CN1711306A - Optical switch microfilms - Google Patents
Optical switch microfilms Download PDFInfo
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- CN1711306A CN1711306A CN 200380103191 CN200380103191A CN1711306A CN 1711306 A CN1711306 A CN 1711306A CN 200380103191 CN200380103191 CN 200380103191 CN 200380103191 A CN200380103191 A CN 200380103191A CN 1711306 A CN1711306 A CN 1711306A
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Abstract
A method of making a light diffusing microfilm, includes providing a carrier substrate; coating a coating fluid onto the carrier substrate; drying the coating fluid on the carrier substrate to form a releasable light diffusing microfilm on the carrier substrate; and separating the light diffusing microfilm from the carrier substrate.
Description
The present invention relates generally to prepare the method for resin molding, more specifically, relate to the improvement preparation method who is used in the electro-mechanical conversion film in optical device such as flat-panel monitor and other electronic console.
Authorize the United States Patent (USP) 4113360 of Bauer and described a kind of display unit, comprise that first laminate and first laminate that serve as photoconduction or fluorescent material separate second laminate that certain distance is placed, and the thin removable mocromembrane between this two-ply.The mocromembrane that uses in the application's book is meant that thickness is less than 500 microns thin flexible membrane.This removable meagre be flexible, can make it contact first laminate in the part, and make light to pass on the mocromembrane from first laminate.If making up mocromembrane is to be used for diffused light, this removable mocromembrane serves as light switch so, when it contacts with first laminate or separates, produces area pellucida and dark space respectively on these plates.The quick contact of the mocromembrane and first laminate with separate, can be used for forming gray area.
As authorize as described in the United States Patent (USP) 4113360 of Bauer, the motion of mocromembrane can be controlled by electrical devices.For example, mocromembrane can comprise the extremely thin tin oxide layer of pluging with molten metal, and allows electric charge to be applied on this mocromembrane.Similarly conductive layer can be put on the plate.Electrical bias between plate and the mocromembrane can be used for mocromembrane shifted to or remove photoconduction.Alternately, the United States Patent (USP) 5771321 of authorizing Stern has been described the electronic-mechanical device that the control mocromembrane moves.
Typically, these plates are inflexible, and thickness is millimeter level, by such as glass or plastics (as, Plexiglas or polycarbonate) transparent material constitute.On the other hand, mocromembrane must be flexible, and thickness is micron order.Mocromembrane can be by resin material, as authorizes polycarbonate or the vinylbenzene that the United States Patent (USP) 5771321 of Stern mentions and constitute.
A shortcoming that adopts aforesaid optical switch device to prepare panel of information display unit is that needs are economical and simple method is made flexible mocromembrane.The United States Patent (USP) 5771321 of authorizing Stern has been described micro diaphragm has been immersed the solution that contains bead has the mocromembrane of the face of slightly making a list with preparation method.After micro diaphragm shifted out from solution, bead sticked on the micro diaphragm owing to capillary effect.The postheating micro diaphragm is permanently affixed on the micro diaphragm bead.The irregular surface that forms is exactly the light diffusion surface.But, authorize the United States Patent (USP) 5771321 of Stern and do not describe how to prepare precursor sheets.And the United States Patent (USP) 5771321 of authorizing Stern does not provide the method for the roughness of independent each side of control mocromembrane.In addition, may need to prepare mocromembrane with interior lights diffusing device and surface light diffusion device.Also need to prepare the low mocromembrane of double refraction.About this preparation that is used for the mocromembrane of photoswitch, also do not report.
Be used to prepare the resin microfilm of various types of optical components as mentioned above, need have good light diffusion ability, transparency, high uniformity and low-birefringence usually.And, according to the difference of final application, may need the mocromembrane of different thickness.
Usually, resin microfilm or by melt extrusion methods preparation perhaps prepares by casting method.Melt extrusion methods relates to the heating resin until fusion (viscosity is greatly about the 100000cp grade), by overflow mould the fused thermopolymer is applied on press polished metal strip or the roller then, allows film cool off, and at last film is peeled from metal support.But owing to many reasons, the film for preparing by melt extrusion methods is not suitable for optical application usually.Major cause in these former consolidating is this fact of optical birefringence that the film of melt extruded presents height.For the rhodia that highly replaces, the fusion of polymkeric substance is the another one problem.The cellulose triacetate melt temperature is very high, is 270-300 ℃, and this temperature is higher than the temperature that begins to decompose.As the United States Patent (USP) 5219510 of authorizing Machell instructed, and by rhodia and various softening agent are mixed, prepared film by melt extruded at a lower temperature.But, be not the cellulose triacetate that replaces fully at the polymkeric substance described in the United States Patent (USP) 5219510 of authorizing Machell, but replace aceticoceptor with the alkyl replacement of less degree or with the propionic acid group.Nonetheless, as described at the United States Patent (USP) 5753140 of authorizing Shigenmura, the planarization of the acetyl cellulose film of melt extruded is very poor.Consider that these are former solid, comprise the cellulose triacetate film to preparing many resin films, melt extrusion methods is also impracticable usually.On the contrary, casting method is generally used for preparing these films.
The art methods of curtain coating resin microfilm as shown in Figure 8.As shown in Figure 8, sticky polymers dope (dope) is transported to by feed-pipe 200 from pressure-pot 204 and squeezes into hopper 202 under the effect of pump 206.Dope is cast onto on the press polished metallic roll 208, and this metallic roll is positioned at first drying zone 210 of loft drier 212.Make the mocromembrane 214 of curtain coating in the roller 208 top dryings of rotating, peel off from roller 208 then.The mocromembrane 214 of curtain coating is sent to final drying zone 216 subsequently, removes remaining solvent.The mocromembrane 218 of final oven dry is rolled into volume subsequently in curling workshop section 220.The mocromembrane typical thickness that the prior art curtain coating becomes is the 40-200 micron.
Usually, because, being thinner than 40 microns thin mocromembrane in the fragility of stripping bench and drying stage, wet mocromembrane is very difficult to adopt the casting method preparation.Undesirable gauffer or wrinkle may appear in the mocromembrane of curtain coating.Peeling off in the subsequent disposal with drying stage or mocromembrane of casting method, the artifact on the size appears in thin mocromembrane especially easily.In addition, the mocromembrane of many curtain coatings is owing to the influence of moisture, and distortion over time naturally may become.For optical microfilm, good dimensional stability all is essential in storage and subsequent group process of assembling.The mocromembrane of melt extruded and the mocromembrane of curtain coating have many same problems.In addition, have only some polymer materials can be used for preparing the mocromembrane of melt extruded, because with so that the heat of polymer liquidization may make this polymer degradation.
So the improved method of needs prepares the mocromembrane as switching element.
This need be met by one aspect of the present invention, and a kind of method for preparing the light diffusion mocromembrane promptly is provided, and comprises carrier substrate is provided; On carrier substrate, apply coating fluid; Coating fluid on the drying support base material is to form strippable light diffusion mocromembrane on carrier substrate; The light diffusion mocromembrane is separated from carrier substrate.According to a further aspect in the invention, the optical thin film goods comprise carrier substrate; With the strippable light diffusion mocromembrane that on this carrier substrate, forms.
Have the method for the mocromembrane of textured surface according to a further aspect in the invention for preparation, comprise carrier substrate is provided; Adopt the coating fluid that forms bubble on carrier substrate, to be coated in lower floor (subbing layer); Drying makes this microporosity occur in lower floor in lower floor; In lower floor, apply film forming coating fluid at this; Dry film forming coating fluid in lower floor forms strippable mocromembrane with decorative pattern, and its textured surface is limited by the microporosity in lower floor; With mocromembrane from separating with carrier substrate in lower floor.
Have the method for the mocromembrane of textured surface according to a further aspect in the invention for preparation, comprise carrier substrate is provided; The employing coating fluid that is separated is coated in lower floor on carrier substrate; The dry surface that in lower floor, forms decorative pattern that makes in lower floor; Film forming coating fluid is coated in lower floor; Dry film forming coating fluid in lower floor, formation has the peelable mocromembrane of textured surface, and its textured surface is limited by the textured surface in lower floor; With mocromembrane from separating with carrier substrate in lower floor.
Be the mocromembrane goods according to a further aspect in the invention, comprise carrier substrate; Have textured surface in lower floor; In the peelable mocromembrane with textured surface that forms in lower floor, its textured surface is determined by the textured surface in lower floor.
Have the method for the mocromembrane of textured surface according to a further aspect in the invention for preparation, comprise carrier substrate is provided; In apply film forming coating fluid in lower floor, this film forming coatings fluid contains solids; Dry film forming coatings fluid in lower floor, formation has the peelable mocromembrane of textured surface, and its textured surface is limited by solids; Mocromembrane is separated from carrier substrate.
Fig. 1 is the illustrative diagram of operable coating and drying installation in the enforcement of method of the present invention.
Fig. 2 is the coating of Fig. 1 and the example schematic diagram of drying installation, comprises isolating light-diffusing film from base material is rolled up the workshop section of scratching separately.
Fig. 3 is the illustrative diagram of operable multiple-grooved coating unit in the enforcement of method of the present invention.
Fig. 4 is the diagrammatic cross-section of individual layer light diffusion mocromembrane, and this mocromembrane part is peeled off from carrier substrate, forms by method of the present invention.
Fig. 5 is the diagrammatic cross-section of individual layer light diffusion mocromembrane, and this mocromembrane part is peeled off from carrier substrate, form by method of the present invention, wherein carrier substrate have form thereon in lower floor.
Fig. 6 is the diagrammatic cross-section of multilayer, light-diffusing mocromembrane, and this mocromembrane part is peeled off from carrier substrate, forms by method of the present invention.
The diagrammatic cross-section of Fig. 7 multilayer, light-diffusing mocromembrane, this mocromembrane part is peeled off from carrier substrate, form by method of the present invention, wherein carrier substrate have form thereon in lower floor.
Fig. 8 is used for the synoptic diagram of casting apparatus of curtain coating resin microfilm in the prior art.
Mocromembrane produced according to the present invention, method are to adopt painting method at mobile carrier substrate On apply the low viscosity fluid that contains fluoropolymer resin. Resin solution also can comprise the light of dispersion The diffusion particle is such as metal oxide. In preferred embodiments, the light diffusion particle is average particle The titanium dioxide that the footpath is about 0.3 micron. Resin microfilm can be coated to the carrier with textured surface On the base material.
The surface texturing of carrier substrate can be controlled by being applied to lower floor at carrier substrate System. At the decorative pattern of lower floor by controlling in lower floor, having a mind to produce the micropore. This slightly Thereby the formation of hole be by Fast Heating wet in lower floor in lower floor, bringing out bubble-shaped Nuclear. After dry and cooling, bubble-break forms the homogeneous micropore of series, and the degree of depth is 0-100 Nanometer, width are the 50-2000 nanometer. By changing baking temperature, the use of cosolvent, table The concentration of surface-active agent and at the integral thickness of lower floor can be controlled the degree of depth of micropore and straight Directly. For example, contain 0.04% the surfactant (name that for example, can buy when coating Be Triton X-100TMThe polyoxyethylene octyl phenol) the polyvinyl alcohol of complete hydrolysis, its Middle solvent system is 92 % by weight: the water of 8 % by weight: during ethanol, forming dry thickness is 2 The micron have the micropore in lower floor. The temperature branch that dry section 66 and dry section 68-82 adopt It not 25 ℃ and 100 ℃.
The micropore approximately is that 20 nanometers are dark, and 300 nanometers are wide. Do not use ethanol or surface-active What agent prepared does not generate the micropore in lower floor. Instead, can contain particle by coating Form the base material of decorative pattern in lower floor, this particle is dried outstanding in lower floor. As Replace, producing at lower floor's fluid of incompatible resin can be contained by applying in the surface of decorative pattern Give birth to. In the dry run that wets in lower floor, incompatible polymer is separated, in lower floor Form little micropore and projection on the surface. For example, the polymethyl methacrylate of equal proportion and Polystyrene can be dissolved in the methyl ethyl ketone, and is coated on the polyethylene supporter and forms two The layer of micron thickness. After the drying, by the microcosmic decorative pattern, dark with its 50 nanometer, 1000 in lower floor The projection of the wide grade of nanometer and hole. As an alternative, do not have to provide non-at the base material of lower floor The surface that ordinary light is sliding, mean roughness is less than 1 nanometer.
In some cases, optical switch microfilms may be difficult to peeling off in lower floor from decorative pattern. In these situations, can will strip down together in lower floor and optical switch microfilms, the formation decorative pattern Optical switch microfilms. After peeling off, can wash off from optical switch microfilms in lower floor. For example, acetic acid The polyvinyl alcohol of the decorative pattern that the cellulose optical switch microfilms can apply at the PET supporter is in lower floor Upper formation. Subsequently, cellulose acetate mocromembrane and polyvinyl alcohol are shelled from the PET base material in lower floor From, be immersed in the water, thereby wash polyvinyl alcohol off in lower floor. Because cellulose acetate is water insoluble, So only there is final optical switch microfilms to preserve, its back is the mirror in lower floor of decorative pattern Picture.
More than discuss and relate to the method that the surface texturing of optical switch microfilms is controlled, this mocromembrane With contacting in lower floor of carrier substrate or carrier substrate. In order to control the opposite of optical switch microfilms Or the decorative pattern of the side that contacts with air, this mocromembrane is to adopt the multi-layer compound structure preparation. Usually, The individual layer mocromembrane that contains the titanium dioxide of dispersion forms scraggly optical switch microfilms. Projection Highly the typical case is 200 nanometers. In order to prepare mocromembrane outstanding or that projection is lower, can exist simultaneously Apply the layered composite that the superiors do not contain titanium dioxide on the carrier substrate.
In this case, solvent and resin are only contained in the superiors.By changing the wet thickness of the superiors, can control the decorative pattern of the dry rear surface of mocromembrane.As an alternative, the method that decorative pattern is controlled can be to adopt second coating that only contains solvent and resin to apply optical switch microfilms and carrier substrate, thereby forms more slick final mocromembrane.The bright and clean degree of mocromembrane can be controlled by the thickness that reduces by second coating.
After the optical switch microfilms that applies is dry basically (residual solvent＜10 weight %), just it is separated from carrier substrate.In fact, the composite structure of resin microfilm and carrier substrate can be rolled into and be saved in when needing.At this moment, carrier substrate supports optical switch microfilms, and the shearing force when protecting it to avoid in drying process carrying.And, because resin microfilm finally is in dried solid state when carrier substrate is peeled off, so in mocromembrane, can not occur owing to peel off the shearing or the orientation of the polymkeric substance of generation.Therefore, by the amorphous degree height of mocromembrane of the present invention's preparation, double refraction is very low in the face.
Utilize method of the present invention, can prepare the polymeric microfilms of the about 1-500 micron of thickness.Can prepare with the linear velocity that art methods can not reach less than 40 microns resin microfilm as thin as a wafer.Adopt carrier substrate to help the preparation of mocromembrane as thin as a wafer, the wet mocromembrane of this substrate support is by drying step, eliminated the described casting method of prior art required to before final drying step, peel off mocromembrane from metal strip or roller.And mocromembrane was (if not dried fully) of doing before separating from carrier substrate basically.
In all cases, in the dried resin microfilm residual solvent content less than 10 weight %.In a preferred embodiment of the invention, amount of residual solvent most preferably is less than 1% less than 5%.Therefore, the very fine thin mocromembrane that the invention enables existing casting method not prepare is easy to make.In addition, the mocromembrane that is thicker than 40 microns also can adopt method preparation of the present invention.In order to prepare thicker mocromembrane, can in serial operation or off-line procedure, on mocromembrane-base material composite structure, apply other coating, and can not damage optical quality.In this manner, the restriction of having removed solvent when method of the present invention has overcome the thicker mocromembrane of preparation is because before applying the wet mocromembrane of back one deck, the mocromembrane that had before applied has been drying.Therefore, the present invention allows the thickness of the final mocromembrane scope more feasible than casting method bigger.
The preparation process of resin microfilm comprises, sliding surface at the hopper that applies forms the single or multiple lift mixture, this layered composite comprises low viscous bottom, one or more middle layer and the optional top layer that contains tensio-active agent, make layered composite flow down described coating hopper sliding surface and flow out the discharge port of hopper, layered composite is applied on mobile the base material.Especially, adopt laminated coating to allow to apply a plurality of unique liquid levels of forming that contain.
Can in certain layer, add coatings additive(s) and additive, with performance or the raising processing tolerance level that improves mocromembrane.For example, multilayer applies and makes tensio-active agent can be positioned at required top to spread out layer, rather than in the whole wet mocromembrane.In other example, undermost polymer concentration can be adjusted with the realization low viscosity, and is convenient to layered composite is applied on the carrier substrate at a high speed.So, the invention provides the convenient preparation method of the required MULTILAYER COMPOSITE mocromembrane of some optical element or other like.Adopt method of the present invention, minimum by using carrier substrate that gauffer and wrinkle are dropped to.By the rigidity backing that provides resin microfilm to use, it is minimum that carrier substrate drops to the dimensional distortion of optical microfilm.This is for processing and handle less than for about 40 microns mocromembrane as thin as a wafer, and is especially convenient.
And, utilize method of the present invention to eliminate scratch and wearing and tearing artifact that known casting method can generate.Because carrier substrate is in resin microfilm with have between the delivery roll of potential abradability in all drying operationes.Gu this, method of the present invention does not need the required cosolvent of curtain coating operation, lubricant or protection laminate layers to come the minimum wear artifact.In addition, the binding feature of carrier substrate has also been eliminated resin microfilm and has been changed the tendency that distortion or gauffer occur becoming along with the time owing to humidity.Therefore, method of the present invention guaranteed the polymkeric substance optical microfilm preparation and store and final treatment step that the preparation optical element is required in dimensional stability.
In the enforcement of the inventive method, carrier substrate is preferably such as the reticulation (Web) of polyethylene terephthalate (PET).The pet vector base material can carry out pre-treatment in lower floor with coarse, the physical template that should serve as the optical switch microfilms of coating in lower floor.Coarse decorative pattern in lower floor can pass through in obtaining in the medium and small bubble nucleating of lower floor.For example, can adopt electric discharge device to change bonding between resin microfilm and the PET base material.Especially, can improve bonding between mocromembrane and the base material in lower floor or discharge process, but still allow mocromembrane to peel off from base material afterwards.
Though with particular reference to sliding pearl formula coating operation, person of skill in the art will appreciate that the present invention can utilize other to apply operation and implement when the present invention discusses herein.For example, the no upholder mocromembrane with path difference in the low degree should apply operation and single or multiple lift curtain coating by the single or multiple lift channel mould and operates and be prepared.And, it will be understood by those skilled in the art that the present invention can be convenient to use as alternative carrier substrate to implement.For example, the low mocromembrane of double refraction also can be finished on other resin upholder [for example, Polyethylene Naphthalate (PEN), rhodia, PET], paper upholder, resin laminated layer paper upholder and metal support (as aluminium) in the release surface.
Practical application of the present invention comprises the polymeric microfilms of preparation as optical microfilm.Especially, the optical element during the prepared according to the methods of the invention resin microfilm can be produced as the electronic console that uses optical switch microfilms.The example of optical resin comprise described herein these, that is, and cellulose triacetate, polyvinyl alcohol, polycarbonate, polyethersulfone, polymethylmethacrylate and polyvinyl butyral acetal.Other potential optical resin can comprise fluoropolymer (polyvinylidene difluoride (PVDF), fluorinated ethylene propylene and polychlorotrifluoroethylene), other Mierocrystalline cellulose (secondary cellulose acetate, cellulose acetate butyrate, acetate propionic acid fiber, ethyl cellulose), polyolefine (cyclic olefin polymer), polystyrene, aromatic polyester (polyarylate and polyethylene terephthalate), sulfone (polysulfones, polyethersulfone, polyarylsulphone) and Copolycarbonate, and other.
Forward Fig. 1 now to, provided and be suitable for implementing the exemplary and known coating of the inventive method and the synoptic diagram of dehumidification system 10.Coating and dehumidification system 10 typical cases are used for applying extremely thin mocromembrane on moving substrate 12, get on to desolventize at moisture eliminator 14 subsequently.Single coating unit 16 shows that system 10 has only a coating application point and a moisture eliminator 14, but known in the thin mocromembrane of preparation mixture, adopts 2 or three (even nearly 6) other coating application point and corresponding drying zone.Order applies with drying step and is called series connection coating operation in the art.
Coating and drying installation 10 comprise unwinding workshop section 18, and in order to the base material 12 that moves around supporting roll 20 chargings, wherein coating unit 16 applies coating at supporting roll 20 places.The reticulation 22 that applies is subsequently forward by moisture eliminator 14.In the practice of the inventive method, the final dried mocromembrane 24 that comprises the resin microfilm that is positioned on the base material 12 is rolled into volume in coiling workshop section 26.
As shown in the figure, on the reticulation 12 that moves, four layers of coating have exemplarily been applied.The coating liquid of each layer is contained in 28,30,32 and 34 li of paint delivery pipes respectively.Coating liquid is transported to 44,46,48 and 50 li in the conduit of coating unit 16 respectively from the paint delivery pipe by pump 36,38,40,42.In addition, coating and dehumidification system 10 can also comprise electric discharge device, and as corona or glow discharge device 52, perhaps polar charge assist device 54, in order to before applying coating base material 12 is made amendment.
The difference of coating method and casting method is every kind of processing step that technology is required.These processing steps influence many tangible parameters again, as fluid viscosity, conversion auxiliary agent, base material and the hardware of every kind of method uniqueness.Usually, coating method relate to will dilution low-viscosity (mobile) liquid be applied on the thin flexible parent metal, in loft drier evaporating solvent and dried mocromembrane/substrate composite be rolled into volume.On the contrary, casting method relates to high density viscosity dope is applied on press polished metallic roll or the belt, the wet mocromembrane on the dry metal base of part, released part exsiccant mocromembrane from the base material, in loft drier, remove other solvent in the dry mocromembrane of part, and the mocromembrane of doing is rolled into volume.With regard to viscosity, coating method requires very low viscosity, less than 5000cp.In practice of the present invention, the viscosity of coating liquid is usually less than 2000cp, more generally less than 1500cp.And in the method for the invention, the viscosity of the lowest layer is preferably less than 200cp, for the high speed application most preferably less than 100cp.On the contrary, casting method requires the dope of high density, and the viscosity under the actual operational speed is the 10000-100000cp grade.With regard to the conversion auxiliary agent, coating method is usually directed to adopt tensio-active agent as the conversion auxiliary agent, flowing after occurring with control coating artifact such as spot, repellency, orange-peel and cissing.On the contrary, casting method does not need tensio-active agent.On the contrary, the conversion auxiliary agent only is used for up-stripping and conveying operations in casting method.For example, when cast optical microfilms, adopt lower alcohol sometimes, so that the friction artifact when transmitting by loft drier drops to minimum as the conversion auxiliary agent.With regard to base material, coating method adopts thin (10-250 micron) flexible support thing usually.On the contrary, casting method adopts thick (1-100 millimeter), successive, press polished metallic roll or rigid strip.Owing to there is the difference on these processing steps, that uses in the hardware that uses in the coating and the curtain coating is remarkable different, and this point can be by comparison diagram 1 and synoptic diagram shown in Figure 8 are understood respectively.
Forward Fig. 2 below to, provided synoptic diagram, operating winding is as an alternative wherein arranged at same exemplary coating shown in Fig. 1 and dehumidification system 10.Accordingly, adopted identical drawing reference numeral among the figure, up to operating winding.In the enforcement of the inventive method, contain the dried mocromembrane 24 that has applied resin-coated base material (can be the paper or the metal of resin microfilm, paper, resin-coating) thereon and be placed between opposed roller 56 and 58.After resin microfilm 60 was peeled off from base material 12, optical microfilm was delivered to coiling workshop section 62, and base material 12 is delivered to coiling workshop section 64.In a preferred embodiment of the invention, polyethylene terephthalate (PET) is as base material 12.Base material 12 can adopt the pre-treatment in lower floor, with the mocromembrane 60 of promotion coating and the bonding of base material 12.
The coating unit 16 that is used for coating liquid is applied on the moving substrate 12 can be such as the multilayer applicator of sliding pearl formula hopper.Just as the United States Patent (USP) 2761791 of authorizing Russell is instructed, or the sliding pearl formula hopper of in the United States Patent (USP) 3508947 of authorizing Hughes, being instructed.As an alternative, coating unit 16 can be the individual layer applicator, as fluting mould hopper or jet-type hopper.In a preferred embodiment of the invention, bringing device 16 is the sliding pearl formula of multilayer hoppers.
As mentioned above, coating and dehumidification system 10 comprise moisture eliminator 14, and the typical case is a loft drier, in order to remove the solvent in the mocromembrane that applies.The exemplary moisture eliminator 14 that uses in the practice of the inventive method comprises first drying zone 66, and the back is the drying zone 68-82 of 8 independent controlled temperature of other energy and air-flow.Though illustrated moisture eliminator 14 contains 9 independently drying zones, known also have comprise less sectional loft drier and can be used for implementing method of the present invention.In a preferred embodiment of the invention, moisture eliminator 14 has at least two independently drying zone or dryer section.
Preferably, each drying zone 68-82 controlled temperature and air-flow independently.At each drying zone, temperature can be adjusted to 5 ℃-150 ℃.The defective that produces in order to make wet mocromembrane that case-hardening or decortication take place when the drying drops to minimum, needs optimized drying rate in the first district of moisture eliminator 14.When the first temperature of distinguishing of drying is improper, produce many artifacts.For example, when the temperature of drying zone 66,68 and 70 is arranged to 25 ℃, the atomizing or the blushing of polycarbonate microfilms will be examined now.When adopting high-vapor-pressure solvent (methylene dichloride and acetone) in the coating fluid, the defective of turning white is a problem especially.Too high temperature also can cause resin microfilm other artifact to occur, such as case-hardening, netted decorative pattern and micropore.In one embodiment of the invention, the working temperature of first drying zone 66 is at least about 25 ℃, but is lower than 95 ℃, and the wet coating of the reticulation 22 that applies can not be subjected to the direct impact of air.In another embodiment of the inventive method, drying zone 68 and 70 working temperature also are at least about 25 ℃, but are lower than 95 ℃.The actual drying temperature of drying zone 66,68 can rule of thumb be optimized in this scope by those skilled in the art.
With reference now to Fig. 3,, provided the synoptic diagram of exemplary coating device 16 in detail.Coating unit 16 with the cross-sectional view signal of side top comprises proparea 92, second district 94, the 3rd district 96, the 4th district 98 and back plate 100.There is the opening for feed 102 that enters second district 94,, forms the lowest layer 108 in order to provide coating liquid to the first metering slit 104 by pump 106.There is the opening for feed 110 that enters the 3rd district 96, in order to provide coating liquid, form layers 116 to the second metering slit 112 by pump 114.There is the opening for feed 118 that enters the 4th district 98, in order to provide coating liquid, form layers 124 to metering slit 120 by pump 122.There is the opening for feed 126 that enters back plate 100, in order to provide coating liquid, form layers 132 to metering slit 128 by pump 130.
Each slit 104,112,120,128 all contains the cavity of lateral distribution.Proparea 92 comprises the slipping plane 134 of inclination and applies sword 136.Second inclined slide 138 is arranged at the top in second district 94.The 3rd inclined slide 140 is arranged at the top in the 3rd district 96.The 4th inclined slide 142 is arranged at the top in the 4th district 98.Back plate 100 extends on the inclined slide 142, forms innerland face (back land surface) 144.What nestle up this coating unit or hopper 16 is to apply backing roller 20, and reticulation 12 is around its transmission.Coating 108,116,124,132 forms layered composite, and this mixture forms coating bead 146 between sword 136 and base material 12.Typically, coating hopper 16 can move on to the coating position from non-coating position towards applying backing roller 20 directions.Though illustrated coating unit 16 has four current limliting grooves, known also have have a plurality of metering slits the coating mould of (nearly 9 or more) can be used for implementing method of the present invention.
Coating fluid mainly comprises the fluoropolymer resin that is dissolved in the appropriate solvent.The light diffusion particle also can be dispersed in the coating liquid.Appropriate resin comprises any polymer materials that can be used to form transparent microfilm.The current example that is used for forming the practical resin of light mocromembrane comprises polyvinyl alcohol, polybutene butyral, vinylformic acid, with polystyrene, Mierocrystalline cellulose, polycarbonate and polyarylate, polyolefine, fluoroplastics (for example, fluorinated ethylene propylene and polyvinylidene difluoride (PVDF)), sulfone.In the method for the invention, the polymer type or the mixture of polymers that can be used for forming optical switch microfilms there is not particular restriction.
With regard to the solvent that is used for resin material above-mentioned, suitable solvent comprises, for example, chlorating solvent (methylene dichloride and 1, the 2-ethylene dichloride), alcohol (methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pyranton, phenol and hexalin), ketone (acetone, butanone, methyl iso-butyl ketone (MIBK) and pimelinketone), ester (methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate and n-butyl acetate), aromatics (toluene and dimethylbenzene) and ether (tetrahydrofuran (THF), 1, the 3-dioxolane, 1, the 2-dioxolane, 1, the 3-diox, 1,4-diox and 1, the 5-diox).Water also can be used as solvent.Coating solution also can be prepared with the mixture of above-mentioned solvent.
Coating liquid can also comprise the additive as the conversion auxiliary agent.The conversion auxiliary agent comprises softening agent and tensio-active agent, and these additives are used in particular for the polymeric microfilms of certain type usually.For example, the softening agent that is applicable to polycarbonate, polyethersulfone and cellulose triacetate microfilms comprises phthalic ester (diethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dioctyl phthalate (DOP) and butyl octyl phthalate), adipic acid ester (Octyl adipate) and phosphoric acid ester (stupid ester of tripotassium phosphate and triphenylphosphate).On the other hand, for water-soluble poval, suitable manufacturing methods comprises such as the polyvalent alcohol of glycerine and ethylene glycol and such as the hydramine of thanomin.
Softening agent can make the mocromembrane premature setting phenomenon at coating hopper place drop to minimum as the coatings additive(s) in the conversion operations herein, and improves the drying property of wet mocromembrane.In the method for the invention, softening agent can be used for dropping to foaming, warpage and the delamination of resin microfilm in the drying operation minimum.In a preferred embodiment of the invention, in order to reduce the defective in the final resin microfilm, the relative polymer concentration of total concn that can add softening agent in the coating fluid can be up to 50 weight %.
Coating fluid also can comprise tensio-active agent as coatings additive(s), thus control and the mobile relevant artifact in coating back.The artifact that the mobile phenomenon causes after applying comprises spot, tangerine peel (Bernard hole) and cissing.For being dissolved in the fluoropolymer resin in the organic solvent, being used for controlling the tensio-active agent that applies back mobile artifact and comprising siloxanes and fluorochemicals.The example of commercial silicone-type tensio-active agent comprises: 1.) polydimethylsiloxane, DC200 Fluid as Dow Corning, 2.) poly-(dimethyl, aminomethyl phenyl) siloxanes, DC510 Fluid as Dow Corning, 3.) the polydimethylsiloxane of many alkyl replacements, DC190 and DC1248 as Dow Corning, and the L7000 Silwet series (L7000, L7001, L7004 and L7230) of Union Carbide, with 4.) poly-(dimethyl that replaces of many alkyl, aminomethyl phenyl) siloxanes is as the SF1023 of General Electric.The example of commercial fluorochemical surfactant comprises: 1.) fluorinated alkyl esters, Fluorad series (FC430 and FC431) as 3M company, 2.) fluorinated polyoxyethylene ether, Zonyl series (FSN, FSN100, FSO, FSO100) as Du Pont, 3.) the poly-perfluoroalkyl vinylformic acid ethyl ester of acrylate, as the F series (F270 and F600) of NOF company, and 4.) perfluoroalkyl derivatives, as the Surflon series (S383, S393 and S8405) of Asahi Glass company.
For being dissolved in the fluoropolymer resin in the water-containing solvent, suitable tensio-active agent comprises that those tensio-active agents that are suitable for aqueous coating of describing are (referring to for example Surfactant:Static and Dynamic surface tension by YM Tricotin Liquid Film Coating in countless publications, Deng the 99-136 page or leaf, SE Kistler and PM Schweitzer edit, Chapman and Hall[1997]).Tensio-active agent can comprise non-ionic type, anionic, cationic and amphoteric.The example of practical tensio-active agent comprises Soxylat A 25-7, and as polyoxyethylene (8) iso-octyl phenyl ether, polyoxyethylene (10) iso-octyl phenyl ether, and polyoxyethylene (40) iso-octyl phenyl ether and fluorinated polyoxyethylene ether are as the commercial Zonyl series of Du Pont.
Type to used tensio-active agent does not have particular restriction.The available tensio-active agent is non-ionic type normally.In a preferred embodiment of the invention, when having adopted organic solvent when mocromembrane prepares, the non-ionic compound of siloxanes or fluorinated type is added in the superiors.With regard to the distribution of tensio-active agent, tensio-active agent is the most effective when the superiors of laminated coating.In the superiors, surfactant concentrations is 0.001-1.000 amount amount % preferably, most preferably is 0.010-0.500 weight %.In addition, can use a spot of slightly tensio-active agent, make tensio-active agent drop to minimum to external diffusion from the superiors on second upper strata.The surfactant concentration on second upper strata is 0.000-0.200 weight % preferably, most preferably is 0.000-0.100 weight %.Because tensio-active agent only need be in the superiors, so the tensio-active agent total amount of remnants is very little in the final dried mocromembrane.
Forward Fig. 4-7 below to, the cross-sectional view that provides has shown the various film configuration with method preparation of the present invention.In Fig. 4, demonstration be that single-layer optical switch microfilm 150 parts are peeled off from carrier substrate 152.Optical microfilm 150 both can form by apply single liquid level on carrier substrate 152, can form by applying layered composite again, and the composition of this layered composite is substantially the same between the layer fully.As an alternative, in Fig. 5, carrier substrate 154 can adopt in lower floor 156 pretreated, should change cohesive force between individual layer light mocromembrane 158 and the base material 154 in lower floor.Fig. 6 has provided and has comprised four multilayer mocromembranes 160 of forming different layers, and it comprises the orlop 162 of the most close carrier support 170, two middle layers 164 and 166, and the superiors 168.
Fig. 6 has also described whole layered composite 160 and can peel off from carrier substrate 170.Fig. 7 has described the layered composite mocromembrane of just peeling off from carrier substrate 182 172, comprises the lowest layer 174 near carrier substrate 182, two middle layers 176,178, and the superiors 180.Carrier substrate 182 has adopted in lower floor 184 and had handled, to change the cohesive force between composite microfilm 172 and the base material 182.
Can constitute by many polymer materialss in lower floor 156 and 184, as polyvinyl acetal, polycarbonate, urethane, Mierocrystalline cellulose, acrylic resin, gelatin and poly-(vinyl cyanide-altogether-vinylidene chloride-altogether-vinylformic acid).Selection at lower floor's material therefor can rule of thumb be optimized by those skilled in the art.
Method of the present invention can also be included in the step that applies on the resin microfilm that prepared and the carrier substrate mixture.For example, coating and dehumidification system 10 illustrated in figures 1 and 2 can be used for applying second layer multilayer mocromembrane on existing optical microfilm/substrate composite.If before applying follow-up coating film/substrate composite is rolled into volume, this step is called hyperchannel coating operation so.If apply and drying operation is that order is carried out on the machine with a plurality of coating workshop sections and loft drier, this step is called polyphone and applies and operate so.In this manner, thick mocromembrane can prepare under high linear speed, and can not occur and the relevant problem of a large amount of solvents of removal from very thick wet mocromembrane.And the practice that hyperchannel or series connection apply also has and drops to minimum advantage with other artifact such as severe streak, severe spot and overall microfilm are inhomogeneous.
Series connection applies or hyperchannel is coated in the bonding that requires to have certain minimum degree when using between first channel mocromembrane and carrier substrate.In some cases, find in multi-channel operation that after having applied the second or the 3rd wet coating, bubble appears in the weak film/substrate composite of cohesive force.For fear of blister defects, the cohesive force between first channel resin microfilm and carrier substrate must be greater than 0.3N/m.The cohesive force of this grade can be by various web treatments, comprise variously obtaining in lower floor and various discharge process.But, between mocromembrane that applies and base material, do not need the over-drastic cohesive force, because in follow-up strip operation, may destroy this mocromembrane.Specifically, have been found that cohesive force is very poor greater than the separability of mocromembrane/substrate composite of 250N/m.The mocromembrane of peeling off from the too good mixture of this bonding presents owing to tear and/or owing to the destroyed defective that produces of the force of cohesion in the mocromembrane.In a preferred embodiment of the invention, the cohesive force between resin microfilm and the carrier substrate is less than 250N/m.Most preferred, the cohesive force between resin microfilm and the carrier substrate is 0.5-25N/m.
Method of the present invention is suitable for resin coating is applied to various base materials, on polyethylene terephthalate (PET), Polyethylene Naphthalate (PEN), polystyrene, cellulose triacetate and other polymeric microfilms.Polymeric substrate can be mocromembrane tensile, unilateral stretching or two-way stretch or sheet.Other base material can comprise laminate layers and polymeric microfilms, glass, cloth, aluminium and other metal support of paper, paper.In some cases, base material can adopt in lower floor or electric discharge device and carry out pre-treatment.Base material can also utilize and comprise various tackiness agents and accrete functional layer is carried out pre-treatment.Thickness to base material does not have particular requirement.For the optical resin mocromembrane of this place preparation, base material is the PET material, and thickness is 100 or 175 microns.It is that the base material of 5-500 micron is put into practice that method of the present invention can adopt thickness.
Adopt following test to determine the performance of mocromembrane.
Thickness.The thickness of the mocromembrane that finally strips down adopts the ModelEG-225 gauge test of Ono Sokki company, and unit is a micron.
Path difference.Path difference (Re) adopts Woollam M-2000V beam split ellipsometer to measure in the face of the mocromembrane of peeling off, and measuring wavelength is the 370-1000 nanometer, and unit is nanometer (nm).Path difference is that observed value according to 590 nanometers calculates in the face in the table 1.Path difference is by following formula definition in the face:
R
e＝|n
x-n
y|×d
R wherein
eBe the interior path difference of face of 590 nanometers, n
xBe the mocromembrane peeled off specific refraction at slow-axis direction, n
yBe the mocromembrane the peeled off specific refraction at quick shaft direction, d is the thickness of the mocromembrane peeled off, and unit is nanometer (nm).Therefore, R
eBe the thickness that the absolute value of the double refraction difference of slow-axis direction in the mocromembrane face peeled off and quick shaft direction is multiplied by mocromembrane.
Transmittance and turbidity.Total light transmittance (Trans) and turbidity adopt the Haze-Gard Plus (Model HB-4725) of BYK-Gardner company to measure.Total light transmittance is all luminous energy through mocromembrane that absorb on integrating sphere.The printing opacity turbidity is all luminous energy greater than 2.5 ° of diffusions that absorb on integrating sphere.
Surface roughness.Average surface roughness (Ra) adopts the TappingMode of Digital Instruments
TMThe Scanning Probe Microscopy of atomic force microscope Model D300 is measured, and unit is nanometer (nm).
Cohesive force.The cohesive strength of the sample that applies adopts 180 ° to peel off test and improve one's methods and test, and testing apparatus is Instron 1122 stretching testing machines, and load is 500 grams, and unit is Newton/meter (N/m).At first, prepare the sample bar of 0.0254 meter (1 inch) wide coating.
Utilize a slice 3M Magic Tape to form delamination at coating one end.Then another sheet 3M MagicTape is attached to the delamination position of coating, as the clamping point of test.The length of the 3M Magic Tape that stretches out is enough to surpass upholder, thereby makes the Instron anchor clamps can distrubed test.Sample is installed on Instron 1122 stretching testing machines subsequently, wherein base material is fixed on the anchor clamps, and coating 3M Magic/tape assembly is fixed on the end anchor clamps.Note when 180 ° of angles, speed are 2 inch per minutes (50.8 millimeters/minute) coating is peeled off required mean force (unit is newton) from base material.Utilize this power value, calculate cohesive strength with following formula, unit is N/m:
S
A＝F
p(1-cosθ)/w
S wherein
ABe cohesive strength, F
pBe peeling force, θ is that peel angle (180 °) and w are specimen width (0.0254m).
Residual solvent.The method of remaining residual solvent is in the mocromembrane that quantitative estimation is done, and at first peels off mocromembrane from carrier substrate, and the weight of the mocromembrane that weighing is peeled off is incubated 16 hours with mocromembrane in 150 ℃ loft drier, the mocromembrane after the last weighing insulation.Residual solvent is represented divided by the per-cent of the preceding weight of insulation with weight difference.
As previously mentioned, can find that the present invention is very suitable for obtaining all results above-mentioned and target and other conspicuous advantage and this device inherent advantage.
Claims (10)
1. prepare the method for light diffusion mocromembrane, comprising:
A) provide carrier substrate;
B) coating fluid is coated on the carrier substrate;
C) coating fluid on the drying support base material is to form strippable light diffusion mocromembrane on carrier substrate; And
D) the light diffusion mocromembrane is separated from carrier substrate.
2. the method for claim 1 further comprises: the light diffusion mocromembrane is kept on the carrier substrate also separates from carrier substrate before use.
3. the process of claim 1 wherein carrier substrate is carried out decorative pattern, so that provide textured surface for mocromembrane.
4. optical thin film goods comprise:
A) carrier substrate; With
B) the strippable light diffusion mocromembrane that on carrier substrate, forms.
5. preparation has the method for the mocromembrane of textured surface, comprising:
A) provide carrier substrate;
B) utilize the coating fluid that forms bubble on carrier substrate, to be coated in lower floor;
D) dry in lower floor, with in lower floor, producing the microporosity;
E) in lower floor, applying the film forming coatings fluid;
F) dry film forming coatings fluid in lower floor, to form strippable mocromembrane, this mocromembrane has the surface of the decorative pattern that is limited by the microporosity in lower floor; With
G) with mocromembrane from separating with carrier substrate in lower floor.
6. the method for claim 5 further comprises; Mocromembrane is kept on the carrier substrate and separates from carrier substrate before use.
7. preparation has the method for the mocromembrane of textured surface, comprising:
A) provide carrier substrate;
B) utilize the coating fluid that is separated on carrier substrate, to be coated in lower floor;
C) dry in lower floor, with in the surface that in lower floor, forms decorative pattern;
D) in lower floor, applying the film forming coatings fluid;
E) dry film forming coatings fluid in lower floor, to form strippable mocromembrane, this mocromembrane has the surface of the decorative pattern that is limited by the textured surface in lower floor; With
F) with mocromembrane from separating with carrier substrate in lower floor.
8. the method for claim 7 further comprises: mocromembrane is kept on the carrier substrate also separates from carrier substrate before use.
9. mocromembrane goods comprise:
A) carrier substrate;
B) have textured surface in lower floor; With
C) in the strippable mocromembrane that forms in lower floor, this mocromembrane has the surface of the decorative pattern that is limited by the textured surface in lower floor.
10. preparation has the method for the mocromembrane of textured surface, comprising:
A) provide carrier substrate;
B) in apply the film forming coatings fluid in lower floor, this film forming coatings fluid comprises solid particles;
C) dry film forming coatings fluid in lower floor, to form strippable mocromembrane, this mocromembrane has the surface of the decorative pattern that is limited by solid particles; With
D) mocromembrane is separated from carrier substrate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42589802P | 2002-11-13 | 2002-11-13 | |
| US60/425,898 | 2002-11-13 | ||
| US10/434,901 | 2003-05-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110408249A (en) * | 2019-07-22 | 2019-11-05 | 佛山宜可居新材料有限公司 | A kind of preparation method of macromolecule laminated film |
| CN110408250A (en) * | 2019-07-22 | 2019-11-05 | 佛山宜可居新材料有限公司 | A kind of preparation method of macromolecule laminated film |
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| TWI230275B (en) * | 2000-05-12 | 2005-04-01 | Kuraray Co | Polyvinyl alcohol film and polarization film |
| JP2002110512A (en) * | 2000-09-27 | 2002-04-12 | Toshiba Corp | Film formation method and device thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110408249A (en) * | 2019-07-22 | 2019-11-05 | 佛山宜可居新材料有限公司 | A kind of preparation method of macromolecule laminated film |
| CN110408250A (en) * | 2019-07-22 | 2019-11-05 | 佛山宜可居新材料有限公司 | A kind of preparation method of macromolecule laminated film |
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