetate resins, polyethersulfone resin, polycarbonate resin, polyamide, polyimide resin, polyolefin resin, Corvic, polystyrene resin, polyvinyl alcohol resin, poly-allylat resin, polyphenylene sulfide, poly-inclined vinylidene chloride resin and (methyl) acryl resin.
9. the flexible light modulation duplexer that the preparation method in a claim 1-8 described in any one obtains, this duplexer is sequentially laminated with the first flexible and transparent base material, the first transparent electrode layer, polymer dispersed liquid crystal layer, the second transparent electrode layer and the second flexible and transparent base material, it is characterized in that, described first transparent electrode layer and polymer dispersed liquid crystal layer are formed with mutually chimeric recess and protuberance respectively.
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| CN106918940A (en) * | 2017-03-24 | 2017-07-04 | 中山大学 | A kind of preparation method of flexible and transparent light modulation film |
| CN110554529B (en) * | 2018-10-10 | 2022-08-16 | 邝永彪 | Light control laminate, processing method, and processing method for double-layer etching light control laminate |
| CN108949192A (en) * | 2018-10-18 | 2018-12-07 | 国安奇纬光电新材料有限公司 | A kind of polymer dispersed liquid crystals composition, polymer dispersed liquid crystal film and hollow glass |
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