CA2187896A1 - Precision coating process for preparing polymerizable films - Google Patents
Precision coating process for preparing polymerizable filmsInfo
- Publication number
- CA2187896A1 CA2187896A1 CA002187896A CA2187896A CA2187896A1 CA 2187896 A1 CA2187896 A1 CA 2187896A1 CA 002187896 A CA002187896 A CA 002187896A CA 2187896 A CA2187896 A CA 2187896A CA 2187896 A1 CA2187896 A1 CA 2187896A1
- Authority
- CA
- Canada
- Prior art keywords
- substrate
- die
- fluid
- coating
- land
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
- B05C5/0254—Coating heads with slot-shaped outlet
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Apparatus (AREA)
Abstract
A method of coating the surface of a substrate with an essentially solvent-free polymerizable fluid that includes passing the fluid through a die onto the surface of the substrate as the substrate moves relative to the die. The die includes a channel adapted to receive the fluid and an adjustable width slot in with said channel through which the fluid is passed formed between a substantially straight, sharp edge located on the downstream side of the substrate and a land located on the upstream side of the substrate.
Description
~WO 95129766 ~ C~
__ COATIN¢ PROCB88 POR
PRTdP7 PqT.~rMT~nT~ PT T~ F~ 8 RA~ r uu~d of the Invention Field of the Invention This invention relates to a coating process for preparing polymerizable f ilms .
Descril~tiQn of the Related Art The bead coating method of applying fluids to substrates i5 known. According to this method, coating fluid is fed via a metering pump to a die which deposits the coating fluid on the surface of a moving substrate as the substrate moves past the die. As the 15 coating fluid leaves the die it forms a continuous coating bead between the upstream die lip, the fl~: ..=,L.c:~.a die lip, and the web. The moving substrate is wetted by the bead as the substrate moves past the bead to create a layer of coating fluid on the 20 substrate. To improve the stability of the bead (and thus reduce coating i nh~ ~ J - ities), a vacuum may be applied to a vacuum chamber located upstream of the coating bead.
r rv of the Invention In general, the invention features a method of coating the surface of a sub8trate with an ~:5--~t;A1 1Y
solvent-free (i.e., 100% solids1 polymerizable fluid by passing the fluid through a die onto the surface of the substrate as the substrate moves relative to the die.
The die includes a channel adapted to receive the fluid and an adjustable width slot in communication with the channel through which the f luid is passed .
The slot is formed between the C9 .~ L~ u bar 66 and the U~JD~LC:OIU bar 64. The ~1 I.D~Leam bar lip is formed 35 as a sharp edge 70 and the ll~- ~L~ U bar lip is formed as a land 68 which substAnt i A 1 1 Y corresponds in shape WO95/29766 21 87896 P~J~ ~''0I1~ --to the shape of the substrate in the immediate area of coating fluid application. As used herein, "upstream"
and "d .~.Lr~ l" are relative to the direction of the moving substrate.
In preferred ~ s, the edge radius of the sharp edge (as defined in Fig. 3) measures no more than about 10 microns, and more preferably ranges from about 2 to about 4 micron6. The edge angle Al of the sharp edge (as defined in Fig. 3) preferably ranges from about 20 to about 75 and preferably is about 50 -60 .
The Cu~ve:Ly_.~Ce of the die C (as defined in Fig.
__ COATIN¢ PROCB88 POR
PRTdP7 PqT.~rMT~nT~ PT T~ F~ 8 RA~ r uu~d of the Invention Field of the Invention This invention relates to a coating process for preparing polymerizable f ilms .
Descril~tiQn of the Related Art The bead coating method of applying fluids to substrates i5 known. According to this method, coating fluid is fed via a metering pump to a die which deposits the coating fluid on the surface of a moving substrate as the substrate moves past the die. As the 15 coating fluid leaves the die it forms a continuous coating bead between the upstream die lip, the fl~: ..=,L.c:~.a die lip, and the web. The moving substrate is wetted by the bead as the substrate moves past the bead to create a layer of coating fluid on the 20 substrate. To improve the stability of the bead (and thus reduce coating i nh~ ~ J - ities), a vacuum may be applied to a vacuum chamber located upstream of the coating bead.
r rv of the Invention In general, the invention features a method of coating the surface of a sub8trate with an ~:5--~t;A1 1Y
solvent-free (i.e., 100% solids1 polymerizable fluid by passing the fluid through a die onto the surface of the substrate as the substrate moves relative to the die.
The die includes a channel adapted to receive the fluid and an adjustable width slot in communication with the channel through which the f luid is passed .
The slot is formed between the C9 .~ L~ u bar 66 and the U~JD~LC:OIU bar 64. The ~1 I.D~Leam bar lip is formed 35 as a sharp edge 70 and the ll~- ~L~ U bar lip is formed as a land 68 which substAnt i A 1 1 Y corresponds in shape WO95/29766 21 87896 P~J~ ~''0I1~ --to the shape of the substrate in the immediate area of coating fluid application. As used herein, "upstream"
and "d .~.Lr~ l" are relative to the direction of the moving substrate.
In preferred ~ s, the edge radius of the sharp edge (as defined in Fig. 3) measures no more than about 10 microns, and more preferably ranges from about 2 to about 4 micron6. The edge angle Al of the sharp edge (as defined in Fig. 3) preferably ranges from about 20 to about 75 and preferably is about 50 -60 .
The Cu~ve:Ly_.~Ce of the die C (as defined in Fig.
3) preferably ranges from about 0 to about 2.29, more preferably from about 0 to about 1.5.
The 6harp edge and the land are pref erably configured such that the sharp edge is displaced towards the surface of the substrate relative to the land. The degree of ~ pl~ L is referred to as "overbite" 0. Preferably, the overbite i8 no greater 20 than about 0 . 64 mm.
The sharp edge is substantially straight. For example, along a distance of about 25 cm measured anywhere along the sharp edge, the straightness of the edge does not vary by more than about 2 . 5 microns, and 25 pref erably no more than about 1 micron .
The rate at which the f luid passes through the die and the rate at which the 6ubstrate moves relative to the die are adjusted to provide a substantially uniform caliper coating on the substrate.
The viscosity of the coating fluid is preferably at least about 10 cps, and may be 100 cps or greater, or even 1000 cps or greater. The method may be adapted to apply both thin and thick coatings. During coating, a vacuum may be applied to the upstream side of the die 35 to improve coating quality if desired. The sub8trate may be a web.
~ WO ss/29766 2 ~ ~ 7~ ~ 6 ~ o l l ~
The invention enables the p~-:~aL~tion of solvent-free coatings having uniform caliper in both the downweb and uL~e- _b directions. Both thick and thin films can be prc~aI6d. The invention i5 useful in a 5 variety of settings, ;nnl~ in~ the preparation of optical quality thin films and adhesive films.
Other features and advantages of the invention will be apparent from the following description of the preferred ' ' i- -nts thereof, and from the claims .
Brief Descrit~tion of the Drawi n-~c The invention will be more fully understood with reference to the following drawings in which:
Figure 1 is a cross-sectional view of an extrusion die of the present invention.
Figure 2 is an enlarged ~;Lo58 s~ ional view of the slot and lip of the die of Figure 1.
Figure 3 is a ~iL uss-sectional view of the slot and lip similar to that of Figure 2.
Figure 4 is a ~iLùss~ nt;nnAl view of an 20 alternative vacuum chamber alL , L.
Figure 5 is a cross-sectional view of another alternative vacuum chamber aL~ y. ~.
Figure 6 is a ~iLOSS se.il irnAl view of an alternative extrusion die of the present invention.
Figures 7A and 7B are enlarged ~:L~Sfi-C~ Li~n~l views of the slot, face, and vacuum chamber of the die of Figure 6.
Figures 8A and 8B are schematic views of the die of Figure 6.
Descri~tion of the Preferred F~ i c This invention is a die coating method for coating polymerizable fluids onto substrates (e.g., webs) the die includes an U~Lt:CUU die lip formed as a sharp edge and a il .,D~L-:am die lip formed as a land. The shape 35 of the land substantially :~L' e:DpOIldS to the shape of the substrate in the immediate area of coating f luid Wo 95/29766 2 l 81 ~ 9 6 r~~
application. The 6hape of the ~iub~LL~te may be flat or curved .
Figure 1 shows an extrusion die 40 with a vacuum chamber 42 useful in the coating method according to 5 the present invention. Polymerizable fluid 44 is supplied by a pump 46 to the die 40 for application to a moving substrate 48, supported by a backup roll 50.
Polymerizable f luid 44 is supplied through a channel 52 to a manifold 54 for distribution through a slot 56 and 10 coating onto the moving substrate 48. The height and width of slot 56 can be controlled by means of a U-shaped 6him 41. The shim is typically made of brass or stainless steel.
As shown in Figure 2, the polymerizable fluid 44 15 passes through the slot 56 and forms a continuous coating bead 58 between the ' ...,LLeam edge 72 of land 68, the lip of d~ LL t ~llu bar 66, and the substrate 48 .
Vacuum chamber 42 (Figure 1) applies vacuum u~LLe:a~ of the bead to s~hil i 7e the coating bead. If desired, 20 the ~ Lu~c: of both die 40 and backup roll 50 may be controlled to improve coating rheology.
The polymerizable f luid can be one of ~u~
compositions. Polymerization may be th~-l ly induced or radiation induced (e.g., ultraviolet radiation or 25 electron beam). r ~ of suitable polymerizable f luids include epoxies, acrylates, methacrylates, vinyl ethers, isocyanates, and mixtures thereof. The resulting coatings are useful in a variety of applications, ;n~ ;n~ adhesive6, optical quality 30 films (e.g., polymer dispersed liquid crystal or "PDLC"
films and optical adhesives), precision caliper films, and vibration damping materials. The coatings are particularly useful in applications reS~uiring thin films with uniform caliper control.
The lip of the upstream bar 64 is formed as a curved land 68 and the lip of the downstream bar 66 is 21 ~7~96 095129766 P~l/~ s lt~
formed a6 a sharp edge 70. Sharp edge 70 should be clean and free of nicks and burrs, and should be straight within 1 micron in 25 cm of length measured anywhere along the edge. The edge radius should be no 5 greater than 10 microns. The radius of the curved land 68 should be egual to the radius of the backup roll 50 plus a minimal, and non-critical, 0.13 mm allowance for coating gap and substrate th; rlrn~B5.
Figure 3 show6 dimensions of geometric operating 10 parameters f or single layer extrusion . The length L~ of the curved land 68 on the u~:.LLe:all~ bar 64 can range from 1. 6 mm to 25 . 4 mm. The preferred length L~ is 12 . 7 mm. The edge angle Al of the downstream bar 66 can range from 20 to 75, and is preferably 50-60O. The 15 dle attack angle A2 between the downstream bar 66 surface of the coating slot 56 and the tangent plane P
through a line on the substrate 48 surface parallel to, and directly opposite, the sharp edge 70 can range from 60 to 120 and is preferably 90 to 95. The coating 20 gap G~ is the distance between the sharp edge 70 and the substrate 48.
Slot height H is the distance between u~JD~L~a~ bar 64 and ~ .DL~am bar 66, and is controlled by controlling the thickness of shim 41 (shown in Figure 25 1). In general, the slot height ranges from 0.076 mm to 1.27 mm.
overbite O is a positioning of the sharp edge 70 of the ~ all~ bar 66, with respect to the ;' IID~Le:alll edge 72 of the curved land 68 on the 30 U~DLLe:alll bar 64, in a direction toward the substrate 48. Overbite also can be viewed as a retraction of the d~..llDLLC:am edge 72 of the curved land 68 away from the substrate 48, with respect to the sharp edge 70, for any given coating gap G~. Overbite can range from 0 mm 35 to 0.64 mm, and the set~;ng~ at opposite ends of the die slot should be within 2 . 5 microns of each other.
WO 95/29766 2 ~ 8 7 8 9 6 P~"~
CGIIVeL~ Ce C is a counterclockwise, as shown in Figure 3, positioning of the curved land 68 away from a location parallel to the substrate 48, with the f du...,~LL~ am edge 72 being the center of rotation.
5 Cvll~_ly~ e can range from oo to 2.29, and the ~ett;n~c at opposite ends of the die slot should be within O . 023 of each other .
Overbite, slot height and ~;u~ y~l~. e together affect the ability of the coating die to hold a steady 10 bead. The interaction between these variable6 depends upon the rheology of the polymerizable coating;
accordingly, these variables, along with the substrate speed, are adjusted based upon the particular polymerizable coating being uaed.
Optimum coating quality is achieved when the die coating ~l~aL~Lus is isolated from ambient sources of vibration and/or other disrupting factors.
The vacuum chamber 4 2, as shown in Figure 4, can be an integral part of, or clamped securely to, the 20 U~DLL~:~III bar 64 to allow precise, repeatable vacuum system gas flow. The vacuum chamber 42 is formed using a vacuum bar 74 and can be .:ul,,,c:uLed through a vacuum restrictor 76 and a vacuum manifold 78 to a vacuum source channel 80. As shown in Figure 4, a curved 25 vacuum land 82 is attached directly to the u~LLe:~uu bar 64. The vacuum land 82 has the same radius of ;ULV~LULa as the curved land 68. The curved land 68 and the vacuum land 82 can be f inish-ground together 80 they are "in line" with each other. The vacuum land 82 30 and the curved land 68 then have the same cu"veLyellce with respect to the substrate 48.
The vacuum land gap G2 is the distance between the vacuum land 82 and the substrate 48, and is the sum total of the coating gap G~, the overbite, and the 35 displacement caused by the u"v~l4t:l~ce C of the curved land. When the vacuum land gap G2 is large, an ~ 1 8~96 wog5/29766 r l~l a _7 eYce6sive inrush of ambient air to the vacuum chamber 42 occurs. Even though the vacuum 60urce may have 6ufficient capacity to ~ Le and maintain the specified vacuum ,ULe:~~ULe level at the vacuum chamber 5 42, the inrush of air can have undesirable effect6.
In Figure 5, the vacuum land 82 is part of a vacuum bar 74 which is attached to the u~LLe~ bar 64.
During fabrication, the curved land 68 is finished with the uC~v~ e "ground in. " The vacuum bar 74 i6 then 10 attached and the vacuum land 82 is fini6h ground, using a different grind center, such that the vacuum land 82 i8 parallel to the 6ub6trate 48, and the vacuum land gap G2 is equal to the coating gap G, for one pre6elected value of the overbite. The vacuum land 15 length L2 may range from 6.35 mm to 25.4 mm. The preferred length L2 i6 12.7 mm. This ~-~i L has greater overall coating r~r~hi l ity in difficult coating situations compared to the ' i r L of Figure 4, but it is always finish ground for one specific set of 20 operating conditions. Consequently, as coating gap G~
or overbite 0 are changed vacuum land gap G2 may move away from its optimum value.
In Figure6 6, 7A, and 7B, the die 40 is mounted on an upstream bar positioner 84, and the vacuum bar 74 is 25 mounted on a vacuum bar positioner 86. The curved land 68 on the u~_LLe~m bar 64 and the vacuum land 82 on the vacuum bar 74 are not cAnnPctP~l directly to each other.
The vacuum chamber 4 2 is connected to its vacuum source through the vacuum bar 74 and the positioner 86. The 30 mounting and positioning for the vacuum bar 74 are separate from those for the U~U~LL~:~IU bar 64. A
flexible vacuum seal strip 88 seals between the U~.LLe~llll bar 64 and the vacuum bar 74.
The gap G2 between the vacuum land 82 and the 35 substrate 48 i8 not affected by coating gap G~, overbite, or ullveL~ ce change6, and may be held at Wog~/29766 2~87896 ~ tl~o ~
it6 optimum value continuously, during coating. The vacuum land gap G2 may be set within the range from 0.076 mm to 0.508 mm. The preferred value for the gap G2 is 0.15 mm. The ~L~fe:~L~d angular position for the 5 vacuum land is parallel to the substrate 48.
Figures 8A and 8B show some positioning adjustments and the vacuum chamber closure. Overbite adjustment OA translates the downstream bar 66 with respect to the u~LL~z~lu bar 64 such that the sharp edge 10 70 moves toward or away from the substrate 48 with respect to the ~ ",.~L-:am edge 72 of the curved land 68. C~llvc~yt~ adjustment CA rotates the upstream bar 64 and the ~ D~Leam bar 66 together around an axis running through the d~...llDLLt:alU edge 72, such that the 15 curved land 68 moves counterclockwise from the position shown in Figures 8A and 8B, away from parallel to the substrate 48, or clockwise back toward parallel.
Coating gap adjustment CGA translates the upstream bar 64 and the ~ "~.LL~:a u bar 66 together to change the 20 distance between the sharp edge 70 and the DUL:~LLC~te 48, while the vacuum bar remains s tationary on its mount 86, and the vacuum seal strip 88 flexes to prevent air leakage during a-ljuDi L6. Air leakage at the ends of the die into the vacuum chamber 42 is 25 m;n;m;7~-1 by end plates 90 attached to the ends of the vacuum bar 74 which overlap the ends of the u~LLt:-llu bar 64. The vacuum bar 74 is 0.10 mm to 0.15 mm longer than the upstream bar 64, so, in a centered condition, the clearance between each end plate 90 and the 30 U~ Le:~:lIU bar 64 will range from 0.050 mm to 0.075 mm.
The width of the coating yLvduced by a given die is reduced where indicated by ~Ac.rlrl ;nq~ the die and the vacuum chamber by ~ ;ULLC:llLly inc~,L~,L~-ting a) shaped plugs to reduce the widths of the die cavity 35 manifold 54 and vacuum chamber 42 to the rl~rl~l; ng width ~W095/29766 2~878~ P~ s~ --and b) a shim into the die that has a shim slot width ..u...,~ in~ to the ~rkl ing width.
During coating, it has been found that, as a cc~nseyue:~U of the ,i~ U~LUL~ of die 40, bead 58 does 5 not move down to any appreciable extent into the space between curved land 68 and the moving substrate 48, even as vacuum is increased. This allows the use of relatively high vacuum levels. M~ ,v~:., good results are obtained even in the absence of vacuum. In 10 addition, the effect of "runout" in back-up roll 50 on downweb coating weight i8 min1mi7~1.
The abu~ des.;.ibed die ~L~ U~ coupled with careful control of (a) the rate at which the polymerizable composition is delivered to the die 15 (through control of pump speed) and (b) the substrate speed results in coatings having uniform caliper in both the downweb and ~;L ~ directions .
For applications where optical ~eaLc.~.~e of the article is critical, r~nt~minAtion resulting from 20 airborne particulates can be reduced by coating substrate6 in a clean room environment.
The invention will now be more fully understood with reference to the following examples which are not to be construed as limiting the scope of the invention.
2 5 1! ~ANPLE8 Test P~ ,r~ A
The ele. L.~, ~,~Lical rPRp~n~PP: of the PDLC devices were characterized using a computer-co~.L~ ~,lled test stand consisting of an IBM personal computer interfaced 30 with Kepco 125-lKVA-3T power supply, a Dyn-Optics Optical Nonitor 590, and a Valhalla Scientific 2300 Series Digital Power Analyzer. The optics of the Dyn-optics Optical Monitor were adjusted such that the ~rec~ r tr~n~ fiit -l of photopically-filter light at 35 an approximate 6 collection half angle was measured relative to an open beam.
Wos5ng766 2 l ~7 ~ r~.,, s 11~ ~
A sample of a PDLC film/electrode sandwich measuring several square centimeters was attached to the lead6 of the power supply using a cnnn~ctnr such as that described in the aforementioned Engfer et al.
5 application. A 60 Hz voltage ranging from zero to 120 volts AC tVAC) was applied to the sample in 5 VAC
inUL- LE and the SrerlllAr tr~n-miccil~n recorded.
Test PL . .~. .1 . I e B
The haze of the powered tl20 VAC, 60 Hz) PDLC
10 devices was measured using a Pacif ic Scientif ic Gardner XL-835 Colorimeter according to the manufacturer's instructions .
A series of adhesives were prepared from 15 prepolymer syrups consisting of a mixture of 90 wt. %
lsooctyl acrylate and 10 wt. % acrylic acid tAldrich, Nilwaukee, WI) containing 0 . 04 wt. % photoinitiator 2-phenyl-2,2-~ii LLU"Y acetorhPnnn~ tK13-1, Sartomer, West Chester, PA) as described in U.S. Pat. No. 4,330,590 tVesley), which is incuL~,Lc~ted herein by reference.
The syrups were partially photopolymerized to viscosities of 360, 1950 and 5600 cps tas ~ ed on a Brookf ield viscometer using a t4 spindle operating at 60 rpm) by varying the e~lJo~uLe times.
After the syrups had been advanced to the indicated viscosities, an additional 0.1 wt.% RB-l photoinitiator and 0 . 2 wt. % hPY~n~ ; Ol diacrylate (Sartomer, West Chester, PA) were added to the syrups and the mixtures agitated until ~ f luids were 3 o obtained. The resulting f luids were coated on the substrates at the th; rlrn--cR~c indicated in Table 1 using a precision coating die as described above and the lamination ~aL~.Lu~ described in Vesley et al., PCT International application No.
35 (Attorney's Docket No. 50777PCT7A) entitled "Lamination Process for Coatings," filed u ul~uuLLellLly with the ~WO9s/29766 27~7~9~ P ~
present application and assigned to the 6ame assignee as the present application.
During the coating operation, the first substrate was unwound from a first unwind roll and passed over a 5 Ls~ e "hrrl in~, unheated steel backup roll 25.4 cm (10 inches) in d~ t~Pr where a 10.2 cm (4 inch) wide strip of the prepolymer syrup, which was delivered to the precision coating die using a precision gear pump (available from Zenith Corp. ), was coated onto the 10 first surface of the first substrate using a 10.2 cm (4 inch) die with no vacuum applied to the vacuum chamber.
In EYamples 1-4, a coating die similar to that illustrated in Figure 4 was configured with a 0 . 50 mm (20 mil) shim, a 0 cu~velyt:nCe~ an overbite of 0.076 15 mm (3 mil), a coating land L~ of 12.7 mm, a vacuum land L2 f 12 . 7 mm, and a die attack angle A2 of 90. In Examples 5-6, a 20.3 cm (8 inch) wide strip of the prepolymer syrup was coated onto the first surface of the first substrate using a 20.3 cm (8 inch) die 20 similar to that used for Examples 1-4 except that it was configured with a 0.048 mm (19 mil) shim and an overbite Or 0.254 mm (10 mil). The coating gap was adjusted as indicated in Table 1 along with the pump speed and substrate speed to produce coatings having 25 the indicated th i rknPccPs . No vacuum was applied to the vacuum chamber during the coating operation.
The second substrate was unwound f rom a second unwind roll and passed around a 2 . 54 cm ( 1 inch) diameter sintered metal laminator bar where it was 30 laminated to the coated face of the first sub6trate according to the pl~,ceduLe: described in the aforementioned Vesley et al. application. The laminator bar was located approximately 12 cm (4.7 inches) ~ Lr ~ from the backup roll such that the 35 coated substrate was not in contact with the backup roll or other idler or takeup roll at the point of Wog~tt9766 21 8789~ 1~1,1 5 ~l6~ ~
lamination, and positioned 80 that the uncoated first substrate was d~ aDsed approximately 3.8 mm (150 mils) below the plane def ined by the f irst substrate as it passed between the backup roll and the idler roll; the 5 extent of depression is hereinafter referred to as "interference. " Air ~JL~DnULe: (approximately 2 . l bar) through the sintered metal bar was adjusted to provide a cushion of air between the laminator bar and the second substrate.
The thus ~Lulu~.ed uncured laminate construction was cured to a high per~ormance ~LaDauLa sensitive adhe6ive by passing the construction under a bank of fluuL_6ce.,~ black lights lamps (F20T12-350BL, available from Osram Sylvania, Danvers, MA). The laminate 15 .ullDLLuuLion was exposed to 360 mJ/cm2 of irradiation as - .:d with a WIRAD radiometer (model number UR365C~3, available from Electronic InDLLI Ltltion and Technology, Inc., Sterling, VA) equipped with a glass filter responsive between 300 and 400 nm, with a 20 maximum tr~n-~i C-cion at 365 nm. The average light intensity in the curing zone was about 2 . 3 mW/cm2.
Coating speeds were controlled by a vacuum pull roll positioned at the end of the cûating line and were maintained at approximately 5.5 m/min. (11 feet/min).
Table 1 shows typical coating variations for various coating thi 1~ ~p~6ec and viscosities. The cured adhesives of examples 5 and 6 adhered to the polyester when the laminated collDLL ... Lion was peeled apart.
Adhesive and shear properties of the cured polymer 30 syrupS of r 1PC 5-6 were consistent with the properties obtained from similar formulations cured under the conditions described in U. S . Pat. No.
The 6harp edge and the land are pref erably configured such that the sharp edge is displaced towards the surface of the substrate relative to the land. The degree of ~ pl~ L is referred to as "overbite" 0. Preferably, the overbite i8 no greater 20 than about 0 . 64 mm.
The sharp edge is substantially straight. For example, along a distance of about 25 cm measured anywhere along the sharp edge, the straightness of the edge does not vary by more than about 2 . 5 microns, and 25 pref erably no more than about 1 micron .
The rate at which the f luid passes through the die and the rate at which the 6ubstrate moves relative to the die are adjusted to provide a substantially uniform caliper coating on the substrate.
The viscosity of the coating fluid is preferably at least about 10 cps, and may be 100 cps or greater, or even 1000 cps or greater. The method may be adapted to apply both thin and thick coatings. During coating, a vacuum may be applied to the upstream side of the die 35 to improve coating quality if desired. The sub8trate may be a web.
~ WO ss/29766 2 ~ ~ 7~ ~ 6 ~ o l l ~
The invention enables the p~-:~aL~tion of solvent-free coatings having uniform caliper in both the downweb and uL~e- _b directions. Both thick and thin films can be prc~aI6d. The invention i5 useful in a 5 variety of settings, ;nnl~ in~ the preparation of optical quality thin films and adhesive films.
Other features and advantages of the invention will be apparent from the following description of the preferred ' ' i- -nts thereof, and from the claims .
Brief Descrit~tion of the Drawi n-~c The invention will be more fully understood with reference to the following drawings in which:
Figure 1 is a cross-sectional view of an extrusion die of the present invention.
Figure 2 is an enlarged ~;Lo58 s~ ional view of the slot and lip of the die of Figure 1.
Figure 3 is a ~iL uss-sectional view of the slot and lip similar to that of Figure 2.
Figure 4 is a ~iLùss~ nt;nnAl view of an 20 alternative vacuum chamber alL , L.
Figure 5 is a cross-sectional view of another alternative vacuum chamber aL~ y. ~.
Figure 6 is a ~iLOSS se.il irnAl view of an alternative extrusion die of the present invention.
Figures 7A and 7B are enlarged ~:L~Sfi-C~ Li~n~l views of the slot, face, and vacuum chamber of the die of Figure 6.
Figures 8A and 8B are schematic views of the die of Figure 6.
Descri~tion of the Preferred F~ i c This invention is a die coating method for coating polymerizable fluids onto substrates (e.g., webs) the die includes an U~Lt:CUU die lip formed as a sharp edge and a il .,D~L-:am die lip formed as a land. The shape 35 of the land substantially :~L' e:DpOIldS to the shape of the substrate in the immediate area of coating f luid Wo 95/29766 2 l 81 ~ 9 6 r~~
application. The 6hape of the ~iub~LL~te may be flat or curved .
Figure 1 shows an extrusion die 40 with a vacuum chamber 42 useful in the coating method according to 5 the present invention. Polymerizable fluid 44 is supplied by a pump 46 to the die 40 for application to a moving substrate 48, supported by a backup roll 50.
Polymerizable f luid 44 is supplied through a channel 52 to a manifold 54 for distribution through a slot 56 and 10 coating onto the moving substrate 48. The height and width of slot 56 can be controlled by means of a U-shaped 6him 41. The shim is typically made of brass or stainless steel.
As shown in Figure 2, the polymerizable fluid 44 15 passes through the slot 56 and forms a continuous coating bead 58 between the ' ...,LLeam edge 72 of land 68, the lip of d~ LL t ~llu bar 66, and the substrate 48 .
Vacuum chamber 42 (Figure 1) applies vacuum u~LLe:a~ of the bead to s~hil i 7e the coating bead. If desired, 20 the ~ Lu~c: of both die 40 and backup roll 50 may be controlled to improve coating rheology.
The polymerizable f luid can be one of ~u~
compositions. Polymerization may be th~-l ly induced or radiation induced (e.g., ultraviolet radiation or 25 electron beam). r ~ of suitable polymerizable f luids include epoxies, acrylates, methacrylates, vinyl ethers, isocyanates, and mixtures thereof. The resulting coatings are useful in a variety of applications, ;n~ ;n~ adhesive6, optical quality 30 films (e.g., polymer dispersed liquid crystal or "PDLC"
films and optical adhesives), precision caliper films, and vibration damping materials. The coatings are particularly useful in applications reS~uiring thin films with uniform caliper control.
The lip of the upstream bar 64 is formed as a curved land 68 and the lip of the downstream bar 66 is 21 ~7~96 095129766 P~l/~ s lt~
formed a6 a sharp edge 70. Sharp edge 70 should be clean and free of nicks and burrs, and should be straight within 1 micron in 25 cm of length measured anywhere along the edge. The edge radius should be no 5 greater than 10 microns. The radius of the curved land 68 should be egual to the radius of the backup roll 50 plus a minimal, and non-critical, 0.13 mm allowance for coating gap and substrate th; rlrn~B5.
Figure 3 show6 dimensions of geometric operating 10 parameters f or single layer extrusion . The length L~ of the curved land 68 on the u~:.LLe:all~ bar 64 can range from 1. 6 mm to 25 . 4 mm. The preferred length L~ is 12 . 7 mm. The edge angle Al of the downstream bar 66 can range from 20 to 75, and is preferably 50-60O. The 15 dle attack angle A2 between the downstream bar 66 surface of the coating slot 56 and the tangent plane P
through a line on the substrate 48 surface parallel to, and directly opposite, the sharp edge 70 can range from 60 to 120 and is preferably 90 to 95. The coating 20 gap G~ is the distance between the sharp edge 70 and the substrate 48.
Slot height H is the distance between u~JD~L~a~ bar 64 and ~ .DL~am bar 66, and is controlled by controlling the thickness of shim 41 (shown in Figure 25 1). In general, the slot height ranges from 0.076 mm to 1.27 mm.
overbite O is a positioning of the sharp edge 70 of the ~ all~ bar 66, with respect to the ;' IID~Le:alll edge 72 of the curved land 68 on the 30 U~DLLe:alll bar 64, in a direction toward the substrate 48. Overbite also can be viewed as a retraction of the d~..llDLLC:am edge 72 of the curved land 68 away from the substrate 48, with respect to the sharp edge 70, for any given coating gap G~. Overbite can range from 0 mm 35 to 0.64 mm, and the set~;ng~ at opposite ends of the die slot should be within 2 . 5 microns of each other.
WO 95/29766 2 ~ 8 7 8 9 6 P~"~
CGIIVeL~ Ce C is a counterclockwise, as shown in Figure 3, positioning of the curved land 68 away from a location parallel to the substrate 48, with the f du...,~LL~ am edge 72 being the center of rotation.
5 Cvll~_ly~ e can range from oo to 2.29, and the ~ett;n~c at opposite ends of the die slot should be within O . 023 of each other .
Overbite, slot height and ~;u~ y~l~. e together affect the ability of the coating die to hold a steady 10 bead. The interaction between these variable6 depends upon the rheology of the polymerizable coating;
accordingly, these variables, along with the substrate speed, are adjusted based upon the particular polymerizable coating being uaed.
Optimum coating quality is achieved when the die coating ~l~aL~Lus is isolated from ambient sources of vibration and/or other disrupting factors.
The vacuum chamber 4 2, as shown in Figure 4, can be an integral part of, or clamped securely to, the 20 U~DLL~:~III bar 64 to allow precise, repeatable vacuum system gas flow. The vacuum chamber 42 is formed using a vacuum bar 74 and can be .:ul,,,c:uLed through a vacuum restrictor 76 and a vacuum manifold 78 to a vacuum source channel 80. As shown in Figure 4, a curved 25 vacuum land 82 is attached directly to the u~LLe:~uu bar 64. The vacuum land 82 has the same radius of ;ULV~LULa as the curved land 68. The curved land 68 and the vacuum land 82 can be f inish-ground together 80 they are "in line" with each other. The vacuum land 82 30 and the curved land 68 then have the same cu"veLyellce with respect to the substrate 48.
The vacuum land gap G2 is the distance between the vacuum land 82 and the substrate 48, and is the sum total of the coating gap G~, the overbite, and the 35 displacement caused by the u"v~l4t:l~ce C of the curved land. When the vacuum land gap G2 is large, an ~ 1 8~96 wog5/29766 r l~l a _7 eYce6sive inrush of ambient air to the vacuum chamber 42 occurs. Even though the vacuum 60urce may have 6ufficient capacity to ~ Le and maintain the specified vacuum ,ULe:~~ULe level at the vacuum chamber 5 42, the inrush of air can have undesirable effect6.
In Figure 5, the vacuum land 82 is part of a vacuum bar 74 which is attached to the u~LLe~ bar 64.
During fabrication, the curved land 68 is finished with the uC~v~ e "ground in. " The vacuum bar 74 i6 then 10 attached and the vacuum land 82 is fini6h ground, using a different grind center, such that the vacuum land 82 i8 parallel to the 6ub6trate 48, and the vacuum land gap G2 is equal to the coating gap G, for one pre6elected value of the overbite. The vacuum land 15 length L2 may range from 6.35 mm to 25.4 mm. The preferred length L2 i6 12.7 mm. This ~-~i L has greater overall coating r~r~hi l ity in difficult coating situations compared to the ' i r L of Figure 4, but it is always finish ground for one specific set of 20 operating conditions. Consequently, as coating gap G~
or overbite 0 are changed vacuum land gap G2 may move away from its optimum value.
In Figure6 6, 7A, and 7B, the die 40 is mounted on an upstream bar positioner 84, and the vacuum bar 74 is 25 mounted on a vacuum bar positioner 86. The curved land 68 on the u~_LLe~m bar 64 and the vacuum land 82 on the vacuum bar 74 are not cAnnPctP~l directly to each other.
The vacuum chamber 4 2 is connected to its vacuum source through the vacuum bar 74 and the positioner 86. The 30 mounting and positioning for the vacuum bar 74 are separate from those for the U~U~LL~:~IU bar 64. A
flexible vacuum seal strip 88 seals between the U~.LLe~llll bar 64 and the vacuum bar 74.
The gap G2 between the vacuum land 82 and the 35 substrate 48 i8 not affected by coating gap G~, overbite, or ullveL~ ce change6, and may be held at Wog~/29766 2~87896 ~ tl~o ~
it6 optimum value continuously, during coating. The vacuum land gap G2 may be set within the range from 0.076 mm to 0.508 mm. The preferred value for the gap G2 is 0.15 mm. The ~L~fe:~L~d angular position for the 5 vacuum land is parallel to the substrate 48.
Figures 8A and 8B show some positioning adjustments and the vacuum chamber closure. Overbite adjustment OA translates the downstream bar 66 with respect to the u~LL~z~lu bar 64 such that the sharp edge 10 70 moves toward or away from the substrate 48 with respect to the ~ ",.~L-:am edge 72 of the curved land 68. C~llvc~yt~ adjustment CA rotates the upstream bar 64 and the ~ D~Leam bar 66 together around an axis running through the d~...llDLLt:alU edge 72, such that the 15 curved land 68 moves counterclockwise from the position shown in Figures 8A and 8B, away from parallel to the substrate 48, or clockwise back toward parallel.
Coating gap adjustment CGA translates the upstream bar 64 and the ~ "~.LL~:a u bar 66 together to change the 20 distance between the sharp edge 70 and the DUL:~LLC~te 48, while the vacuum bar remains s tationary on its mount 86, and the vacuum seal strip 88 flexes to prevent air leakage during a-ljuDi L6. Air leakage at the ends of the die into the vacuum chamber 42 is 25 m;n;m;7~-1 by end plates 90 attached to the ends of the vacuum bar 74 which overlap the ends of the u~LLt:-llu bar 64. The vacuum bar 74 is 0.10 mm to 0.15 mm longer than the upstream bar 64, so, in a centered condition, the clearance between each end plate 90 and the 30 U~ Le:~:lIU bar 64 will range from 0.050 mm to 0.075 mm.
The width of the coating yLvduced by a given die is reduced where indicated by ~Ac.rlrl ;nq~ the die and the vacuum chamber by ~ ;ULLC:llLly inc~,L~,L~-ting a) shaped plugs to reduce the widths of the die cavity 35 manifold 54 and vacuum chamber 42 to the rl~rl~l; ng width ~W095/29766 2~878~ P~ s~ --and b) a shim into the die that has a shim slot width ..u...,~ in~ to the ~rkl ing width.
During coating, it has been found that, as a cc~nseyue:~U of the ,i~ U~LUL~ of die 40, bead 58 does 5 not move down to any appreciable extent into the space between curved land 68 and the moving substrate 48, even as vacuum is increased. This allows the use of relatively high vacuum levels. M~ ,v~:., good results are obtained even in the absence of vacuum. In 10 addition, the effect of "runout" in back-up roll 50 on downweb coating weight i8 min1mi7~1.
The abu~ des.;.ibed die ~L~ U~ coupled with careful control of (a) the rate at which the polymerizable composition is delivered to the die 15 (through control of pump speed) and (b) the substrate speed results in coatings having uniform caliper in both the downweb and ~;L ~ directions .
For applications where optical ~eaLc.~.~e of the article is critical, r~nt~minAtion resulting from 20 airborne particulates can be reduced by coating substrate6 in a clean room environment.
The invention will now be more fully understood with reference to the following examples which are not to be construed as limiting the scope of the invention.
2 5 1! ~ANPLE8 Test P~ ,r~ A
The ele. L.~, ~,~Lical rPRp~n~PP: of the PDLC devices were characterized using a computer-co~.L~ ~,lled test stand consisting of an IBM personal computer interfaced 30 with Kepco 125-lKVA-3T power supply, a Dyn-Optics Optical Nonitor 590, and a Valhalla Scientific 2300 Series Digital Power Analyzer. The optics of the Dyn-optics Optical Monitor were adjusted such that the ~rec~ r tr~n~ fiit -l of photopically-filter light at 35 an approximate 6 collection half angle was measured relative to an open beam.
Wos5ng766 2 l ~7 ~ r~.,, s 11~ ~
A sample of a PDLC film/electrode sandwich measuring several square centimeters was attached to the lead6 of the power supply using a cnnn~ctnr such as that described in the aforementioned Engfer et al.
5 application. A 60 Hz voltage ranging from zero to 120 volts AC tVAC) was applied to the sample in 5 VAC
inUL- LE and the SrerlllAr tr~n-miccil~n recorded.
Test PL . .~. .1 . I e B
The haze of the powered tl20 VAC, 60 Hz) PDLC
10 devices was measured using a Pacif ic Scientif ic Gardner XL-835 Colorimeter according to the manufacturer's instructions .
A series of adhesives were prepared from 15 prepolymer syrups consisting of a mixture of 90 wt. %
lsooctyl acrylate and 10 wt. % acrylic acid tAldrich, Nilwaukee, WI) containing 0 . 04 wt. % photoinitiator 2-phenyl-2,2-~ii LLU"Y acetorhPnnn~ tK13-1, Sartomer, West Chester, PA) as described in U.S. Pat. No. 4,330,590 tVesley), which is incuL~,Lc~ted herein by reference.
The syrups were partially photopolymerized to viscosities of 360, 1950 and 5600 cps tas ~ ed on a Brookf ield viscometer using a t4 spindle operating at 60 rpm) by varying the e~lJo~uLe times.
After the syrups had been advanced to the indicated viscosities, an additional 0.1 wt.% RB-l photoinitiator and 0 . 2 wt. % hPY~n~ ; Ol diacrylate (Sartomer, West Chester, PA) were added to the syrups and the mixtures agitated until ~ f luids were 3 o obtained. The resulting f luids were coated on the substrates at the th; rlrn--cR~c indicated in Table 1 using a precision coating die as described above and the lamination ~aL~.Lu~ described in Vesley et al., PCT International application No.
35 (Attorney's Docket No. 50777PCT7A) entitled "Lamination Process for Coatings," filed u ul~uuLLellLly with the ~WO9s/29766 27~7~9~ P ~
present application and assigned to the 6ame assignee as the present application.
During the coating operation, the first substrate was unwound from a first unwind roll and passed over a 5 Ls~ e "hrrl in~, unheated steel backup roll 25.4 cm (10 inches) in d~ t~Pr where a 10.2 cm (4 inch) wide strip of the prepolymer syrup, which was delivered to the precision coating die using a precision gear pump (available from Zenith Corp. ), was coated onto the 10 first surface of the first substrate using a 10.2 cm (4 inch) die with no vacuum applied to the vacuum chamber.
In EYamples 1-4, a coating die similar to that illustrated in Figure 4 was configured with a 0 . 50 mm (20 mil) shim, a 0 cu~velyt:nCe~ an overbite of 0.076 15 mm (3 mil), a coating land L~ of 12.7 mm, a vacuum land L2 f 12 . 7 mm, and a die attack angle A2 of 90. In Examples 5-6, a 20.3 cm (8 inch) wide strip of the prepolymer syrup was coated onto the first surface of the first substrate using a 20.3 cm (8 inch) die 20 similar to that used for Examples 1-4 except that it was configured with a 0.048 mm (19 mil) shim and an overbite Or 0.254 mm (10 mil). The coating gap was adjusted as indicated in Table 1 along with the pump speed and substrate speed to produce coatings having 25 the indicated th i rknPccPs . No vacuum was applied to the vacuum chamber during the coating operation.
The second substrate was unwound f rom a second unwind roll and passed around a 2 . 54 cm ( 1 inch) diameter sintered metal laminator bar where it was 30 laminated to the coated face of the first sub6trate according to the pl~,ceduLe: described in the aforementioned Vesley et al. application. The laminator bar was located approximately 12 cm (4.7 inches) ~ Lr ~ from the backup roll such that the 35 coated substrate was not in contact with the backup roll or other idler or takeup roll at the point of Wog~tt9766 21 8789~ 1~1,1 5 ~l6~ ~
lamination, and positioned 80 that the uncoated first substrate was d~ aDsed approximately 3.8 mm (150 mils) below the plane def ined by the f irst substrate as it passed between the backup roll and the idler roll; the 5 extent of depression is hereinafter referred to as "interference. " Air ~JL~DnULe: (approximately 2 . l bar) through the sintered metal bar was adjusted to provide a cushion of air between the laminator bar and the second substrate.
The thus ~Lulu~.ed uncured laminate construction was cured to a high per~ormance ~LaDauLa sensitive adhe6ive by passing the construction under a bank of fluuL_6ce.,~ black lights lamps (F20T12-350BL, available from Osram Sylvania, Danvers, MA). The laminate 15 .ullDLLuuLion was exposed to 360 mJ/cm2 of irradiation as - .:d with a WIRAD radiometer (model number UR365C~3, available from Electronic InDLLI Ltltion and Technology, Inc., Sterling, VA) equipped with a glass filter responsive between 300 and 400 nm, with a 20 maximum tr~n-~i C-cion at 365 nm. The average light intensity in the curing zone was about 2 . 3 mW/cm2.
Coating speeds were controlled by a vacuum pull roll positioned at the end of the cûating line and were maintained at approximately 5.5 m/min. (11 feet/min).
Table 1 shows typical coating variations for various coating thi 1~ ~p~6ec and viscosities. The cured adhesives of examples 5 and 6 adhered to the polyester when the laminated collDLL ... Lion was peeled apart.
Adhesive and shear properties of the cured polymer 30 syrupS of r 1PC 5-6 were consistent with the properties obtained from similar formulations cured under the conditions described in U. S . Pat. No.
4,330,590.
~ Wo 95K9766 2 J 8 7 8 9 6 T~bl-- 1 First Socoud Viscosily Contin~ Co-tiug E~mple Subst~te Substnte (cps)~ G-p (mm) Ibicl~ness (mm) 5 IPETI PETQ 365 0.175 0.223 i 0.004 2PET2 PET~ 365 0.175 0.154iO.003 3PET2 PET2 1,950 0.175 0.116iO.001 4PEI~ PET2 1,950 0.175 0.221iO.001 SRdense PElq 5,600 0127 O.150iO.OOI
P pa' 10 6 Rde~so PET2 5,600 0.05 0.93io 08 P~lpe~
1. Measured on a Brookfield vLacometer u~ing A ~4 ~pindle operating at 60 rpm.
2. Bia~ lly oriented PET ~ilm, 51 mLcrona (2 mila) thick.
15 3. Polyethyl _u.lLe~ p~per provided with ~ ailicone rele~ae co~tinq .
Ex~m~l~ 7 A PDLC device was ~Leua~ed from a fluid cmnt I;n;n~
(a) 55 parts of a mixture consisting of 30.0 wt.% RCC-15C curable matrix mixture obtained without initiator and with 50% less thiol (W.R. Grace, Atlanta, GA), 7.5 wt.9c acrylic acid, 30.0 wt.% isooctyl acrylate, 15.0 wt.~6 2~phel1u~LyeL11yl acrylate (Sartomer, West Chester, PA), 15 . 0 wt. % divinyl ether of triethylene glycol (International Specialty Products, Wayne, NJ), and 2.5 wt. % KB-l photoinitiator, and (b) 45 parts BL036 liquid crystal mixture (EN Industries, Hav L1.u...e, NY) having a 30 solution viscosity of 42 cps (measured on a Brookfield viscometer using a t3 spindle operating at 60 rpm).
The fluid, which was d~ s~d under vacuum for - approximately 2 minutes at ambient t~ ~lLULe, wa6 applied as a 15 . 2 cm ( 6 inch) wide strip to the 35 electrode surface of an ITO-coated polyester film (90/lO indium/tin oxide ratio, 80 ohms/square, 51 microns (2 mil) thick PET, available from Southwall Technologies, Palo Alto, CA) at a rate of approximately w0 95/29766 2 ~ 8 7 ~ 9 ~ P ~ s ~
152.4 cm/min (5 ft/minute) using the precision coating process described in r , ~ 6 eYcept that a 88 . 9 cm die similar to that illustrated in Figure 7a was used.
This die was deckled to produce a narrower coating and 5 configured with a 152 micron shim, a coating land having a length (L~) of 12.7 mm, a vacuum land having a length L2 f 12.7 mm, a 0.57 cvl~c,Lg~llce~ a 33 micron overbite, a vacuum land gap G~ of 0.152 mm, a die attack angle A2 Of 95, and a coatlng gap G~ of 102 microns.
10 The cv.lv_L~ ce of the vacuum bar was o and no vacuum was applied to the vacuum chamber during coating. Both the die and back-up roll were temperature controlled at 21C. A ~LeS~UL~ of 1.7 bar was maintained to the sintered metal bar during lamination and the lamination 15 bar was adjusted to provide an interference of 3 . 6 mm.
The uncured laminate vll~u~ LiOn was cured by passing the CVI-~ U- ~ion through a cooled curing chamber cvl-=,LLu~ed of ultraviolet transparent AcrylitelM OP-4 (available from Cyro Industries, Nt.
20 Arlington, NJ), extending approximately 61 cm (2 feet) into a cure chamber equipped with two banks of fluvL~sce,.l~ black lights (F20T12-350BL, available from osram Sylvania, Danvers, NA), one bank positioned on each side of the laminate. Air temperature in the 25 cooling chamber wa~ monitored by a Ule ~_ le mounted in the chamber under the second fluvLesc~ bulb and controlled at the indicated tl _ ~oLuL~a by ill-Lvdu~ ing temperature controlled air. Each side of the laminate uv~LLu~;Lion was exposed to approximately 530 mJ/cm2 of 30 radiation calculated from light intensities of 1.1 mW/cm2 as measured through the conductive electrode used in the PDLC device by means of a uvl~S~ll~; r~ c.r (model number UBM365M0, available from Electronic In_LL, Lcltion and Technology, Inc., Sterling, VA) 35 equipped with a glass filter responsive between 300 and 400 nm, with a maximum tr~n~ on at 365 nm. The ~ W095/29766 ;~l 81l~9~; r~l~u. ~
radiometer was specially calibrated to read in absolute lntensity .
The backup roll 50 was a pacer roll driven by a Torquer T~ Pr precision motor (available from 5 Inland Motor Division, Bradford, VA).
The cured coating th;~ knPGG of the resulting PDLC
film was 24+1 microns. The PDLC device had on- and off-state ~rAn^~;CCions of 73.1% and 1.2%, respectively, and a haze of 5. 8% .
r l-- 8 A PDLC device was prepared as described in Example 7 except that the coating fluid had the following composition: (a) 5û parts of a mixture consisting of 20.0 wt.% Vectomer 2020 tAllied-Signal, Inc., 15 Norri6town, NJ), 5.0 wt.% acrylic acid, 25.0 wt.%
isooctyl acrylate, 15.0 wt.% 2-phel.o..yéL~.yl acrylate, 10 wt.% trimethylolpropane tris(3 ~ pLopropionate) (Aldrich, Nilwaukee, WI), 22.5 wt.% cy--]nhPvlnp dimethanol divinyl ether (International Specialty 20 Products, Wayne, NJ) and 2.5 wt.9~ Escacure RB-1, and (b) 50 parts BL036 liquid crystal mixture. The viscosity of the coating fluid was 134 cps (measured on a Brookfield vis~ Pr using a ~3 spindle operating at 60 rpm). The coating t~ ~LuLe was 21C and during 25 lamination an air ples:~uLe of 2.4 bar was maintained to the laminator bar which was adjusted to provide an interference of 3 . 8 mm. The fluid was applied as a 15.2 cm (6 inch) wide strip to the electrode surface of an IT0-coated polyester f ilm at a rate of approximately 30 152.4 cm/min (5 ft/minute) using the precision coating process described in Example 7 except that the die was configured with a 46 micron overbite, a coating gap of 102 microns, and a vacuum of 1.9 mm Hg (1 inch of water) was used to apply the solution at 22C. The film 35 was cured at 21C by PYposin~ each side to approximately W09~l29766 ~ ~ 1 ~7~ P l/~ 5 ~ ~ ~
530 mJ/cm2 at an intensity of 1. 0 mW/cm2 to produce a PDLC film with a thicknes6 of 23+1 microns.
The PDLC device had on- and off-state transmissions of 71.9% and 1.1%, respectively, and a 5 haze of 4 . 8% .
1~ 9 A PDLC device was prepared as described in Example 7 except that the fluid contained 500 parts of BL036 liquid crystal mixture and 333 parts of a mixture 10 having the composition of 2 . 5 wt . % Esacure KB-1 photoinitiator, 7.5 wt.% acrylic acid, 30.0 wt.%
isooctyl acrylate, 15 . O wt. % 2~ph~ ye ~l~yl acrylate 15.0 wt.% Uralac 3004-102 (DSM Resins, U.s., Inc., Elgin, IL), and 30.0 wt.% Uralac 3004-300 (DSN Resins, 15 U.S., Inc., Elgin, IL). The 88.9 cm wide die was configured with a slot width of 88.9 cm, an overbite of 43 microns, a vacuum land gap G2 Of 24.5 mm and a vacuum of 1. 9 mm Hg was applied to the vacuum chamber during coating. The IT0-coated polyester film used for the 20 ele~ LL~,des was approximately 130 microns (5 mils) thick. An air ~La5r UL~: of 3.4 bar wa6 maintained to the laminator bar which was adjusted to provide an interference of 6.35 mm. The resulting laminate was exposed W light having an average intensity of approximately 1. 68 mW/cm2 at about 23 C to produce a PDLC f ilm approximately 18 microns thick .
The PDLC device had on- and of f -state trAnr~ sion~ of 73.4% and 1.7%, respectively, and a haze of 5 3%
lSx~mpl-t 10 A PDLC device was prepared as described in Example 7 except that a fluid containing (a) 57.5 parts of a mixture consisting of 13 . 7 wt . % lauryl methacrylate (Rhom Tech, Inc., Malden, MA), 3.9 wt.% methacrylic acid (Aldrich, Iqilwaukee, WI), 80 . 4 wt. % RCC-15C
obtained without initiator (W.R. Grace, Atlanta, GA), ~woss/29766 2 1 8 78 ~6 r~ r 1~
~nd 2 wt.~6 photoinitiator KB-l, and (b) 42.5 parts of BL036 liquid crystal mixture, with a solution viscosity of 210 Cp5 ~measured on a Brookfield viscometer using a #4 spindle operating at 60 rpm~, was used. The die was 5 conf igured with a 152 mm shim having a slot width of 88 . 9 cm, a 76 micron coating gap, and a 51 micron overbite . The coating was applied as a 88 . 9 cm wide strip of the uncured matrix on the IT0 coated PET film at a substrate speed of 0.91 m/minute (3 feet/minute).
10 During coating, a 3.7 mm Hg (2 inches water) vacuum was applied to the vacuum chamber. During lamination, an interference of 3 . 8 mm was used. The laminate co~ L-u~;~ion was exposed to 330 mJ/cm2 of W light having an average intensity of 1. 7 mW/cm2.
The thickness of the cured coating was 21+0 . 6 microns. The PDLC device had on- and off-state tr~n~ n~ of 74% and 2.7%, respectively, and a haze of 4 . 59~ .
r lo 11 A PDLC device was ~ d as described in Example 7 except that a fluid containing (a) 45 parts of a mixture consisting of 2 . 5 wt. % KB-l photoinitiator, 20 . O wt. 96 9460 allyl aliphatic urethane (Monomer Polymer & Dajac, Trevose, PA), 35.0 wt.% isooctyl 25 acrylate, 7.5 wt.% acrylic acid, 20 wt.~ 2 pllelloy~LII2~1 acrylate, and 15.0 wt.% Uralac 3004-102, and (b) 55 parts of BL036 liquid crystal mixture, with a solution viscosity of 64 cps (- ~ d on a Brookfield viscometer using a #3 spindle operating at 60 rpm), was 3 o used . The die was conf igured with a 152 micron shim having a slot width of 88.9 cm, an overbite of 30 microns and the coating applied to the IT0 coated PET
substrate at a rate of 3 m/min. at 20C with a vacuum of 2 . 8 mm Hg applied to the vacuum chamber. An air 35 ~Lesc,u-e of 3.4 bar was maintained to the lamination bar which was adjusted to provide an interference of W0 9s/29766 2 1 8 7 8 9 ~ "~( ~
3.8 mm. The laminate col.DL~u~Lion was exposed to 303 mJ/cm2 of W light having an average intensity of 1. 6 mW/cm~ .
The cured coating th;~l-no~6 was 17.4+0.6 microns.
5 The PDLC device had on- and off-state transmissions of 70.0% and 0.8%, respectively, and a haze of 8.6~.
E 1~ 12 An adhesive composition was prepared as described in Example 5 except that the prepolymer syrup was 10 prepared from a solution containing 90 wt.% isooctyl acrylate, 10 wt.9~ acrylic acid, and 0.04 wt.% KB-1 photoinitiator that had been advanced to a viscosity of 430 cps (measured on a Brookfield viscometer using a 4 spindle operating at 60 rpm) and to which an 15 additional 0.1 wt. % KB-1 had been added was used as the coating fluid. The die was configured with a 0.25 mm shim, an overbite of 76 microns and a coating gap of 76 microns. The polymer syrup was cured in a N~ a~ re without a second substrate being applied to the coating 20 by ~ ODUL,2 to UV lights having an average intensity of 1.2 mW/cm~ to produce a IJ~-sssuL~ sensitive adhesive having a th1~ 1rnP~fi of 21.5+0.5 microns.
~ Wo 95K9766 2 J 8 7 8 9 6 T~bl-- 1 First Socoud Viscosily Contin~ Co-tiug E~mple Subst~te Substnte (cps)~ G-p (mm) Ibicl~ness (mm) 5 IPETI PETQ 365 0.175 0.223 i 0.004 2PET2 PET~ 365 0.175 0.154iO.003 3PET2 PET2 1,950 0.175 0.116iO.001 4PEI~ PET2 1,950 0.175 0.221iO.001 SRdense PElq 5,600 0127 O.150iO.OOI
P pa' 10 6 Rde~so PET2 5,600 0.05 0.93io 08 P~lpe~
1. Measured on a Brookfield vLacometer u~ing A ~4 ~pindle operating at 60 rpm.
2. Bia~ lly oriented PET ~ilm, 51 mLcrona (2 mila) thick.
15 3. Polyethyl _u.lLe~ p~per provided with ~ ailicone rele~ae co~tinq .
Ex~m~l~ 7 A PDLC device was ~Leua~ed from a fluid cmnt I;n;n~
(a) 55 parts of a mixture consisting of 30.0 wt.% RCC-15C curable matrix mixture obtained without initiator and with 50% less thiol (W.R. Grace, Atlanta, GA), 7.5 wt.9c acrylic acid, 30.0 wt.% isooctyl acrylate, 15.0 wt.~6 2~phel1u~LyeL11yl acrylate (Sartomer, West Chester, PA), 15 . 0 wt. % divinyl ether of triethylene glycol (International Specialty Products, Wayne, NJ), and 2.5 wt. % KB-l photoinitiator, and (b) 45 parts BL036 liquid crystal mixture (EN Industries, Hav L1.u...e, NY) having a 30 solution viscosity of 42 cps (measured on a Brookfield viscometer using a t3 spindle operating at 60 rpm).
The fluid, which was d~ s~d under vacuum for - approximately 2 minutes at ambient t~ ~lLULe, wa6 applied as a 15 . 2 cm ( 6 inch) wide strip to the 35 electrode surface of an ITO-coated polyester film (90/lO indium/tin oxide ratio, 80 ohms/square, 51 microns (2 mil) thick PET, available from Southwall Technologies, Palo Alto, CA) at a rate of approximately w0 95/29766 2 ~ 8 7 ~ 9 ~ P ~ s ~
152.4 cm/min (5 ft/minute) using the precision coating process described in r , ~ 6 eYcept that a 88 . 9 cm die similar to that illustrated in Figure 7a was used.
This die was deckled to produce a narrower coating and 5 configured with a 152 micron shim, a coating land having a length (L~) of 12.7 mm, a vacuum land having a length L2 f 12.7 mm, a 0.57 cvl~c,Lg~llce~ a 33 micron overbite, a vacuum land gap G~ of 0.152 mm, a die attack angle A2 Of 95, and a coatlng gap G~ of 102 microns.
10 The cv.lv_L~ ce of the vacuum bar was o and no vacuum was applied to the vacuum chamber during coating. Both the die and back-up roll were temperature controlled at 21C. A ~LeS~UL~ of 1.7 bar was maintained to the sintered metal bar during lamination and the lamination 15 bar was adjusted to provide an interference of 3 . 6 mm.
The uncured laminate vll~u~ LiOn was cured by passing the CVI-~ U- ~ion through a cooled curing chamber cvl-=,LLu~ed of ultraviolet transparent AcrylitelM OP-4 (available from Cyro Industries, Nt.
20 Arlington, NJ), extending approximately 61 cm (2 feet) into a cure chamber equipped with two banks of fluvL~sce,.l~ black lights (F20T12-350BL, available from osram Sylvania, Danvers, NA), one bank positioned on each side of the laminate. Air temperature in the 25 cooling chamber wa~ monitored by a Ule ~_ le mounted in the chamber under the second fluvLesc~ bulb and controlled at the indicated tl _ ~oLuL~a by ill-Lvdu~ ing temperature controlled air. Each side of the laminate uv~LLu~;Lion was exposed to approximately 530 mJ/cm2 of 30 radiation calculated from light intensities of 1.1 mW/cm2 as measured through the conductive electrode used in the PDLC device by means of a uvl~S~ll~; r~ c.r (model number UBM365M0, available from Electronic In_LL, Lcltion and Technology, Inc., Sterling, VA) 35 equipped with a glass filter responsive between 300 and 400 nm, with a maximum tr~n~ on at 365 nm. The ~ W095/29766 ;~l 81l~9~; r~l~u. ~
radiometer was specially calibrated to read in absolute lntensity .
The backup roll 50 was a pacer roll driven by a Torquer T~ Pr precision motor (available from 5 Inland Motor Division, Bradford, VA).
The cured coating th;~ knPGG of the resulting PDLC
film was 24+1 microns. The PDLC device had on- and off-state ~rAn^~;CCions of 73.1% and 1.2%, respectively, and a haze of 5. 8% .
r l-- 8 A PDLC device was prepared as described in Example 7 except that the coating fluid had the following composition: (a) 5û parts of a mixture consisting of 20.0 wt.% Vectomer 2020 tAllied-Signal, Inc., 15 Norri6town, NJ), 5.0 wt.% acrylic acid, 25.0 wt.%
isooctyl acrylate, 15.0 wt.% 2-phel.o..yéL~.yl acrylate, 10 wt.% trimethylolpropane tris(3 ~ pLopropionate) (Aldrich, Nilwaukee, WI), 22.5 wt.% cy--]nhPvlnp dimethanol divinyl ether (International Specialty 20 Products, Wayne, NJ) and 2.5 wt.9~ Escacure RB-1, and (b) 50 parts BL036 liquid crystal mixture. The viscosity of the coating fluid was 134 cps (measured on a Brookfield vis~ Pr using a ~3 spindle operating at 60 rpm). The coating t~ ~LuLe was 21C and during 25 lamination an air ples:~uLe of 2.4 bar was maintained to the laminator bar which was adjusted to provide an interference of 3 . 8 mm. The fluid was applied as a 15.2 cm (6 inch) wide strip to the electrode surface of an IT0-coated polyester f ilm at a rate of approximately 30 152.4 cm/min (5 ft/minute) using the precision coating process described in Example 7 except that the die was configured with a 46 micron overbite, a coating gap of 102 microns, and a vacuum of 1.9 mm Hg (1 inch of water) was used to apply the solution at 22C. The film 35 was cured at 21C by PYposin~ each side to approximately W09~l29766 ~ ~ 1 ~7~ P l/~ 5 ~ ~ ~
530 mJ/cm2 at an intensity of 1. 0 mW/cm2 to produce a PDLC film with a thicknes6 of 23+1 microns.
The PDLC device had on- and off-state transmissions of 71.9% and 1.1%, respectively, and a 5 haze of 4 . 8% .
1~ 9 A PDLC device was prepared as described in Example 7 except that the fluid contained 500 parts of BL036 liquid crystal mixture and 333 parts of a mixture 10 having the composition of 2 . 5 wt . % Esacure KB-1 photoinitiator, 7.5 wt.% acrylic acid, 30.0 wt.%
isooctyl acrylate, 15 . O wt. % 2~ph~ ye ~l~yl acrylate 15.0 wt.% Uralac 3004-102 (DSM Resins, U.s., Inc., Elgin, IL), and 30.0 wt.% Uralac 3004-300 (DSN Resins, 15 U.S., Inc., Elgin, IL). The 88.9 cm wide die was configured with a slot width of 88.9 cm, an overbite of 43 microns, a vacuum land gap G2 Of 24.5 mm and a vacuum of 1. 9 mm Hg was applied to the vacuum chamber during coating. The IT0-coated polyester film used for the 20 ele~ LL~,des was approximately 130 microns (5 mils) thick. An air ~La5r UL~: of 3.4 bar wa6 maintained to the laminator bar which was adjusted to provide an interference of 6.35 mm. The resulting laminate was exposed W light having an average intensity of approximately 1. 68 mW/cm2 at about 23 C to produce a PDLC f ilm approximately 18 microns thick .
The PDLC device had on- and of f -state trAnr~ sion~ of 73.4% and 1.7%, respectively, and a haze of 5 3%
lSx~mpl-t 10 A PDLC device was prepared as described in Example 7 except that a fluid containing (a) 57.5 parts of a mixture consisting of 13 . 7 wt . % lauryl methacrylate (Rhom Tech, Inc., Malden, MA), 3.9 wt.% methacrylic acid (Aldrich, Iqilwaukee, WI), 80 . 4 wt. % RCC-15C
obtained without initiator (W.R. Grace, Atlanta, GA), ~woss/29766 2 1 8 78 ~6 r~ r 1~
~nd 2 wt.~6 photoinitiator KB-l, and (b) 42.5 parts of BL036 liquid crystal mixture, with a solution viscosity of 210 Cp5 ~measured on a Brookfield viscometer using a #4 spindle operating at 60 rpm~, was used. The die was 5 conf igured with a 152 mm shim having a slot width of 88 . 9 cm, a 76 micron coating gap, and a 51 micron overbite . The coating was applied as a 88 . 9 cm wide strip of the uncured matrix on the IT0 coated PET film at a substrate speed of 0.91 m/minute (3 feet/minute).
10 During coating, a 3.7 mm Hg (2 inches water) vacuum was applied to the vacuum chamber. During lamination, an interference of 3 . 8 mm was used. The laminate co~ L-u~;~ion was exposed to 330 mJ/cm2 of W light having an average intensity of 1. 7 mW/cm2.
The thickness of the cured coating was 21+0 . 6 microns. The PDLC device had on- and off-state tr~n~ n~ of 74% and 2.7%, respectively, and a haze of 4 . 59~ .
r lo 11 A PDLC device was ~ d as described in Example 7 except that a fluid containing (a) 45 parts of a mixture consisting of 2 . 5 wt. % KB-l photoinitiator, 20 . O wt. 96 9460 allyl aliphatic urethane (Monomer Polymer & Dajac, Trevose, PA), 35.0 wt.% isooctyl 25 acrylate, 7.5 wt.% acrylic acid, 20 wt.~ 2 pllelloy~LII2~1 acrylate, and 15.0 wt.% Uralac 3004-102, and (b) 55 parts of BL036 liquid crystal mixture, with a solution viscosity of 64 cps (- ~ d on a Brookfield viscometer using a #3 spindle operating at 60 rpm), was 3 o used . The die was conf igured with a 152 micron shim having a slot width of 88.9 cm, an overbite of 30 microns and the coating applied to the IT0 coated PET
substrate at a rate of 3 m/min. at 20C with a vacuum of 2 . 8 mm Hg applied to the vacuum chamber. An air 35 ~Lesc,u-e of 3.4 bar was maintained to the lamination bar which was adjusted to provide an interference of W0 9s/29766 2 1 8 7 8 9 ~ "~( ~
3.8 mm. The laminate col.DL~u~Lion was exposed to 303 mJ/cm2 of W light having an average intensity of 1. 6 mW/cm~ .
The cured coating th;~l-no~6 was 17.4+0.6 microns.
5 The PDLC device had on- and off-state transmissions of 70.0% and 0.8%, respectively, and a haze of 8.6~.
E 1~ 12 An adhesive composition was prepared as described in Example 5 except that the prepolymer syrup was 10 prepared from a solution containing 90 wt.% isooctyl acrylate, 10 wt.9~ acrylic acid, and 0.04 wt.% KB-1 photoinitiator that had been advanced to a viscosity of 430 cps (measured on a Brookfield viscometer using a 4 spindle operating at 60 rpm) and to which an 15 additional 0.1 wt. % KB-1 had been added was used as the coating fluid. The die was configured with a 0.25 mm shim, an overbite of 76 microns and a coating gap of 76 microns. The polymer syrup was cured in a N~ a~ re without a second substrate being applied to the coating 20 by ~ ODUL,2 to UV lights having an average intensity of 1.2 mW/cm~ to produce a IJ~-sssuL~ sensitive adhesive having a th1~ 1rnP~fi of 21.5+0.5 microns.
Claims (9)
1. A method of coating the surface of a substrate with an essentially solvent-free polymerizable fluid comprising passing said fluid through a die onto the surface of said substrate as said substrate moves relative to said die, said die comprising a channel adapted to receive said fluid and an adjustable width slot in communication with said channel, through which said fluid is passed, formed between a downstream bar and an upstream bar, said downstream bar having a die lip formed as a sharp edge and said upstream bar having a die lip formed as a land in a shape corresponding substantially to the shape of said substrate in the immediate area of coating fluid application to said substrate.
2. The method of claim 1 further comprising adjusting the rate at which said fluid passes through said die and rate at which said substrate moves relative to said die to produce a substantially uniform caliper coating on said substrate.
3. The method of claim 1 comprising configuring said sharp edge and said land such that said sharp edge is displaced towards the surface of said substrate relative to said land.
4. The method of claim 1 comprising providing a substantially straight, sharp edge in which the straightness of said edge measured along a distance of about 25 cm at any point along said sharp edge does not vary by more than about 2.5 microns.
5. The method of claim 1 comprising providing said land in the form of a curved land.
6. The method of claim 1 comprising providing said die with a convergence ranging from about 0° to about 2.29°.
7. The method of claim 1 comprising providing said substrate in the form of a web.
8. The method of claim 1 comprising providing a polymerizable fluid having a viscosity of at least 10 cps.
9. A method of coating the surface of a substrate with an essentially solvent-free polymerizable fluid comprising the steps of:
(a) passing said fluid through a die onto the surface of said substrate as said substrate moves relative to said die, said die comprising a channel adapted to receive said fluid and an adjustable width slot in communication with said channel through which said fluid is passed formed between a substantially straight, sharp edge located on the downstream side of said substrate and a land located on the upstream side of said substrate; and (b) adjusting the rate at which said fluid passes through said die and rate at which said substrate moves relative to said die to produce a substantially uniform caliper coating on said substrate.
(a) passing said fluid through a die onto the surface of said substrate as said substrate moves relative to said die, said die comprising a channel adapted to receive said fluid and an adjustable width slot in communication with said channel through which said fluid is passed formed between a substantially straight, sharp edge located on the downstream side of said substrate and a land located on the upstream side of said substrate; and (b) adjusting the rate at which said fluid passes through said die and rate at which said substrate moves relative to said die to produce a substantially uniform caliper coating on said substrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US23542394A | 1994-04-29 | 1994-04-29 | |
| US08/235423 | 1994-04-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2187896A1 true CA2187896A1 (en) | 1995-11-09 |
Family
ID=22885435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002187896A Abandoned CA2187896A1 (en) | 1994-04-29 | 1995-04-07 | Precision coating process for preparing polymerizable films |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0759812B1 (en) |
| JP (1) | JP3826184B2 (en) |
| KR (1) | KR100351593B1 (en) |
| CA (1) | CA2187896A1 (en) |
| DE (1) | DE69514795T2 (en) |
| WO (1) | WO1995029766A1 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999037408A1 (en) * | 1998-01-21 | 1999-07-29 | Alcan International Limited | Process and apparatus for multi-layer coating of elongated strip articles |
| US6168682B1 (en) | 1998-02-10 | 2001-01-02 | 3M Innovative Properties Company | Method of manufacturing an optical recording medium |
| US6235387B1 (en) | 1998-03-30 | 2001-05-22 | 3M Innovative Properties Company | Semiconductor wafer processing tapes |
| US6599602B2 (en) | 1999-06-02 | 2003-07-29 | 3M Innovative Properties Company | Polycarbonate articles and adhesive composition therefor |
| US6813820B2 (en) | 2001-12-19 | 2004-11-09 | 3M Innovative Properties Company | Method of improving coating uniformity |
| KR20050042626A (en) * | 2003-11-03 | 2005-05-10 | (주)아이컴포넌트 | Hard coating method of transparent film for use display panel and apparatus for the same |
| US7845214B2 (en) * | 2007-12-26 | 2010-12-07 | Industrial Technology Research Institute | Device and method for optical nanoindentation measurement |
| FR2942405A1 (en) | 2009-02-23 | 2010-08-27 | Oreal | PROGRESSIVE PHOTOMAQUILING METHOD |
| FR2942403A1 (en) | 2009-02-23 | 2010-08-27 | Oreal | PHOTOMAQUILING METHOD WITH APPLICATION OF A BASE LAYER AND ASSEMBLY FOR IMPLEMENTING SUCH A METHOD |
| FR2942400B1 (en) | 2009-02-23 | 2011-04-22 | Oreal | PHOTOMAKING METHOD IN WHICH OPTICAL AGENT IS USED TO PROTECT THE RESULT OBTAINED |
| FR2942404B1 (en) | 2009-02-23 | 2011-08-26 | Oreal | PHOTOMAQUILLING PROCESS USING PHOTOCHROMIC COMPOSITION IN THE STATE ALREADY REVEALED |
| FR2942406B1 (en) | 2009-02-23 | 2011-04-22 | Oreal | MAKE-UP METHOD AND COSMETIC CLEANSING COMPOSITION |
| FR2942401A1 (en) | 2009-02-23 | 2010-08-27 | Oreal | COSMETIC PROCESSING METHOD COMPRISING THE PROJECTION OF AN IMAGE ON THE AREA TO BE TREATED |
| WO2010103420A2 (en) | 2009-03-12 | 2010-09-16 | L'oreal | A method of making up with light-sensitive makeup with mechanical protection of the light-sensitive makeup |
| FR2947725A1 (en) | 2009-07-07 | 2011-01-14 | Oreal | METHOD FOR SMOOTHING THE SKIN BY FILLING HOLLOW PORTIONS |
| FR2947726A1 (en) | 2009-07-07 | 2011-01-14 | Oreal | METHOD FOR SMOOTHING THE SKIN BY FILLING HOLLOW PORTIONS |
| FR2963887A1 (en) | 2010-08-20 | 2012-02-24 | Oreal | COSMETIC PROCESSING METHOD USING A PHOTOREVELABLE COMPOUND COMPRISING A PHOTOCLIVABLE FUNCTION. |
| JP7152378B2 (en) * | 2019-09-30 | 2022-10-12 | 富士フイルム株式会社 | Coating device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4445458A (en) * | 1982-07-21 | 1984-05-01 | E. I. Du Pont De Nemours And Company | Beveled edge metered bead extrusion coating apparatus |
| FI105533B (en) * | 1992-10-26 | 2000-09-15 | Valmet Paper Machinery Inc | Spray Coating Apparatus and Method |
-
1995
- 1995-04-07 EP EP95917560A patent/EP0759812B1/en not_active Expired - Lifetime
- 1995-04-07 WO PCT/US1995/004466 patent/WO1995029766A1/en active IP Right Grant
- 1995-04-07 JP JP52825395A patent/JP3826184B2/en not_active Expired - Fee Related
- 1995-04-07 KR KR1019960706086A patent/KR100351593B1/en not_active IP Right Cessation
- 1995-04-07 CA CA002187896A patent/CA2187896A1/en not_active Abandoned
- 1995-04-07 DE DE69514795T patent/DE69514795T2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69514795T2 (en) | 2000-08-31 |
| KR970702756A (en) | 1997-06-10 |
| JPH10500057A (en) | 1998-01-06 |
| EP0759812A1 (en) | 1997-03-05 |
| EP0759812B1 (en) | 2000-01-26 |
| WO1995029766A1 (en) | 1995-11-09 |
| DE69514795D1 (en) | 2000-03-02 |
| KR100351593B1 (en) | 2002-10-25 |
| JP3826184B2 (en) | 2006-09-27 |
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