EP0773472A1 - Verfahren zur Erhöhung der Beschichtungsgeschwindigkeit - Google Patents

Verfahren zur Erhöhung der Beschichtungsgeschwindigkeit Download PDF

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Publication number
EP0773472A1
EP0773472A1 EP96203091A EP96203091A EP0773472A1 EP 0773472 A1 EP0773472 A1 EP 0773472A1 EP 96203091 A EP96203091 A EP 96203091A EP 96203091 A EP96203091 A EP 96203091A EP 0773472 A1 EP0773472 A1 EP 0773472A1
Authority
EP
European Patent Office
Prior art keywords
coating
gelatin
curtain
particles
layer
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.)
Withdrawn
Application number
EP96203091A
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English (en)
French (fr)
Inventor
Andrew Michael Howe
William James Harrison
Terence Desmond Blake
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kodak Ltd
Eastman Kodak Co
Original Assignee
Kodak Ltd
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kodak Ltd, Eastman Kodak Co filed Critical Kodak Ltd
Publication of EP0773472A1 publication Critical patent/EP0773472A1/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor

Definitions

  • the present invention relates to improvements in or relating to coating processes, and is more particularly concerned with the use of colloidal particles to optimise the rheology of solutions used in such coating processes.
  • Coating processes such as, extrusion, bead and curtain coating, are well-known and widely used for the application of one or more liquid layers on to the surface of a moving support.
  • coating processes may be used for manufacturing photographic products.
  • a support is coated by forming a freely-falling vertical curtain of liquid so that it impinges on to the support.
  • the curtain is stable and has a uniform flow rate across its width.
  • a controlled relationship is maintained between the flow rate of the liquid and the speed at which the support is moved so that a thin layer, of specified thickness, of the coating liquid is formed on the support.
  • Apparatus for forming the curtain include a hopper having a downwardly inclined slide surface over which the coating liquid flows by gravity until it reaches a lip. The lip is spaced vertically above the moving support and the coating liquid flows downwards in a freely-falling curtain from the lip.
  • US-A-3 867 901 describes a method in which single layers are coated on to a support.
  • US-A-3 508 947 discloses a method for coating multiple layers on to a support.
  • coating window In coating processes, a uniform layer or layers are only obtained if the operational variables are held within fairly precise limits. These limits define the so-called “coating window”. It is to be noted that the "coating window” obtained depends on the nature of the liquid material which is to be coated onto the support. It is convenient to define the “coating window” in terms of the variables of coating speed and flow rate per unit width. One of the boundaries of the coating window is formed due to the occurrence of air-entrainment.
  • the passage of a splice can provide a sufficient disturbance to precipitate air-entrainment when none had previously existed. Imperfections in the support can similarly precipitate air-entrainment, as can transient disturbances encountered at the start of a coating. Good practice dictates that curtain coating within the metastable region is to be avoided. Thus coating speed may be undesirably limited.
  • US-A-4 569 863 discloses the use of a thin, low-viscosity bottom layer to increase speeds in curtain coating.
  • Such a thin layer would not necessarily be a functional layer in a product, and so a separate delivery system, together with a hopper with an additional slot would usually be necessary.
  • a low-viscosity bottom layer also promotes "puddling" at the point where the freely-falling liquid curtain impinges on the moving support.
  • a "heel” appears at the foot of the curtain. If the heel is sufficiently large, it may contain an eddy in which air bubbles and debris may become trapped, thereby generating a line or streak in the coating. A large heel can also oscillate, producing non-uniformities in the coating along and across the direction of support motion.
  • the low-viscosity bottom layer may have to be kept thin, even though a functional bottom layer may not be thin, and the curtain height low, though this adversely affects curtain stability and restricts the room beneath the hopper for other equipment, such as a start pan.
  • EP-A-0 563 086 describes an improved curtain coating process in which the coating window is enlarged. This is achieved by inserting a coating material adjacent the support onto which the liquid material is to be coated which readily shear-thins. At least the layer of liquid material adjacent the support is a pseudoplastic liquid having a viscosity greater than 20mPas at shear rates less than 500s -1 , and a viscosity of less than 10mPas at shear rates greater than 10 6 s -1 . The viscosity of the pseudoplastic liquid approaches a substantially constant value at a shear rate which lies in a range between 10 4 and 10 8 s -1 .
  • US-A-3 767 410 and US-A-3 811 897 describe the use of water-soluble polymers as thickening agents for photographic coating applications.
  • DD-A-0 286 436 describes the use of a combination of two polymer dispersions to increase the viscosity of gelatin-containing coating solutions for the preparation of photographic materials.
  • the dispersions are formulated such that one is alkali-soluble at a pH greater than 7, the other insoluble under the same pH conditions.
  • silicon dioxide (silica)
  • colloidal silicon dioxide (silica) is also known for use in a subbing layer as described in US-A-4 048 357.
  • US-A-3 776 726 describes the use of colloidal silica to increase the viscosity of a film-forming polymer in diffusion transfer photographic development processes.
  • colloidal silica in current photographic products to improve layer toughness and to change matt-gloss characteristics, but not to enhance coatability.
  • US-A-3 359 108 discloses silver halide photographic emulsions in which colloidal silica is used in a synthetic resin latex hydrophobic binder to provide improved permability of the emulsion to processing solutions.
  • Facilitation of the coating of photographic emulsions dispersed in said hydrophobic binder is also disclosed wherein materials are added as thickeners.
  • a method of increasing the maximum coating speed of a coating process and substantially eliminating wetting failure hysteresis wherein a material is coated onto a substrate, the material comprising at least a first layer which lies adjacent the support after coating, characterized in that the first layer includes a dispersion of colloidal particles in a hydrophilic colloid.
  • the hydrophilic colloid comprises aqueous gelatin.
  • the particles comprise colloidal silica. It is preferred that the particles are negatively charged, and have a size in the range of 1nm to 10mm, preferably, in the range of 5 to 50nm.
  • a coating formulation which is applied directly to a moving support, characterized in that the formulation comprises a dispersion of colloidal particles in a hydrophilic colloid.
  • an aqueous dispersion of small, solid, negatively charged colloidal silica particles can be used as a thickener and rheology modifier for aqueous gelatin solutions for coating applications.
  • the colloidal silica particles have sizes in a range of 5 to 50nm.
  • the solid particle dispersion can be added directly to the bottom layer of an existing product or, alternatively, can be coated in aqueous gelatin as a bottom layer of a multilayer pack.
  • the colloidal particles have been found to synergistically boost the viscosity of an alkali-processed gelatin at low rates of shear due to the strong interactions between the polymer and the solid particle. High viscosities at low shear rates improve widthwise uniformity on the hopper slide and coated material or web.
  • gelatin-based dispersions are much more pronounced and commences at a lower, more desirable rate of shear than observed in the absence of such colloidal particles.
  • the viscosity of dispersions in accordance with the present invention at shear rates of the order of ⁇ 10 5 s -1 is substantially lower than that for pure gelatin solutions possessing the same low-shear viscosity. Low viscosities at high shear rates favour high coating speeds without air-entrainment.
  • the overall rheological profiles (viscosity as a function of shear rate) of the gelatin-based colloidal silica dispersions also appear to be superior to pseudoplastic systems based on water-soluble polymeric additives (for example, in EP-A-0 563 086 discussed above and incorporated herein by reference). Specifically, the flow characteristics of the colloidal dispersion in accordance with the present invention more closely resemble the preferred rheological profiles described therein.
  • colloidal particles are defined as particles having sizes in the range of 1nm to 10mm, and in particular, for small particles in the range of 5 to 50nm.
  • the present invention relates specifically to the use of colloidal particles which interact attractively with an aqueous hydrophilic colloid comprising the continuous phase of a coating formulation, such as gelatin, to give the desired rheological properties for coating, the colloidal particles being ones to which the hydrophilic colloid, e.g. gelatin, adsorbs, and in particular, silica particles which have negatively charged surfaces.
  • a coating formulation such as gelatin
  • Ludox AM also supplied by DuPont
  • a silica-aluminate 12nm average diameter.
  • the rheological profile for a 3% w/w aqueous regular gelatin, 6% w/w Ludox AM colloidal silica dispersion is shown in Figure 2.
  • the specific rheological profiles of these Ludox-containing aqueous gelatin melts may be manipulated simply by changing the concentrations and ratios of the solution components.
  • a preferred rheological profile for coating is shown by the solid line. This profile is consistent with that defined as the optimum rheological profile in EP-A-0 563 086.
  • the dashed lines illustrate non-optimal profiles given by simple gelatin melts of different concentrations and hence varying low shear viscosities and rheological profiles.
  • the solid line illustrates a preferred profile achieved by adding an appropriate thickening agent to a dilute gelatin.
  • the stippled area on the graph indicates the range of shear rates expected at the wetting line in coating processes. Low values of viscosities in this region promote high coating speeds as will be described in detail below.
  • the operational coating window is conveniently represented by plotting a map of coating speed, S (cms -1 ), versus flow rate per unit width of the coating hopper, Q (cm 2 s -1 ). A line drawn through the origin then connects all points having a constant wet thickness or laydown, Q/S (cm).
  • FIG. 4 An example of a curtain coating map for a moderately shear-thinning aqueous gelatin solution (15% w/w aqueous gelatin, 67mPas) coated at a curtain height of 10.2cm, at an application angle of 0° (top dead centre on the coating roller), is shown in Figure 4.
  • the corresponding rheological profile is shown in Figure 5.
  • the curve ABCD defines the overall wetting failure boundary beyond which gross air-entrainment occurs and coating uniformity is destroyed.
  • the coating speed at the onset of wetting failure is inversely dependent on the solution viscosity expressed close to the wetting line, that is, the lower the viscosity, the higher the coating speed.
  • a Newtonian (non-shear thinning) liquid for example, aqueous glycerol
  • aqueous glycerol of comparable low-shear viscosity
  • shear-thinning nature of coating solutions is an important benefit.
  • the wetting failure boundary bifurcates above a certain critical flowrate (corresponding to point B) to produce wetting failure hysteresis as discussed above and in detail in EP-A-0 563 086.
  • the coating liquid is Newtonian over the range of shear rates that occur inside the hopper (typically less than 10 3 s -1 ), then widthwise uniformity may be improved.
  • Current practice indicates that the preferred viscosity range is from ⁇ 30mPas to ⁇ 200mPas for curtain coating applications.
  • the Ludox-based aqueous gelatin dispersions discussed above conform to these requirements.
  • aqueous polymer solutions which are micron-thin, and exhibiting the desired rheological profile
  • carrier layers composed of an aqueous Ludox-gelatin dispersion exhibiting the desired rheology (for example, a 3% w/w aqueous regular gelatin + 6% w/w colloidal silica, Ludox AM).
  • the rheological profile and coating map for this formulation are as shown in Figures 2 and 6.
  • the results of using this formulation for carrier layers are summarised in Table 1 below.
  • Figure 7 shows a coating window for curtain coating of 15% w/w aqueous regular gelatin coated onto a gelatin-subbed Estar support using a curtain height of 3cm and an application angle of 0°.
  • the practical coating window is confined within the area defined by the boundary ABE.
  • the maximum practical coating speed achieved, defined by point B is ⁇ 380cms -1 .
  • the maximum coating speed is ⁇ 817cms -1 , as shown in Figure 8, and the overall practical coating window has been significantly enlarged.
  • bottom layers having high viscosities at low shear rates containing Ludox AM may be coated rapidly at low curtain heights at a wide range of laydowns if so desired.
  • coating speed increases in excess of 30% are readily available. In some cases, coating speed increases of almost 100% are obtained.
  • solid colloidal silica particles in aqueous gelatin it will be readily appreciated that other solid colloidal particle types may also be useful.
  • other inorganic or organic charged particles for example, clays may be used.
  • the present invention may also be extended to include liquid colloidal particles, such as, surfactant micelles and liquid crystal droplets, and oil-in-water emulsions, such as, photographic colour coupler dispersions.
  • liquid colloidal particles such as, surfactant micelles and liquid crystal droplets
  • oil-in-water emulsions such as, photographic colour coupler dispersions.
  • the colloidal particles may have hydrophobic surfaces instead of charged surfaces as described above, or have surfaces stabilised by charged surfactants or polymers. However, in each case, the colloidal particles must interact with the hydrophilic colloid to produce the desired rheological profile.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP96203091A 1995-11-11 1996-11-06 Verfahren zur Erhöhung der Beschichtungsgeschwindigkeit Withdrawn EP0773472A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9523138 1995-11-11
GBGB9523138.7A GB9523138D0 (en) 1995-11-11 1995-11-11 Improvements in or relating to coating processes

Publications (1)

Publication Number Publication Date
EP0773472A1 true EP0773472A1 (de) 1997-05-14

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EP96203091A Withdrawn EP0773472A1 (de) 1995-11-11 1996-11-06 Verfahren zur Erhöhung der Beschichtungsgeschwindigkeit

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EP (1) EP0773472A1 (de)
JP (1) JPH09173975A (de)
GB (1) GB9523138D0 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0883022A1 (de) * 1997-06-06 1998-12-09 Fuji Photo Film Co., Ltd. Beschichtungsverfahren für ein thermographisches Bildaufzeichnungselement, Beschichtungslösung für eine thermographische Bildaufzeichnungsschicht, thermographisches Bildaufzeichnungselement und photothermographisches Bildaufzeichnungselement
EP0996033A1 (de) * 1998-10-20 2000-04-26 Eastman Kodak Company Verfahren zur schnellen Vorhangbeschichtung
EP0996034A1 (de) * 1998-10-20 2000-04-26 Eastman Kodak Company Verfahren zur elektrostatisch assistierten schnellen Vorhangbeschichtung
US6666946B2 (en) 2001-03-14 2003-12-23 3M Innovative Properties Company Method of high speed coating pigment-containing liquid coating materials
WO2019190623A1 (en) * 2018-03-28 2019-10-03 Dow Global Technologies Llc Methods for curtain coating substrates

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006158993A (ja) * 2004-12-02 2006-06-22 Fuji Photo Film Co Ltd カーテン塗布方法

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3359108A (en) 1964-04-02 1967-12-19 Eastman Kodak Co Photographic emulsion having a low modulus of elasticity and process for its manufacture
US3508947A (en) 1968-06-03 1970-04-28 Eastman Kodak Co Method for simultaneously applying a plurality of coated layers by forming a stable multilayer free-falling vertical curtain
US3632374A (en) 1968-06-03 1972-01-04 Eastman Kodak Co Method of making photographic elements
US3767410A (en) 1972-02-22 1973-10-23 Eastman Kodak Co Photographic hydrophilic colloids and method of coating
US3776726A (en) 1972-04-24 1973-12-04 Polaroid Corp Color diffusion transfer photographic products,processes and compositions
US3811897A (en) 1972-03-29 1974-05-21 Eastman Kodak Co Method for increasing the viscosity of dilute photographic emulsions and elements prepared thereby
US3867901A (en) 1968-06-03 1975-02-25 Eastman Kodak Co Apparatus for production of photographic elements
US4048357A (en) 1972-10-10 1977-09-13 Agfa-Gevaert N.V. Method of coating multi-layer graphic film
US4113903A (en) 1977-05-27 1978-09-12 Polaroid Corporation Method of multilayer coating
US4308344A (en) 1979-03-20 1981-12-29 Fuji Photo Film Co., Ltd. Process for production of a photographic light-sensitive material
US4384015A (en) 1979-04-03 1983-05-17 Agfa-Gevaert Ag Process and an apparatus for simultaneously coating several layers to moving objects, particularly webs
US4569863A (en) 1982-10-21 1986-02-11 Agfa-Gevaert Aktiengesellschaft Process for the multiple coating of moving objects or webs
US4572849A (en) 1982-10-21 1986-02-25 Agfa-Gevaert Aktiengesellschaft Process for the multiple coating of moving webs
EP0239363A2 (de) * 1986-03-25 1987-09-30 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial, das für schnelle Entwicklung verwendbar ist
EP0248390A2 (de) * 1986-06-04 1987-12-09 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial, das für super-schnelle Behandlung ausgezeichnet ist
DD286436A5 (de) 1985-07-17 1991-01-24 Veb Filmfabrik Wolfen, Verfahren zur steuerung der viskositaet von gelatinehaltigen begiessloesungen
EP0450977A2 (de) * 1990-04-05 1991-10-09 Konica Corporation Verfahren zur Herstellung von photographischen Silberhalogenidmaterialien
US5096803A (en) * 1989-04-20 1992-03-17 Fuji Photo Film Co., Ltd. Method for the manufacture of silver halide photographic materials
EP0532076A1 (de) * 1991-09-10 1993-03-17 Agfa-Gevaert N.V. Flachdruckplatte vom Silbersalzdiffusionübertragungstyp
EP0563086A1 (de) 1990-12-20 1993-10-06 Kodak Ltd Beschichtungsverfahren.
US5292628A (en) * 1992-04-28 1994-03-08 Agfa Gevaert Ag Photographic silver halide element with gelatin layer containing silica
EP0609539A2 (de) * 1992-12-18 1994-08-10 Fuji Photo Film Co., Ltd. Photographischer Papierschichtträger
JPH07244356A (ja) * 1994-03-04 1995-09-19 Mitsubishi Paper Mills Ltd 写真印画紙の製造方法
EP0679938A2 (de) * 1994-04-27 1995-11-02 Konica Corporation Verfahren zur Herstellung eines photographischen lichtempfindlichen Silberhalogenidmaterials

Patent Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3359108A (en) 1964-04-02 1967-12-19 Eastman Kodak Co Photographic emulsion having a low modulus of elasticity and process for its manufacture
US3508947A (en) 1968-06-03 1970-04-28 Eastman Kodak Co Method for simultaneously applying a plurality of coated layers by forming a stable multilayer free-falling vertical curtain
US3632374A (en) 1968-06-03 1972-01-04 Eastman Kodak Co Method of making photographic elements
US3867901A (en) 1968-06-03 1975-02-25 Eastman Kodak Co Apparatus for production of photographic elements
US3767410A (en) 1972-02-22 1973-10-23 Eastman Kodak Co Photographic hydrophilic colloids and method of coating
US3811897A (en) 1972-03-29 1974-05-21 Eastman Kodak Co Method for increasing the viscosity of dilute photographic emulsions and elements prepared thereby
US3776726A (en) 1972-04-24 1973-12-04 Polaroid Corp Color diffusion transfer photographic products,processes and compositions
US4048357A (en) 1972-10-10 1977-09-13 Agfa-Gevaert N.V. Method of coating multi-layer graphic film
US4113903A (en) 1977-05-27 1978-09-12 Polaroid Corporation Method of multilayer coating
US4308344A (en) 1979-03-20 1981-12-29 Fuji Photo Film Co., Ltd. Process for production of a photographic light-sensitive material
US4384015A (en) 1979-04-03 1983-05-17 Agfa-Gevaert Ag Process and an apparatus for simultaneously coating several layers to moving objects, particularly webs
US4572849A (en) 1982-10-21 1986-02-25 Agfa-Gevaert Aktiengesellschaft Process for the multiple coating of moving webs
US4569863A (en) 1982-10-21 1986-02-11 Agfa-Gevaert Aktiengesellschaft Process for the multiple coating of moving objects or webs
DD286436A5 (de) 1985-07-17 1991-01-24 Veb Filmfabrik Wolfen, Verfahren zur steuerung der viskositaet von gelatinehaltigen begiessloesungen
EP0239363A2 (de) * 1986-03-25 1987-09-30 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial, das für schnelle Entwicklung verwendbar ist
EP0248390A2 (de) * 1986-06-04 1987-12-09 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial, das für super-schnelle Behandlung ausgezeichnet ist
US5096803A (en) * 1989-04-20 1992-03-17 Fuji Photo Film Co., Ltd. Method for the manufacture of silver halide photographic materials
EP0450977A2 (de) * 1990-04-05 1991-10-09 Konica Corporation Verfahren zur Herstellung von photographischen Silberhalogenidmaterialien
EP0563086A1 (de) 1990-12-20 1993-10-06 Kodak Ltd Beschichtungsverfahren.
EP0532076A1 (de) * 1991-09-10 1993-03-17 Agfa-Gevaert N.V. Flachdruckplatte vom Silbersalzdiffusionübertragungstyp
US5292628A (en) * 1992-04-28 1994-03-08 Agfa Gevaert Ag Photographic silver halide element with gelatin layer containing silica
EP0609539A2 (de) * 1992-12-18 1994-08-10 Fuji Photo Film Co., Ltd. Photographischer Papierschichtträger
JPH07244356A (ja) * 1994-03-04 1995-09-19 Mitsubishi Paper Mills Ltd 写真印画紙の製造方法
EP0679938A2 (de) * 1994-04-27 1995-11-02 Konica Corporation Verfahren zur Herstellung eines photographischen lichtempfindlichen Silberhalogenidmaterials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 95, no. 009 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0883022A1 (de) * 1997-06-06 1998-12-09 Fuji Photo Film Co., Ltd. Beschichtungsverfahren für ein thermographisches Bildaufzeichnungselement, Beschichtungslösung für eine thermographische Bildaufzeichnungsschicht, thermographisches Bildaufzeichnungselement und photothermographisches Bildaufzeichnungselement
EP0996033A1 (de) * 1998-10-20 2000-04-26 Eastman Kodak Company Verfahren zur schnellen Vorhangbeschichtung
EP0996034A1 (de) * 1998-10-20 2000-04-26 Eastman Kodak Company Verfahren zur elektrostatisch assistierten schnellen Vorhangbeschichtung
US6099913A (en) * 1998-10-20 2000-08-08 Eastman Kodak Company Method for curtain coating at high speeds
US6666946B2 (en) 2001-03-14 2003-12-23 3M Innovative Properties Company Method of high speed coating pigment-containing liquid coating materials
WO2019190623A1 (en) * 2018-03-28 2019-10-03 Dow Global Technologies Llc Methods for curtain coating substrates
CN112154035A (zh) * 2018-03-28 2020-12-29 陶氏环球技术有限责任公司 用于帘式涂布基材的方法
US11369988B2 (en) 2018-03-28 2022-06-28 Dow Global Technologies Llc Methods for curtain coating substrates

Also Published As

Publication number Publication date
GB9523138D0 (en) 1996-01-10
JPH09173975A (ja) 1997-07-08

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