CN110471205A - A kind of preparation method of the PDLC liquid crystal light modulation film of the transparent conductive film containing nano-silver thread - Google Patents

A kind of preparation method of the PDLC liquid crystal light modulation film of the transparent conductive film containing nano-silver thread Download PDF

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Publication number
CN110471205A
CN110471205A CN201910850112.9A CN201910850112A CN110471205A CN 110471205 A CN110471205 A CN 110471205A CN 201910850112 A CN201910850112 A CN 201910850112A CN 110471205 A CN110471205 A CN 110471205A
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nano
silver thread
thread layer
layer
light modulation
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林静
黄石娟
李国增
汤立文
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Zhuhai Xingye New Mstar Technology Ltd
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Zhuhai Xingye New Mstar Technology Ltd
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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
    • 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
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • 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
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • 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
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Dispersion Chemistry (AREA)
  • Geometry (AREA)
  • Liquid Crystal (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a kind of preparation methods of the PDLC liquid crystal light modulation film of transparent conductive film containing nano-silver thread.Product includes PET1 layers, the first nano-silver thread layer, PDLC layer, the second nano-silver thread layer and PET2 layers.It is characterized in that once etching through etching laser machining, identical etched line is formed simultaneously in the first nano-silver thread layer or the second nano-silver thread layer；It is formed simultaneously that a shape is identical, equal in magnitude and overlapped corresponding first nano-silver thread independent partitions and the second nano-silver thread layer independent partitions layer by layer with the second nano-silver thread layer layer by layer in the first nano-silver thread.By realizing the function of light modulation film display pattern and/or text to independent partitions and the electrode manipulation respectively arranged on the second nano-silver thread layer independent partitions layer by layer of the first nano-silver thread.It is tediously long that technical solution of the present invention overcomes prior art processes, operating difficulties, the low disadvantage of yield rate；The operability of product is improved, while simplifying electrode control system, improve product pattern and text shows ability.

Description

A kind of preparation method of the PDLC liquid crystal light modulation film of the transparent conductive film containing nano-silver thread
Technical field
The present invention relates to laser ablation fields, and in particular to a kind of PDLC liquid crystal light modulation of the transparent conductive film containing nano-silver thread The preparation method of film.
Background technique
PDLC liquid crystal light modulation film (Polymer Dispersed Liquid Crystal) refers to the liquid crystal by American invention Polymer technology (PDLC) and make optical thin film.This technology mainly applies nematic state liquid crystal and Molecularly Imprinted Polymer is mixed After conjunction, by the ordered state of electric field controls liquid crystal, change liquid-crystal refractive-index, and the macrostate of light transmission and astigmatism is presented Switching.
In the prior art, the preparation of PDLC liquid crystal light modulation film generally includes, and prepares ITO coating on a pet film, produces soft The PET-ITO film of property electrically conducting transparent, and the even spread one layer of polymeric dispersed LCD between two layers of PET-ITO film (PDLC), through light or heat cure, PDLC light modulation film is made.
When PDLC liquid crystal light modulation film is powered (ON state), ordered liquid crystal molecule is arranged under electric field action, molecule aggregation Object and liquid crystal material refractive index reach unanimity, and substantially inhibit light scattering, and colorless and transparent state is presented in PDLC liquid crystal light modulation film；When When PDLC liquid crystal light modulation film powers off (OFF state), liquid crystal molecule disordered orientation, Molecularly Imprinted Polymer and liquid crystal material refractive index are lost Match, PDLC liquid crystal light modulation film generates strong light scattering, and appearance is creamy white or colored or black, is rendered as opaque.
PDLC liquid crystal light modulation film is in the shipment of light modulation film producer, such as the industrial new material Science and Technology Ltd. in Zhuhai, generally For shipment is wrapped, every volume 50-100 meters are differed, and 1000 meters of longest；1.2 meters to 2.0 meters of breadth are differed.Light modulation film client in use, The light modulation film of web-like supplied materials is cut into certain size, does top electrode, is attached on glass or doubling is into layer glass, is powered real The existing transparent and opaque switching of full wafer.But this be unable to satisfy in actual use it is partially transparent in a piece of light modulation film of customer requirement or Opaque and display pattern requirement.
Nano-silver thread (SNW, silver nano wire) technology, is that nano-silver thread ink material is applied to PET base material Or on glass substrate, Laser lithography is then utilized, portrays and is made with the saturating of Nano grade silver wire conductive network pattern Bright conductive film.Physical mechanism is made since its is special, the diameter of the line width of nano-silver thread is very small, about 50nm, far It can be applied on the display screen of various sizes less than 1um because of the problem of Mo Rui interference may be not present.In addition, due to line width Smaller, conductive film made of silver wire technology can achieve higher light transmittance compared to film made of metal grill technology, Such as 3M company can achieve 89% light transmittance using film product made of micro- coining method.Again, nano-silver thread film is compared There is lesser bending radius in metal grill film, and resistance change rate is smaller in bending, applies with curved-surface display Equipment, such as smartwatch is more advantageous when bracelet etc. is upper.
Currently, having there is a large amount of research to have shown that silver nanowires can be used for preparing touch screen, bending Organic Light Emitting Diode (OLED), performance is still in wearable electronic, electronic skin and the bending transparent electrodes such as solar battery, after bending 1000 times It is so very stable.In addition, nano-silver thread just possess raw material sources it is extensive, it is cheap, possess excellent crisp toughness, be suitble to big rule Mould industrialized production.In conclusion nano-silver thread is the ITO substitute that only one has practical application prospect, become flexible The leading role of screen.
In addition, star's product iWatch that Apple Inc. attracts everybody to pay close attention to will use receiving for TPK company according to media report Rice silver wire thin film technique, it was demonstrated that nano-silver thread product has the stability of apparent technical advantage and industrial chain really.
In the prior art, there are many patent document about the preparation of nano-silver thread, as application No. is 201510507980.9 patent name is " preparation method of nano-silver thread "；201510223402.2 patent name of application number is " a kind of nano-silver thread dispersion liquid for being used to prepare conductive film ".But the patent about nano-silver thread transparent conductive film industrialization It is considerably less, especially a kind of industrialized method for the nano-silver thread transparent conductive film that the yields that can produce high quality is high. It is " a kind of production method of nano-silver thread transparent conductive film " application No. is 201410229462.0 patent names.From this application Technical solution can be seen that above nano-silver thread coating be equipped with one layer can be with the protection gel coating of stiffened, the nanometer produced Silver wire transparent conductive film either in process of production, in wrapup procedure, is all held very much during cutting and in use process It easily causes electrically conducting transparent film to be scratched and apparent disadvantage occurs, or even the nano-silver thread in figure layer is drawn and is broken, influence user's It uses；And its nano-silver thread electrically conducting transparent film resistivity produced is to reduce electrically conducting transparent greater than 50ohm/sq The scope of application of film.
Meanwhile this method makes light modulation film, though be able to achieve in a piece of light modulation film can it is partially transparent or opaque and Pattern displaying control, but complex manufacturing technology, equipment investment are big, at high cost, constrain the use and product design of product.
Summary of the invention
In order to overcome the defects of the prior art and improved technology, the present invention provide a kind of transparent conductive film containing nano-silver thread PDLC liquid crystal light modulation film preparation method.
Purpose to realize the present invention, the present invention provides the following technical solutions:
Technical solution disclosed by the invention is specifically related to a kind of PDLC liquid crystal light modulation containing nano-silver thread transparent conductive film The preparation method of film.With the preparation method, the PDLC liquid crystal light modulation film product being prepared, with the preparation method It for Product Level is placed, is described by the way of from top to bottom, comprising: PET1 layers, the first nano-silver thread layer, PDLC layer, the Two nano-silver thread layers and PET2 layers.In other words, described PET1 layers is that top layer, the first nano-silver thread layer and PET1 layers are adjacent；Institute Stating PET2 layers is that bottom, the second nano-silver thread layer and PET2 layers are adjacent；Middle layer is PDLC layer, PDLC layer respectively with first nanometer Silver wire layer and the second nano-silver thread layer are adjacent.
Meanwhile there is etched line on the first nano-silver thread layer and the second nano-silver thread layer.The PDLC liquid crystal light modulation Film is once etched through etching laser machining, is respectively formed etched line in the first nano-silver thread layer and the second nano-silver thread layer, institute Etched line is stated to be formed simultaneously, and shape is identical, equal length and in up and down overlapping corresponding relationship.First nano-silver thread Layer and the second nano-silver thread layer, through laser ablation, the etched line that is formed simultaneously is by the first nano-silver thread layer and the second nano-silver thread Layer is divided into mutually independent region, is referred to as the first nano-silver thread layer independent partitions or the second nano-silver thread layer independently divides Area.
Wherein, the first nano-silver thread layer independent partitions or the second nano-silver thread layer independent partitions are characterized in, in institute It states around the first nano-silver thread layer independent partitions or the second nano-silver thread layer independent partitions by etched line and the first nano-silver thread layer Edge line or the edge line of the second nano-silver thread layer surround, form an independent region；In the first nano-silver thread layer The second nano-silver thread layer in the first nano-silver thread layer or the second nano-silver thread layer independent partitions region in the region of independent partitions It is linked to be electrically conductive one respectively；And two adjacent the first nano-silver thread layer independent partitions or adjacent two second nanometer Silver wire layer independent partitions, due to being etched, line separates completely, mutually non-conductive, in other words its mutually insulated.
The first nano-silver thread layer or the second nano-silver thread layer marked off by etched line each mutually independent first Nano-silver thread layer independent partitions or the second nano-silver thread layer independent partitions, wherein each first nano-silver thread layer independent partitions or It is respectively arranged with an electrode on two nano-silver thread layer independent partitions, the electrode is positioned close to the edge of the light modulation film, Lead-out wire is connected on the electrode.
Wherein, the etched line can be straight-line segment, curved segments, broken line line segment, closed curve, closure fold line or It is their combination.The etched line of the closed curve or closure fold line is referred to as closure etched line.
Wherein, the PDLC liquid crystal light modulation film is once etched through etching laser machining, in the first nano-silver thread layer or Two nano-silver thread layers are formed simultaneously identical etched line.That is, by etching once or twice, in the first nano silver Line layer and the second nano-silver thread layer are formed simultaneously that shape is identical, equal in magnitude and to be overlapped corresponding first nano-silver thread layer up and down only Vertical subregion and the second nano-silver thread layer independent partitions；Meanwhile the shape it is identical, it is equal in magnitude and it is upper and lower overlapping corresponding first One electrode of each setting is distinguished in nano-silver thread layer independent partitions and the second nano-silver thread layer independent partitions, and partner electrode；It is logical The voltage for controlling this to electrode is crossed, manipulates that the shape is identical, the equal in magnitude and corresponding first nano-silver thread layer of upper and lower overlapping Independent partitions and the second nano-silver thread layer independent partitions, achieve the purpose that the optical characteristics for manipulating the PDLC liquid crystal light modulation film.
Further, when the PDLC liquid crystal light modulation film is once etched through etching laser machining, the etched line of formation is that closure is carved When corrosion line, closure etched line ending is connected, and beginning and end is overlapped.Thus the first nano-silver thread layer that primary etching is formed is only Vertical subregion is identical with the second nano-silver thread layer independent partitions shape, equal in magnitude and overlapping correspondence up and down.For this feelings Shape, the first nano-silver thread layer independent partitions and the second nano-silver thread layer independent partitions for etching formation are not provided with electrode, pattern Or text, it is shown by the control of the one pair of electrodes background area for the background area being arranged in except pattern or text.
Preferably, the electrode being arranged on the first nano-silver thread layer or the electrode arrangement being arranged on the second nano-silver thread layer In the ipsilateral of the PDLC liquid crystal light modulation film；The ipsilateral left side for referring to the PDLC liquid crystal light modulation film, right side, upside or Downside.It is to make common electrode for convenience that electrode, which is arranged so,；That is, several adjacent electrodes are linked up, it is made one jointly Electrode.
In the inventive solutions, the preparation of the PDLC liquid crystal light modulation film containing nano-silver thread transparent conductive film Method the following steps are included:
Step 1: substrate prepares: the substrate of selection is PET sheet base, and ready PET sheet base is carried out cure process；
Step 2: the configured coating nano-silver thread coating fluid of coating and protective glue coating fluid: by configured nano silver Line coating fluid and protective glue coating fluid pass through coating apparatus respectively and are applied on PET sheet base；Coated PET sheet base is done It is dry；
Step 3: the PET sheet base that two panels is coated with through nano-silver thread coating fluid is mounted on the dedicated painting of PDLC liquid crystal light modulation film It on cloth machine, is coated, solidified using configured PDLC composition, prepare PDLC liquid crystal light modulation film；
Step 4: laser ablation is carried out to PDLC liquid crystal light modulation film prepared by step 3 using etching laser machining, described PDLC liquid crystal light modulation film etches etched line, and the etched line depth, which is subject to, cuts off nano-silver thread layer；
Step 5: the first nano-silver thread layer independent partitions or each each of on PDLC liquid crystal light modulation film after etching Two nano-silver thread layer independent partitions, prepare an electrode respectively.
Wherein, the preparation method of the PDLC liquid crystal light modulation film of above-mentioned nano-silver thread transparent conductive film is hardened in step 1 Processing is coated with using dimple, slit-aperture type extrusion coated, carries out single side or double spread hardening bath to PET sheet base, is carried out hard Change processing.
Wherein, by weight percentage, above-mentioned hardening bath at being grouped as: pure acrylic resin 2.5%-7%, ten officials Polyurethane resin 7.5-18%, two functional polyurethane resin 16-26%, reactive diluent 5-10%, photoinitiator 1- can be rolled into a ball 4% and solvent 45%-55%.
The group of the reactive diluent becomes lauric acid acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol dipropyl What one or more of olefin(e) acid ester, 1,6- hexanediyl ester and 2- hydroxyethyl methacrylate phosphate were formed Composition.
The group of the photoinitiator becomes methyl benzoylformate, phenyl bis- (2,4,6- trimethylbenzoyls) aoxidizes The group that one or more of phosphine, 1- hydroxy-cyclohexyl-phenyl ketone and 2- hydroxy-2-methyl -1- phenyl -1- acetone are formed Close object.
The solvent is one or more of butanone, ethylene glycol, acetone, methyl ether.
Further, the preparation method of the PDLC liquid crystal light modulation film of above-mentioned nano-silver thread transparent conductive film, in step 1, PET sheet base non-nano silver wire coated face need to be coated with hardening coat, make its hardness in 1H or more, light transmittance is relative to non-hardened place The PET sheet base of reason increases 0.5-3%, and mist degree reduces 0.2-0.8%, light transmittance relative to the PET sheet base of non-hardened processing 90%~93%, mist degree≤0.7%, PET sheet base with a thickness of 25~200 μm, 150~200 DEG C of Yu Wendu, pressure are under 5MPa Hot pressing 20~40 seconds, surface was flawless.
Further, the preparation method of the PDLC liquid crystal light modulation film of above-mentioned nano-silver thread transparent conductive film, in step 2, institute State nano-silver thread coating fluid configuration method: by diameter be 10~100nm, the nano-silver thread of length≤200 μm is dissolved in solid and contains Amount is 0.5~10wt%, average grain diameter is in the colloidal sol of 10~100nm, so that containing silver 1 in every 1Kg nano-silver thread coating fluid ~10g；Solid content is 0.5~11wt% in nano-silver thread coating fluid, and viscosity is 1~25cps, nano-silver thread coating coating weight For 10~50mL/m2。
According to the preparation method of the PDLC liquid crystal light modulation film of above-mentioned nano-silver thread transparent conductive film, in step 2, the guarantor Shield glue coating fluid is metal oxide sol, and the pH of metal oxide sol is 3~6, and solid content is 0.1~10wt%, protection Gel coating coating weight is 10~50mL/m2。
According to the preparation method of the PDLC liquid crystal light modulation film of above-mentioned nano-silver thread transparent conductive film, in step 2, the painting The coating method of cloth is that extrusion coated is flowed on slope, by the primary double-deck extrusion coated technology, disposably by nano-silver thread coating fluid with Protective glue coating fluid is applied on PET sheet base.
According to the preparation method of the PDLC liquid crystal light modulation film of above-mentioned nano-silver thread transparent conductive film, in step 2, the painting The coating method of cloth is micro gravure coating, roller coating, slit type extrusion coated or blade coating, but is once merely able to coating one Layer.
It is described in step 2 according to the preparation method of the PDLC liquid crystal light modulation film of the above-mentioned transparent conductive film containing nano-silver thread At 20 DEG C or more, drying time is greater than 4 minutes drying temperature in drying process.
According to the preparation method of the PDLC liquid crystal light modulation film of the above-mentioned transparent conductive film containing nano-silver thread, in step 2, preparation The PET sheet base being coated with through nano-silver thread coating fluid and protective glue coating fluid: light transmittance is 75~92%, mist degree≤3%, surface Resistivity is 10~300ohm/sq, 3~5H of hardness, is tested 20~30 seconds through 150~200 DEG C of binding item heating bindings, surface electricity Resistance rate is no longer changed.
Further, the coating speed of the step 3 is set as 10-50mm/s, and it is 0.5mW/cm2 that UV, which solidifies power regulation, ~10mW/cm2；It is preferred that coating speed 25-45mm/s, it is 3mW/cm2~8.5mW/cm2 that UV, which solidifies power,.
In the preparation method of the PDLC liquid crystal light modulation film of the above-mentioned transparent conductive film containing nano-silver thread, the electrode, setting exists In the region of each first nano-silver thread layer independent partitions or the second nano-silver thread layer independent partitions, close to the PDLC liquid crystal tune The edge of light film, electrode are positioned close to light modulation film edge, are to be routed for the ease of connection lead-out wire and convenient for lead-out wire, together When, it is also convenient for covering electrode and lead-out wire using frame, increases aesthetics and the safety of product.
In addition, technical solution of the present invention, can also directly use saturating from manufacturer or commercially available nano-silver thread The PDLC liquid crystal light modulation film of bright conductive film, through the above steps four and step 5, complete the preparation method.
As needed, in order to obtain the display effect of ideal pattern or text, etched line first can be drawn as CAD Figure, and necessary fillet processing is carried out to figure peak portion, make adjacent etched line line segment rounding off.In addition, advising simultaneously Pull the position of electrode.If figure or text that etched line is constituted do not need power control, electrode can be put aside Position.
The present invention is using laser ablation equipment directly to step 1 to three preparations the or direct nanometer obtained from market The PDLC liquid crystal light modulation film of silver wire transparent conductive film carries out laser ablation, according to the pattern and/or text of the product being pre-designed Bandwagon effect prepares the PDLC liquid crystal light modulation film of pattern and/or text.
In technical solution disclosed by the invention, by the setting and control to etching laser machining, laser ablation each time Operation, the first nano-silver thread layer and the second nano-silver thread layer can be held in the same time, in the first nano-silver thread layer and the second nano-silver thread Layer is formed simultaneously identical etched line；So the etched line, for example, straight-line segment, curved segments, broken line line segment, Closed curve and/or closure fold line are once etched through laser, what the first nano-silver thread layer and the second nano-silver thread layer needed to etch Part can be held in the same time.To guarantee that pattern for preparing through laser ablation and/or text etc. can connect driving power, first nanometer Each independent first nano-silver thread layer independent partitions on silver wire layer or the second nano-silver thread layer or each independent Two nano-silver thread layer independent partitions are required close to light modulation film edge setting electrode；Further, every a pair is through a laser incising Erosion is formed simultaneously, and shape is identical, equal in magnitude and be overlapped corresponding first nano-silver thread layer independent partitions up and down and receive with second Rice silver wire layer independent partitions, the electrode being disposed thereon partner electrode；By connecting power controling machine structure, this is controlled to electricity The voltage of pole, manipulates that the shape is identical, the equal in magnitude and corresponding first nano-silver thread layer independent partitions of upper and lower overlapping and the The optical characteristics of two nano-silver thread layer independent partitions reaches the optical characteristics for manipulating the PDLC liquid crystal light modulation film, and manipulates it On pattern and text display and the purpose that conceals.
In the present invention, the PDLC liquid crystal light modulation film, PET1 layers or PET2 layers with a thickness of 20-300 μm；It is preferred that PET1 layers or PET2 layers with a thickness of 40-275 μm；More preferably PET1 layers or PET2 layers with a thickness of 90-220 μm.The PDLC Liquid crystal light modulation film, the first nano-silver thread layer or the second nano-silver thread layer with a thickness of 50-150nm；It is preferred that the first nano-silver thread Layer or the second nano-silver thread layer with a thickness of 60-120nm；The most preferably thickness of the first nano-silver thread layer or the second nano-silver thread layer For 90-110nm.The PDLC liquid crystal light modulation film, PDLC layer with a thickness of 5-200 μm；It is preferred that PDLC layer with a thickness of 8-120 μm；More preferable PDLC layer with a thickness of 30-100 μm；Most preferably PDLC layer with a thickness of 55-85 μm.The PDLC liquid crystal light modulation Film, etching line width are 3-100 μm；It is preferred that etching line width is 5-80 μm；More preferably etching line width is 10-60 μm；Most It is preferred that etching line width is 40-50 μm.
In technical solutions according to the invention, between the pattern, between pattern and text, between text and text, pattern or text Between word and electrode, connected by narrow nano-silver thread layer, referred to as nano-silver thread layer bonding pad.For example, in the first nano-silver thread layer Or the second nano-silver thread layer, through etching laser machining multiple etching, in some regions, for conductive purpose, two etched lines it Between, can design to form narrow nano-silver thread layer region so that between pattern, between pattern and text, between text and text, pattern or Conduction is connected between text and electrode, these nano-silver thread layer narrow zones are referred to as nano-silver thread layer bonding pad.In the present invention In, the PDLC liquid crystal light modulation film, nano-silver thread layer bonding pad minimum widith >=50 μm；It is preferred that etching line width is 65-100 μm；More preferably etching line width is 80-90 μm.The nano-silver thread layer connects sector width, according to pattern area and driving power Voltage and change, for whole beauty, the nano-silver thread layer connection sector width is commonly designed as small as possible.
In technical solutions according to the invention, the etching laser machining used is mounted on marble substrate, using vacuum The mode of absorption makes the PDLC liquid crystal light modulation film is smooth to be fixed on the workbench that vacuum pore is distributed with；The solid of use/ Optical fiber laser may be selected one of tri- kinds of 1064nm, 532nm or 355nm, 20 μm ± 5 μm of line width；It is adjustable to etch power 5-30W； Laser head is moved horizontally relative to etching object in the direction XY, maximum horizontal movement speed 600mm/S, and maximum translational acceleration is 1G；Specific etching operation setting are as follows: laser facula fixed-focus is on the first nano-silver thread layer or the second nano-silver thread layer, apart from equipment 50-220 μm of basic point vertical range；Etching speed 1000-4000mm/s, frequency 20-300KHZ, pulse width 5-50ns are stippled Lose time 0.01-0.2ms.It is preferred that laser head maximum horizontal movement speed 550mm/S, maximum translational acceleration is 0.8G；Laser Hot spot fixed-focus is on the first nano-silver thread layer or the second nano-silver thread layer, apart from 80-200 μm of vertical range of equipment basic point；Etching Speed 1500-3800mm/s, frequency 50-280KHZ, pulse width 8-45ns put etch period 0.03-0.18ms.More preferably swash Bare headed horizontal movement velocity 500mm/S, maximum translational acceleration are 0.65G；Laser facula fixed-focus in the first nano-silver thread layer or On second nano-silver thread layer, apart from 100-180 μm of vertical range of equipment basic point；Etching speed 1800-3500mm/s, frequency 80- 250KHZ, pulse width 10-40ns put etch period 0.05-0.15ms.
Using above-mentioned laser ablation equipment, the etching product of preparation, etched line lines are uniform, equidirectional line width difference≤3 μ m；Lines lateral erosion is unilateral≤and 3 μm；Impulse- free robustness, without wave, non-notch chipping；It is received in PDLC layer and the first nano-silver thread layer and second Rice silver wire layer cohesive force will not all generate burst point under normal circumstances, when even if etching is compared with big corner or spiked profiles, and cohesive force is got over Greatly, effect is better.
In addition, laser source can also use pulsewidth for picosecond laser, frequency 100kHz to 1000kHz is this super Short pulse width is enough to carry out " cold " ablation to material.Therefore, femto-second laser effect is more preferable.
Preferably, for a piece of PDLC liquid crystal light modulation film for having completed laser ablation, it is arranged in the first nano-silver thread layer On electrode, be longitudinally arranged the electrode that the second nano-silver thread layer is set in light modulation film left side edge, be longitudinally arranged in light modulation film Right side edge；It is furthermore preferred that ipsilateral and adjacent multiple electrodes, which are arranged in, is fabricated to a common electrode.
In the technical solution of the present invention, independently divide with each first nano-silver thread layer independent partitions and the second nano-silver thread layer The electrode of area's connection, production method, comprising the following steps:
S1: it on the PDLC liquid crystal light modulation film by a piece of transparent conductive film containing nano-silver thread of laser ablation, first determines The position of one the first nano-silver thread layer independent partitions top electrode setting, it is 8mm's that width is then cut at the position of electrode PET2 layers and the second nano-silver thread layer, expose the first following nano-silver thread layer；
S2: 99.99% ethanol solution is used, the residue of the PDLC composition remained on the first nano-silver thread layer is cleaned Afterwards, silver paste is coated on the first nano-silver thread layer using the method for screen printing, then uses air-heater, the silver after drying coating Slurry；
S3: the copper foil of width 5mm is attached to the silver paste surface being oven-dried；
S4: determining the position of second the first nano-silver thread layer independent partitions top electrode setting again, repeats above step；Directly To the production for completing all corresponding electrodes in the first nano-silver thread layer independent partitions；
S5: lead-out wire is welded in the copper foil surface made above；Alternatively, can be received following second in order to easy to operate After the completion of the electrode fabrication of rice silver wire layer, it is unified in all copper foil surface welding lead-out wires；
S6: the position of the electrode of the setting of upper the independent partitions of the second nano-silver thread layer is determined, then in the position of electrode The place of setting cuts the PET1 layer and the first nano-silver thread layer that width is 8mm, exposes the second following nano-silver thread layer；
S7: 99.99% ethanol solution is used, the residue of the PDLC composition remained on the second nano-silver thread layer is cleaned Afterwards, silver paste is coated on the second nano-silver thread layer using the method for screen printing, then uses air-heater, the silver after drying coating Slurry；
S8: the copper foil of width 5mm is attached to the silver paste surface being oven-dried；
S9: the position of second the second nano-silver thread layer independent partitions top electrode setting, repetitive operation, until complete are determined again At the production of all corresponding electrodes in the second nano-silver thread layer independent partitions；
S10: lead-out wire is welded in the copper foil surface made above.
Preferably, a piece of PDLC liquid crystal light modulation film through laser ablation, is arranged in all electricity on the first nano-silver thread layer Pole is arranged on the left of light modulation film, and close to film edge, and part adjacent electrode or whole electrodes are connected a common electrode are made； The electrode of second nano-silver thread layer film setting, is arranged on the right side of light modulation film.
Technical solution of the present invention further includes by the PDLC liquid crystal of the transparent conductive film containing nano-silver thread of above method preparation Light modulation film.The PDLC liquid crystal light modulation film of the transparent conductive film containing nano-silver thread includes PET1 layers, the first nano-silver thread layer, PDLC layer, the second nano-silver thread layer and PET2 layers.
Wherein, there are etched line, the PDLC liquid crystal light modulation film on the first nano-silver thread layer or the second nano-silver thread layer It is once etched through etching laser machining, is formed simultaneously identical quarter in the first nano-silver thread layer or the second nano-silver thread layer Corrosion line.The first nano-silver thread layer or the second nano-silver thread layer is divided into mutually independent region, referred to as through laser ablation First nano-silver thread layer independent partitions and the second nano-silver thread layer independent partitions.
Further, in the first nano-silver thread layer or the second nano-silver thread layer, the first nano-silver thread layer independently divides Area or the second nano-silver thread floor independent partitions are the etched line and the first nano-silver thread floor edge by being located at the first nano-silver thread floor Or etched line positioned at the second nano-silver thread layer and the second nano-silver thread layer edge surround, and form an independent region；Institute It states in the first nano-silver thread layer independent partitions or the second nano-silver thread layer independent partitions region, the first nano-silver thread layer or second receives Rice silver wire layer is linked to be conductive one；And two adjacent the first nano-silver thread layer independent partitions or adjacent two second nanometer Silver wire layer independent partitions, due to being etched, line separates completely, mutually non-conductive, in other words its mutually insulated.Described first receives Each mutually independent first nano-silver thread that rice silver wire layer or the second nano-silver thread layer are marked off by etched line disposed thereon Layer independent partitions or the second nano-silver thread layer independent partitions, are respectively arranged with an electrode, the electrode is positioned close to thereon The edge of the light modulation film is connected with lead-out wire on the electrode.
Wherein, it is once etched, forms identical quarter in the first nano-silver thread layer and the second nano-silver thread layer Corrosion line；That is, in the first nano-silver thread layer and the second nano-silver thread layer, being formed simultaneously one by etching once or twice A shape is identical and the first nano-silver thread layer independent partitions equal in magnitude and the second nano-silver thread layer independent partitions.
It is preferred that the electrode being arranged on the first nano-silver thread layer or the electrode arrangement being arranged on the second nano-silver thread layer exist The PDLC liquid crystal light modulation film it is ipsilateral；The ipsilateral left side for referring to the PDLC liquid crystal light modulation film, right side, upside or under Side.
It is further preferred that linking up ipsilateral several electrodes are arranged in, a common electrode is made.
The invention has the following advantages over the prior art:
1, technical solution of the present invention, it is tediously long to overcome prior art processes, operating difficulties, the low disadvantage of yield rate；Especially It is once etched using etching laser machining, completes the first nano-silver thread layer and the second nano-silver thread layer etches simultaneously, mention The high operability of technical solution, while simplifying electrode control system.
2, ITO conductive film in the prior art in the technical solution of the present invention, is substituted using nano-silver thread transparent conductive film, Cost can be greatly reduced；Meanwhile transmitance can be improved to 90% or more, surface resistance can be made low；It is led with transparent Electrolemma is made into light modulation film and compares to carry out laser ablation, and etching effect is more preferable, and almost without burst point.
3, the product prepared by technical solution disclosed by the invention realizes each nano-silver thread layer formed by etched line The optics of independent partitions controls, and is needing number of electrodes few, in the simple situation of electrode control system, improve product pattern and Text shows ability.
Detailed description of the invention
Fig. 1 is the schematic diagram of PDLC liquid crystal light modulation film one embodiment of the present invention；
Fig. 2 is the cross-sectional view of PDLC liquid crystal light modulation membrane structure of the present invention；
Fig. 3 is the schematic diagram of another embodiment of PDLC liquid crystal light modulation film of the present invention；
Fig. 4 is the schematic diagram of another embodiment of PDLC liquid crystal light modulation film of the present invention；
Fig. 5 is the schematic diagram of another embodiment of PDLC liquid crystal light modulation film of the present invention；
Fig. 6 is the schematic diagram of another embodiment of PDLC liquid crystal light modulation film of the present invention；
Fig. 7 is the schematic diagram of another embodiment of PDLC liquid crystal light modulation film of the present invention；
Fig. 8 is the schematic diagram of another embodiment of PDLC liquid crystal light modulation film of the present invention.
Appended drawing reference in the figures above is as follows:
1 etched line A；2 etched line B；3 electrode As；
4 electrode Bs；5 closure etched lines；6PET1 layers；
7 first nano-silver thread layers；8 PDLC layers；9 second nano-silver thread layers；
10 PET2 layer, 11 nano-silver thread layer bonding pad, 12 common electrode.
To keep purpose and the technical solution of the specific embodiment of the invention clearer, below in conjunction with attached drawing of the invention With the embodiment of specific embodiment, the technical solution of the specific embodiment of the invention is clearly and completely described.It is aobvious So, described specific embodiment is a part of specific embodiment of the invention, rather than whole specific embodiments. Based on described a specific embodiment of the invention, those of ordinary skill in the art are without creative work under the premise of institute All other specific embodiment of preparation, shall fall within the protection scope of the present invention.
Specific embodiment
The specific embodiment of technical solution of the present invention is carried out into one by specific embodiment below in conjunction with attached drawing Step description, these embodiments are for the detailed description to the technical program, rather than in order to limit the technical program.
Fig. 2 is the PDLC liquid crystal light modulation film cross-sectional view of the transparent conductive film of the present invention containing nano-silver thread, such as Fig. 2 It is shown, the PDLC liquid crystal light modulation film of the transparent conductive film of the present invention containing nano-silver thread successively include: from top to bottom PET1 layer 6, First nano-silver thread layer 7, PDLC layer 8, the second nano-silver thread layer 9 and PET2 layer 10.Fig. 2, which is also shown, is set to the first nano silver Electrode A 3 on line layer 7 and the electrode B 4 being set on the second nano-silver thread layer 9.
Fig. 1 shows a specific embodiment of technical solution disclosed by the invention.
Embodiment 1
As shown in Figure 1, being etched on the PDLC liquid crystal light modulation film of the transparent conductive film containing nano-silver thread in the present embodiment 1 Totally three row's pattern from top to bottom, every row's pattern is by two common foliage patterns and two maple leaf patterns totally four alternate group of pattern At.
It is illustrated by taking uppermost row pattern as an example, the pattern is made of etched line A1 and etched line B2, electrode A3 and electrode B 4 are separately positioned on the left and right side of PDLC liquid crystal light modulation film；Meanwhile in the present embodiment 1, the PDLC liquid The electrode A 3 in the left side of brilliant light modulation film is co-located on the first nano-silver thread layer 7, the right side of the PDLC liquid crystal light modulation film Electrode B 4 is co-located on the second nano-silver thread layer 9.
In the present embodiment, the PDLC liquid crystal light modulation film of the transparent conductive film containing nano-silver thread, PET1 layer 6 or PET2 layers 10 with a thickness of 150 μm；First nano-silver thread layer 7 or the second nano-silver thread layer 9 with a thickness of 60nm；PDLC layer 8 with a thickness of 30μm；11 width of nano-silver thread layer bonding pad is 80 μm；Etching line width is 30 μm.The figuratum PDLC liquid crystal tune Light film is prepared by following steps:
In the inventive solutions, the preparation of the PDLC liquid crystal light modulation film containing nano-silver thread transparent conductive film Method the following steps are included:
Step 1: substrate prepares: the substrate of selection is PET sheet base, and ready PET sheet base is carried out cure process；
Step 2: the configured coating nano-silver thread coating fluid of coating and protective glue coating fluid: by configured nano silver Line coating fluid and protective glue coating fluid pass through coating apparatus respectively and are applied on PET sheet base；Coated PET sheet base is done It is dry；
Step 3: the PET sheet base that two panels is coated with through nano-silver thread coating fluid is mounted on the dedicated painting of PDLC liquid crystal light modulation film It on cloth machine, is coated, solidified using configured PDLC composition, prepare PDLC liquid crystal light modulation film；Wherein, coating speed is set It is set to 30mm/s, it is 2.5mW/cm2 that UV, which solidifies power regulation,.
Step 4: laser ablation is carried out to PDLC liquid crystal light modulation film prepared by step 3 using etching laser machining, described PDLC liquid crystal light modulation film etches etched line, and the etched line depth, which is subject to, cuts off nano-silver thread layer；Successively laser incising etches Corrosion line A1 and etched line B2.Three row's pattern etch are completed in repetitive operation.
Wherein, make smooth be fixed on of the PDLC liquid crystal light modulation film that vacuum pore be distributed with by the way of vacuum suction On workbench；The solid of use/optical fiber laser 532nm type, laser head are moved horizontally relative to etching object in the direction XY；Tool Body etching operation setting are as follows: laser facula fixed-focus is on the first nano-silver thread layer or the second nano-silver thread layer, apart from equipment basic point 110 μm of vertical range；Etching speed 2200mm/s, frequency 180KHz, pulse width 38ns put etch period 0.02ms.
Step 5: in the film edge of the PDLC liquid crystal light modulation film after etching, three electrode As 3 in left side are sequentially prepared With three electrode Bs 4 on right side.
In the present embodiment 1, cure process is coated with using dimple in step 1, and it is hard to carry out one side coating to PET sheet base Change liquid, carries out cure process.Wherein, by weight percentage, the group of the hardening bath is grouped as: pure acrylic resin 5.5%, ten functional polyurethane resins 12%, two functional polyurethane resins 23%, reactive diluent 8%, photoinitiator 3.5% and solvent ethylene glycol 48%.
The reactive diluent is lauric acid acrylate.
The photoinitiator is methyl benzoylformate.
It is hot pressing 30 seconds under 5MPa in 180 DEG C of temperature, pressure, surface is flawless.
In addition, it is 30nm, 150 μm of length that the configuration method of the nano-silver thread coating fluid, which includes: by diameter, in step 2 Nano-silver thread be dissolved in that solid content is 8wt%, average grain diameter is in the colloidal sol of 20nm so that every 1Kg nano-silver thread is coated with Contain silver 6g in liquid；Solid content is 8wt%, viscosity 22cps in nano-silver thread coating fluid, and nano-silver thread coating coating weight is 30mL/m2。
In step 2, the protective glue coating fluid is metal oxide sol, and the pH of metal oxide sol is 5.5, Gu Content is 8wt%, and protection gel coating coating weight is 42mL/m2.The coating method of the coating is that extrusion coated is flowed on slope, passes through one Nano-silver thread coating fluid and protective glue coating fluid, are disposably applied on PET sheet base by secondary bilayer extrusion coated.
Drying temperature in the drying process is at 43 DEG C or more, drying time 6 minutes.In addition, the painting of the step 2 Cloth speed is set as 40mm/s, and it is 8mW/cm2 that UV, which solidifies power regulation,；
In 1 step 2 of the present embodiment, the PET sheet of preparation being coated with through nano-silver thread coating fluid and protective glue coating fluid Base: light transmittance 90%, mist degree 2%, surface resistivity 80ohm/sq, hardness 5H, through 180 DEG C of binding item heating binding tests 25 seconds, surface resistivity was no longer changed.
Wherein, in the present embodiment 1, the preparation of electrode A 3 and electrode B 4 includes:
S11: it on PDLC liquid crystal light modulation film of the above-mentioned steps four by laser ablation, at the position of electrode A 3, cuts Width is 10 film of PET2 layer and the second nano-silver thread layer 9 of 8mm, exposes the first following nano-silver thread layer 7；Such as the left side Fig. 2 Shown in side；
S12: 99.99% ethanol solution is used, the residual of the PDLC composition remained on the first nano-silver thread layer 7 is cleaned After object, silver paste is coated on the first nano-silver thread layer 7 using the method for screen printing, air-heater is then used, after drying coating Silver paste；
S13: the copper foil of width 5mm is attached to the silver paste surface being oven-dried；
S14: determining the position of second the first nano-silver thread layer independent partitions top electrode setting again, repeats above step, Complete the production for being located at all corresponding electrodes in the first nano-silver thread layer independent partitions on the left of PDLC liquid crystal light modulation film；
S15: lead-out wire is welded in the copper foil surface made above, completes the electrode fabrication of the first nano-silver thread layer；
S16: the position of the electrode B 4 of the setting of an independent partitions on the second nano-silver thread layer 9 is determined, then in electrode The PET1 layer 6 and the first nano-silver thread layer 7 that width is 8mm are cut at the position of B4, expose the second following nano-silver thread layer 9；As shown in the right side of fig 2；
S17: 99.99% ethanol solution is used, the residual of the PDLC composition remained on the second nano-silver thread layer 9 is cleaned After object, silver paste is coated on the second nano-silver thread layer 9 using the method for screen printing, air-heater is then used, after drying coating Silver paste；
S18: the copper foil of width 5mm is attached to the silver paste surface being oven-dried；
S19: the position of determining second the second nano-silver thread layer independent partitions top electrode B4 setting again, repetitive operation, directly To the production for completing all corresponding electrodes in the second nano-silver thread layer independent partitions；
S20: lead-out wire is welded in the copper foil surface made above.
In conjunction with Fig. 1, it can be seen that, each row's pattern is made of two etched lines, through twice etching, in the first nano silver It is identical, equal in magnitude and be overlapped corresponding first nano-silver thread layer up and down to be formed simultaneously shape for line layer 7 and the second nano-silver thread layer 9 Independent partitions and the second nano-silver thread layer independent partitions, constitute common foliage pattern and maple leaf pattern.Then, each of described First nano-silver thread layer independent partitions or the second nano-silver thread layer independent partitions are respectively arranged an electrode, are located at product Left and right side.The light transmission of row's pattern and opaque, is manipulated by the two electrodes.
Second row and third arrange pattern, design principle and electric steer mode, completely identical as first row.The reality of the product Border uses, second be exactly in together by three electrode As 3 for being in the first nano-silver thread layer 7 together and right side in manipulation left side Three electrode Bs 4 on nano-silver thread layer 9, make three row's patterns generate light transmission and lighttight effect respectively, reach display pattern Purpose.
Specifically, by the different control programs to electrode, may be implemented three row's patterns simultaneously transparent, three row's patterns according to The a variety of different visual effects of secondary transparent, first row pattern and third row's pattern linkage etc.；According to visual design scheme, It is realized by the control to each electrode.
Embodiment 2
Fig. 3 shows another specific embodiment 2 of technical solution disclosed by the invention；Wherein, three electrodes in left side It is prepared into a common electrode 12.It is other to be all made of and embodiment 1 except conditions and data as described below in the present embodiment 2 Identical material, step and parameter.
In the present embodiment 2, cure process is carried out to PET sheet base two-sided using slit-aperture type extrusion coated in step 1 It is coated with hardening bath, carries out cure process.Wherein, by weight percentage, the group of hardening bath is grouped as: pure acrylic resin 7%, Ten functional polyurethane resins 18%, two functional polyurethane resins 26%, reactive diluent 10%, photoinitiator 4% and molten Agent acetone 35%.
The reactive diluent is tripropylene glycol diacrylate.
The photoinitiator is bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of phenyl.
It is hot pressing 20 seconds under 5MPa in 200 DEG C of temperature, pressure, surface is flawless.
In addition, it is 100nm, 200 μ of length that the configuration method of the nano-silver thread coating fluid, which includes: by diameter, in step 2 The nano-silver thread of m is dissolved in that solid content is 1wt%, average grain diameter is in the colloidal sol of 100nm, so that every 1Kg nano-silver thread applies Contain silver 10g in cloth liquid；Solid content is 11wt%, viscosity 25cps, the coating of nano-silver thread coating in nano-silver thread coating fluid Amount is 50mL/m2.
In step 2, the protective glue coating fluid is metal oxide sol, and the pH of metal oxide sol is 3, admittedly contain Amount is 10wt%, and protection gel coating coating weight is 50mL/m2.The coating method of the coating is that extrusion coated is flowed on slope, passes through one Nano-silver thread coating fluid and protective glue coating fluid, are disposably applied on PET sheet base by secondary bilayer extrusion coated.
The step of repeating embodiment 1, wherein S11 step: three electricity on the PDLC liquid crystal light modulation film by laser ablation At the position of pole A3,10 film of PET2 layer and the second nano-silver thread layer 9 that width is 8mm are cut, following first is exposed and receives Rice silver wire layer 7.
In embodiment 2, on the first nano-silver thread layer 7 in the left side of the PDLC liquid crystal light modulation film of laser ablation, production One common electrode 12, the electric control operation of unified first nano-silver thread layer 7.That is, passing through the second nano-silver thread of control right side respectively The voltage of three electrodes and left side common electrode 12 on layer 9, can be controlled separately the optical characteristics of three row's patterns.
Embodiment 3
Fig. 4 shows the embodiment 3 in technical solution of the present invention, in the present embodiment, the PDLC liquid crystal light modulation film, PET1 Layer 6 or PET2 layer 10 with a thickness of 300 μm；First nano-silver thread layer 7 or the second nano-silver thread layer 9 with a thickness of 80nm；PDLC Layer 8 with a thickness of 120 μm；11 width of nano-silver thread layer bonding pad is 80 μm；Etching line width is 60 μm.
As shown in figure 4, being etched with three row's patterns on PDLC liquid crystal light modulation film, every row is made of three monograms, respectively It is tri- monograms of English alphabet B, M and W.Difference from Example 1 is that each letter is carved by individual two Corrosion line is constituted, and through twice etching, is etched etched line A1 and etched line B2 respectively, is formd and independently divided by the first nano-silver thread layer Area with the shape that the second nano-silver thread floor independent partitions form it is identical, equal in magnitude lay equal stress on fold corresponding a pair of of monogram, and And for this to monogram, second nanometer of an electrode A 3 and right side is arranged in the first nano-silver thread layer 7 in left side respectively An electrode B 4 is arranged in silver wire layer 9, which is manipulated by the two electrodes.
The step of repeating embodiment 1, difference is, step 2 coating speed is set as 50mm/s, and UV solidifies power regulation For 10mW/cm2；In step 3, according to from left to right, order from top to bottom, nine letters being sequentially etched in scheme；Using Solid/optical fiber laser 1064nm model, laser facula fixed-focus on the first nano-silver thread layer or the second nano-silver thread layer, away from 220 μm from equipment basic point vertical range；Etching speed 4000mm/s, frequency 300KHZ, pulse width 45ns put etch period 0.2ms；In addition, cure process is coated with using dimple in step 1 in the present embodiment 3, double spread is carried out to PET sheet base Hardening bath carries out cure process.Wherein, by weight percentage, the main component composition of hardening bath: pure acrylic resin 2.5%, ten functional polyurethane resins 10%, two functional polyurethane resins 16%, reactive diluent 5%, photoinitiator 1% With solvent butanone 65.5%.
The reactive diluent is 1,6- hexanediyl ester.
The photoinitiator is 1- hydroxy-cyclohexyl-phenyl ketone.
It is hot pressing 20 seconds under 5MPa in 160 DEG C of temperature, pressure, surface is flawless.
In addition, it is 10nm, 100 μm of length that the configuration method of the nano-silver thread coating fluid, which includes: by diameter, in step 2 Nano-silver thread be dissolved in that solid content is 0.5wt%, average grain diameter is in the colloidal sol of 10nm so that every 1Kg nano-silver thread applies Contain silver 1g in cloth liquid；Solid content is 0.5wt%, viscosity 2.5cps, the painting of nano-silver thread coating in nano-silver thread coating fluid Cloth amount is 10mL/m2.
In step 2, the protective glue coating fluid is metal oxide sol, and the pH of metal oxide sol is 6, admittedly contain Amount is 0.1wt%, and protection gel coating coating weight is 10mL/m2.The coating method of the coating is that extrusion coated is flowed on slope, passes through one Nano-silver thread coating fluid and protective glue coating fluid, are disposably applied on PET sheet base by secondary bilayer extrusion coated.
The characteristics of being shown as described above with Fig. 4, it can be seen that nine monograms of product, respectively by a pair of of electricity Pole control, therefore, using the transparent and opaque two states of each pattern, global pattern can be designed that a variety of variations, The pattern of every kind of variation generates and the length of duration, can be realized by the manipulation to nine pairs of electrodes.
In embodiment 3, the preparation method of monogram is given, similarly, other character patterns can be by identical Principle and similar mode realize.
Embodiment 4
Fig. 5 shows another specific embodiment 4 of technical solution disclosed by the invention；In the present embodiment 4, it is located at Between set up type three electrodes in left side of master pattern be prepared into a common electrode 12.In the present embodiment 4, following explanation is removed, It is all made of and the identical material of embodiment 3 and technical parameter.
In the present embodiment 4, cure process is coated with using dimple in step 1, and it is hard to carry out double spread to PET sheet base Change liquid, carries out cure process.Wherein, by weight percentage, the main component composition of hardening bath: pure acrylic resin 5%, ten Functional polyurethane resin 15%, two functional polyurethane resins 22%, reactive diluent 10%, photoinitiator 3.6% and molten The acetone and methyl ether mixed liquor 44.4% of agent volume ratio 1:1.
The reactive diluent is tetrahydrofurfuryl acrylate.
The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone.
In addition, it is 60nm, 80 μm of length that the configuration method of the nano-silver thread coating fluid, which includes: by diameter, in step 2 Nano-silver thread be dissolved in that solid content is 2.5wt%, average grain diameter is in the colloidal sol of 20nm so that every 1Kg nano-silver thread applies Contain silver 3.5g in cloth liquid；Solid content is 0.5wt%, viscosity 6.5cps, nano-silver thread coating in nano-silver thread coating fluid Coating weight is 30mL/m2.
The step of repeating embodiment 3 completes the production of scheme shown in Fig. 5.
Embodiment 5
In the present embodiment, the PDLC liquid crystal light modulation film, PET1 layer 6 or PET2 layer 10 with a thickness of 20 μm；First receives Rice silver wire layer 7 or the second nano-silver thread layer 9 with a thickness of 50nm；PDLC layer 8 with a thickness of 5 μm；The nano-silver thread layer connection 11 width of area is 50 μm；Etching line width is 3 μm.
Correspondingly, coating speed is set as 10mm/s, it is 1.0mW/cm that UV, which solidifies power regulation,2.Laser head moves horizontally Speed 500mm/S, maximum translational acceleration are 0.65G；Laser facula fixed-focus is in the first nano-silver thread layer or the second nano-silver thread On layer, apart from 150 μm of equipment basic point vertical range；Etching speed 3500mm/s, frequency 100KHZ, pulse width 10ns are stippled Lose time 0.05ms.
The step of repeating embodiment 1 completes the production of scheme shown in Fig. 6.
The difference lies in that such as Fig. 6, each pattern is made of closed curve or closure fold line, that is, by using laser ablation Machine once etches, and in the first nano-silver thread layer and the second nano-silver thread layer, constitutes first by a closure etched line 5 respectively and receives Rice silver wire layer independent partitions and the second nano-silver thread layer independent partitions；In addition, in the present embodiment 5, it is left in PDLC liquid crystal light modulation film The background area of side respectively makes an electrode, is respectively designated as respectively on the first nano-silver thread layer and the second nano-silver thread layer Electrode A 3 and electrode B 4；By the control to 4 this pair of electrodes of electrode A 3 and electrode B, the optical states of background area are manipulated, are reached To the effect for showing or concealing the pattern being made of closure etched line 5.
Embodiment 6
In the present embodiment, the PDLC liquid crystal light modulation film, PET1 layer 6 or PET2 layer 10 with a thickness of 300 μm；First receives Rice silver wire layer 7 or the second nano-silver thread layer 9 with a thickness of 150nm；PDLC layer 8 with a thickness of 200 μm；The nano-silver thread layer connects Connecing 11 width of area is 100 μm；Etching line width is 100 μm.
Correspondingly, 355nm type may be selected in solid/optical fiber laser, coating speed is set as 35mm/s, and UV solidifies power tune Section is 8.6mW/cm2.Laser head maximum horizontal movement speed 500mm/S, maximum translational acceleration are 0.8G；Laser facula fixed-focus On the first nano-silver thread layer or the second nano-silver thread layer, apart from 120 μm of equipment basic point vertical range；Etching speed 1800mm/ S, frequency 120KHZ, pulse width 5ns put etch period 0.15ms.
In the present embodiment 6, by weight percentage, the main component of hardening bath is formed: pure acrylic resin 5%, ten Functional polyurethane resin 16.5%, two functional polyurethane resins 24%, reactive diluent 7.5%, 3.6% and of photoinitiator The acetone and ethylene glycol mixture 43.4% of solvent volume ratio 1:1.
The reactive diluent is 1,6- hexanediyl ester.
The photoinitiator is 1- hydroxy-cyclohexyl-phenyl ketone.
As shown in fig. 7, the program devises nine monograms, it is each to be made of respectively a closure etched line 5.It repeats The preparation of the technical solution shown in Fig. 7 is completed in the operation that embodiment 5 describes；Difference is, the position of electrode A 3 and electrode B 4, It is separately positioned on the medium position of PDLC liquid crystal light modulation film left and right side.It is same as Example 5, the product of the present embodiment 6, It is the optical states by manipulating background area, realizes the display of monogram or conceal effect.
Embodiment 7
Shown in Fig. 8 is the product design figure that a width includes landscape pattern, in the present embodiment, the PDLC liquid crystal light modulation Film, PET1 layer 6 or PET2 layer 10 with a thickness of 188 μm；First nano-silver thread layer 7 or the second nano-silver thread layer 9 with a thickness of 80nm；PDLC layer 8 with a thickness of 40 μm；Etching line width is 15 μm
Its preparation manipulation is as follows:
The step of repeating embodiment 1, difference is, ignores step 1 to three, in the present embodiment 6, directly uses PDLC Liquid crystal light modulation film finished product.
The electrode A 3 being set on the first nano-silver thread layer is arranged in left side or bottom；It is set to the second nano-silver thread layer On electrode B 4, make respectively, be arranged in right side or bottom.Wherein, step 3: the solid of use/optical fiber laser 532nm Type, laser facula fixed-focus is on the first nano-silver thread layer 7 or the second nano-silver thread layer 9, apart from 50 μm of equipment basic point vertical range； Etching speed 1000mm/s, frequency 50KHZ, pulse width 5ns put etch period 0.01ms.
As shown in figure 8, top half, shows the rainbow including being indicated by arc-shaped etched line, by curvilinear etch line The two shell patterns constituted with broken line etched line, and the wave line indicated by curvilinear etch line；Lower half is etched by broken line The LOGO pattern that line and circular arc line etched line are constituted.Such as Fig. 8, positioned at the first nano-silver thread layer independent partitions on upper and lower both sides With the second nano-silver thread layer independent partitions, limited respectively by the nano-silver thread layer edge of PDLC liquid crystal light modulation film and an etched line It is fixed；Multiple first nano-silver thread layer independent partitions and the second nano-silver thread layer independent partitions are located in the middle, are carved respectively by two The nano-silver thread layer of corrosion line and PDLC liquid crystal light modulation film is edge limited.For each first nano-silver thread layer independent partitions or second An electrode is respectively set on the first nano-silver thread layer 7 or the second nano-silver thread layer 9 in nano-silver thread layer independent partitions, is formed A pair of electrodes.
In fig. 8, by way of example, constitute the etched line of two shell patterns, be labeled as etched line A1；Indicate wave line Etched line is labeled as etched line B2；The first nano-silver thread layer 7 and the second nano-silver thread between etched line A1 and etched line B2 Layer 9 is arranged electrode A 3 in left side respectively and electrode B 4 is arranged on right side；By the voltage between coordination electrode A3 and electrode B 4, Manipulate the optical characteristics in region between the shell pattern etch line A1 and wave line etched line B2.
It by the control to each pair of electrode, realizes and the optics of pattern is controlled, reach the effect for showing the design of overall pattern Fruit.The region optics bandwagon effect different from other parts can also be showed by the control to specific region.
It should be pointed out that in the description of the present invention, by term " center ", " top ", " lower section ", " front ", " after Side ", " upper left, lower-left ", " upper right, bottom right ", " left side ", " right side ", "vertical", "horizontal", " top ", " bottom ", " inside ", The orientation or positional relationship of instructions such as " outsides " is the orientation or positional relationship shown based on attached drawing, is merely for convenience of retouching Stating the present invention rather than indication or suggestion meaning device or element must have a particular orientation or with specific orientation structure It makes and operates, therefore should not be construed as limiting the invention.
Term " first ", " second " etc. are used for description purposes only, but should not be understood as indication or suggestion relative importance or Person implicitly indicates the number of related technical characteristic.Therefore, the feature limited by " first ", " second " etc. can clearly or Person impliedly indicates to include feature as one or more.In the description of the present invention, unless otherwise stated, " multiple " It is meant that two or more.
In the description of this specification, disclosed particular features, structures, materials, or characteristics can any one or it is more It is combined in any suitable manner in a embodiment or example.
Above in conjunction with attached drawing, a specific embodiment of technical solution of the present invention is further described, this tool Body embodiment is for the detailed description to the technical program, rather than in order to limit the technical program.Above-described tool Body embodiment, only preferred embodiments of the present invention will be described, not to technical concept and protection of the invention Range is defined, and without departing from the design concept of the invention, those of ordinary skill in the art make the technical program All variations and modifications out should all fall into protection scope of the present invention.

Claims (10)

1. a kind of preparation method of the PDLC liquid crystal light modulation film of transparent conductive film containing nano-silver thread, it is characterised in that the method packet Include following steps:
Step 1: substrate prepares: the substrate of selection is PET sheet base, and ready PET sheet base is carried out cure process；
Step 2: the configured coating nano-silver thread coating fluid of coating and protective glue coating fluid: configured nano-silver thread is applied Cloth liquid and protective glue coating fluid pass through coating apparatus respectively and are applied on PET sheet base；Coated PET sheet base is dried；
Step 3: the PET sheet base that two panels is coated with through nano-silver thread coating fluid is mounted on PDLC liquid crystal light modulation film Special coating machine On, it is coated, solidified using configured PDLC composition, prepare PDLC liquid crystal light modulation film；
Step 4: laser ablation is carried out to PDLC liquid crystal light modulation film prepared by step 3 using etching laser machining, in the PDLC Liquid crystal light modulation film etches etched line, and the etched line depth, which is subject to, cuts off nano-silver thread layer；
Step 5: the first nano-silver thread layer independent partitions or each second being received each of on PDLC liquid crystal light modulation film after etching Rice silver wire layer independent partitions, prepare an electrode respectively.
2. the preparation method of the PDLC liquid crystal light modulation film of the transparent conductive film according to claim 1 containing nano-silver thread, special Sign is in step 4 that the PDLC liquid crystal light modulation film is through a laser ablation, in the first nano-silver thread layer (7) or second Nano-silver thread layer (9) is formed simultaneously identical etched line；The etched line be straight-line segment, curved segments, broken line line segment, Closed curve, polygon either their combination.
3. the preparation method of the PDLC liquid crystal light modulation film of the transparent conductive film according to claim 1 containing nano-silver thread, special Sign is the step 4, and laser head is moved horizontally relative to etching object in the direction XY, horizontal maximum movement speed 600mm/ S, maximum translational acceleration are 1G；Specific etching operation, laser facula fixed-focus is in the first nano-silver thread layer (7) or the second nano silver On line layer (9), apart from 50-220 μm of vertical range of equipment basic point；Etching speed 1000-4000mm/s, frequency 20-300KHZ, arteries and veins Width 5-50ns is rushed, etch period 0.01-0.2ms is put；It is preferred that laser head maximum horizontal movement speed 550mm/S, maximum is mobile Acceleration is 0.8G；Laser facula fixed-focus is on the first nano-silver thread layer (7) or the second nano-silver thread layer (9), apart from equipment base 80-200 μm of vertical range of point；Etching speed 1500-3800mm/s, frequency 50-280KHZ, pulse width 8-45ns, point etching Time 0.03-0.18ms；More preferable laser head horizontal movement velocity 500mm/S, maximum translational acceleration are 0.65G；Laser light Spot fixed-focus is on the first nano-silver thread layer (7) or the second nano-silver thread layer (9), apart from 100-180 μm of vertical range of equipment basic point； Etching speed 1800-3500mm/s, frequency 80-250KHZ, pulse width 10-40ns put etch period 0.05-0.15ms.
4. according to claim 1 to the system of the PDLC liquid crystal light modulation film of the transparent conductive film containing nano-silver thread described in 3 any one Preparation Method, it is characterised in that the step 3, coating speed are set as 10-50mm/s, and it is 0.5mW/cm that UV, which solidifies power regulation,2 ~10mW/cm2；It is preferred that coating speed 25-45mm/s, it is 3mW/cm that UV, which solidifies power,2~8.5mW/cm2。
5. according to claim 1 to the system of the PDLC liquid crystal light modulation film of the transparent conductive film containing nano-silver thread described in 3 any one Preparation Method, it is characterised in that for a piece of PDLC liquid crystal light modulation film for having completed laser ablation, be arranged in the first nano-silver thread The electrode of layer (7) is longitudinally arranged in light modulation film left side edge, the electrode in the second nano-silver thread layer (9) is arranged, is longitudinally arranged Light modulation film right side edge；Preferably, ipsilateral and adjacent multiple electrodes are set and are fabricated to a common electrode (12).
6. the preparation of the PDLC liquid crystal light modulation film of the transparent conductive film containing nano-silver thread described in -5 any one according to claim 1 Method, it is characterised in that the cure process, by weight percentage, hardening bath therein at being grouped as: pure acrylic acid tree Rouge 2.5%-7%, ten functional polyurethane resin 7.5-18%, two functional polyurethane resin 16-26%, reactive diluent 5- 10%, photoinitiator 1-4% and solvent 45%-55%.
7. the preparation method of the PDLC liquid crystal light modulation film of the transparent conductive film according to claim 6 containing nano-silver thread, special Sign is that the group of the reactive diluent becomes lauric acid acrylate, tetrahydrofurfuryl acrylate, two propylene of tripropylene glycol The group that one or more of acid esters, 1,6- hexanediyl ester and 2- hydroxyethyl methacrylate phosphate are formed Close object；
The group of the photoinitiator becomes methyl benzoylformate, phenyl bis- (2,4,6- trimethylbenzoyl) phosphine oxides, 1- The composition that one or more of hydroxy-cyclohexyl-phenyl ketone and 2- hydroxy-2-methyl -1- phenyl -1- acetone are formed；
The solvent is one or more of butanone, ethylene glycol, acetone, methyl ether.
8. a kind of PDLC liquid crystal light modulation film of transparent conductive film containing nano-silver thread, it is characterised in that -7 is any according to claim 1 The product of the preparation of preparation method described in one.
9. the PDLC liquid crystal light modulation film of the transparent conductive film according to claim 8 containing nano-silver thread, it is characterised in that described The transparent conductive film containing nano-silver thread PDLC liquid crystal light modulation film successively include PET1 layers (6), the first nano-silver thread layer (7), PDLC layer (8), the second nano-silver thread layer (9) and PET2 layers (10)；Wherein, the first nano-silver thread layer (7) or second nanometer There are etched line, the first nano-silver thread layer (7) and the second nano-silver thread layer (9) through laser ablation, segmentation on silver wire layer (9) At the mutually independent region of referred to as the first nano-silver thread layer (7) independent partitions and second nano-silver thread layer (9) independent partitions.
10. the PDLC liquid crystal light modulation film of the transparent conductive film according to claim 9 containing nano-silver thread, it is characterised in that in institute It states the first nano-silver thread layer independent partitions or the second nano-silver thread layer independent partitions is the quarter by being located at the first nano-silver thread layer (7) Corrosion line and the first nano-silver thread layer (7) edge or the etched line and the second nano-silver thread layer (9) for being located at the second nano-silver thread layer (9) Edge surrounds, and forms an independent region；It is independent in the first nano-silver thread layer independent partitions or the second nano-silver thread layer In partitioned area, the first nano-silver thread layer (7) or the second nano-silver thread layer (9) are linked to be conductive one respectively；And adjacent two A first nano-silver thread layer independent partitions or adjacent two the second nano-silver thread layer independent partitions, due to be etched line completely every It is disconnected, mutually insulated；The first nano-silver thread layer (7) or the second nano-silver thread layer (9) are divided by etched line disposed thereon Each mutually independent first nano-silver thread layer independent partitions or the second nano-silver thread layer independent partitions out, are respectively set thereon There is an electrode, the electrode is positioned close to the edge of the light modulation film, be connected with lead-out wire on the electrode；
Wherein, it is once etched, is formed in the first nano-silver thread layer (7) and the second nano-silver thread layer (9) identical Etched line；That is, by etching once or twice, in the first nano-silver thread layer (7) and the second nano-silver thread layer (9), together When to form a shape identical, equal in magnitude and be overlapped corresponding first nano-silver thread layer independent partitions and the second nano silver up and down Line layer independent partitions；
It is preferred that setting is in the electrode on the first nano-silver thread layer (7) or the electrode arrangement being arranged on the second nano-silver thread layer (9) In the ipsilateral of the PDLC liquid crystal light modulation film；The ipsilateral left side for referring to the PDLC liquid crystal light modulation film, right side, upside or Downside；
It is further preferred that ipsilateral and adjacent multiple electrodes, which are arranged in, is fabricated to a common electrode (12).
CN201910850112.9A 2019-09-10 2019-09-10 A kind of preparation method of the PDLC liquid crystal light modulation film of the transparent conductive film containing nano-silver thread Pending CN110471205A (en)

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