CA1258572A - Method for producing a spinning nozzle plate - Google Patents
Method for producing a spinning nozzle plateInfo
- Publication number
- CA1258572A CA1258572A CA000513271A CA513271A CA1258572A CA 1258572 A CA1258572 A CA 1258572A CA 000513271 A CA000513271 A CA 000513271A CA 513271 A CA513271 A CA 513271A CA 1258572 A CA1258572 A CA 1258572A
- Authority
- CA
- Canada
- Prior art keywords
- portions
- resist layer
- funnel
- layer
- negatives
- 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.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/08—Perforated or foraminous objects, e.g. sieves
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49428—Gas and water specific plumbing component making
- Y10T29/49432—Nozzle making
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention relates to a method for producing spinning nozzle plates having funnel-shaped preliminary channels in flow communication with nozzle capillaries. Two embodiments of the method are provided which use photolithograhic and electrodeposition techniques. Common to both embodiments of the method is the use of a metal plate provided with funnel-shaped preliminary channels as a self-aligning irradiation mask for irradiating a photoresist layer provided on the metal plate. Nozzle capillaries subsequently defined either in an electrodeposited layer according to a first embodiment of the invention or in electrodeposited tubular projections according to a second embodiment of the invention, have an offset-free, continuous transition between themselves and the preliminary channels. Photolithographic and electrodeposition techniques may also be used to define the funnel-shaped preliminary channels in the metal plates.
The present invention relates to a method for producing spinning nozzle plates having funnel-shaped preliminary channels in flow communication with nozzle capillaries. Two embodiments of the method are provided which use photolithograhic and electrodeposition techniques. Common to both embodiments of the method is the use of a metal plate provided with funnel-shaped preliminary channels as a self-aligning irradiation mask for irradiating a photoresist layer provided on the metal plate. Nozzle capillaries subsequently defined either in an electrodeposited layer according to a first embodiment of the invention or in electrodeposited tubular projections according to a second embodiment of the invention, have an offset-free, continuous transition between themselves and the preliminary channels. Photolithographic and electrodeposition techniques may also be used to define the funnel-shaped preliminary channels in the metal plates.
Description
357;~
B~CKGROUND OF THE INVENTION
-l. Field of the Invention The present invention relates to a method for produc-ing a spinning nozzle plate, and in particular to a metllod for producing a spinning nozzle plate for the spinning of fibers which has funnel-shaped preliminary channels in flow communica-tion with nozzle capillaries.
B~CKGROUND OF THE INVENTION
-l. Field of the Invention The present invention relates to a method for produc-ing a spinning nozzle plate, and in particular to a metllod for producing a spinning nozzle plate for the spinning of fibers which has funnel-shaped preliminary channels in flow communica-tion with nozzle capillaries.
2. Background of the Art A method of thi 5 type is disclosed and illustrated in Canadian Patent Application SN 509,340, filed May 16th, 1986, by ~rwin Becker, and the present inventors Wolfgat-~ El-rfeLd an-1 Peter l~agmann.
When fibers oE organic or inorganic material are produced in large-scale industrial systems, the starting material is pressed, in a flowable state, tl)rougll spinning nozzle plates which are equipped witll a plurality of spinning nozzle channels. In most cases, the spinning nozzle channels are composed oE preliminary channels into which the material to be spun is fed and nozzle capillaries tllrough which the material is discharged in the form of fibers, the nozzle capil-laries being in flow communication with the substantially wider preliminary c)lannels. The preliminary cl-annels 125857;~
frequently have the shape of funnels which become narrower toward the nozzle capillaries with which they structurally communicate.
When preliminary channels and nozzle capillaries are produced separately, such as in the separate lithographic-a~ o ~
~' electrolytic deposition steps according to/~. Patent ~ ,3~f~
Application Serial No. ~t~61~9, an undesirable offset frequently occurs at the point of transition from the narrow end of the funnel-shaped preliminary channel to the nozzle capillary. These offsets are typically caused by photo-lithographic mask misalignments and/or distortions and produce undesirable perturbations in the flow of the material to be spun. The resulting spun fiber thickness and/or thickness continuity may vary unacceptably from product specifications, and a sharp offset edge can cause a non-uniform disruption in the continuity of the fiber as well.
SUMMARY OF THE INVENTION
Based on this state of the art, it is an object of the present invention to provide a method for the production of spinning nozzle plates which assures a continuous, offset-free transition from the preliminary channels to the nozzle capillaries.
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This and other objects are attained by a method which uses the funnel-shaped preliminary channels as a self-aligning irradiation mask for producing the nozzle capillaries by photolithographic techniques. An offset-free, flush transition from each preliminary channel to a nozzle capillary is realized by providing a method wherein a metal plate having opposing first and second surfaces and having a plurality of spaced-apart preliminary channels defined therethrough are provided, each preliminary channel having a funnel-shape including a tapered end which opens at the first surface of the metal plate. A resist layer is provided on the first surface of the metal plate, which resist layer comprises a radiation-sensitive material. First portions of the resis~ layer are subjected to high energy radiation by irradiating the second surface of the metal plate whereby radiation is directed through the preliminary channels of the metal plate onto the resist layer, the metal plate thereby functioning as a self-aligning mask. Negatives of a plurality of nozzle capillaries are provided on the first surface of the metal plate by removing portions of the resist layer to expose portions of the first surface of the metal plate and, either before or after the removing step, depending on whether the resist layer is composed of a negative resist material or a positive resist material, ~2S85~
filling at least the preliminary channels with a removable filler material. A galvanic layer is electrodeposited on the exposed portions of the first surface of the metal plate using the metal plate as an electrode, the galvanic layer thereby defining a plurality of nozzle capillaries. The galvanic layer is planed and the removable filler material and the negatives of the plurality of nozzle capillaries are removed, whereby the fiber spinning nozzle plate is produced.
When the resist layer is composed of a negative resist material, the negatives of the nozzle capillaries are provided by filling the preliminary channels with the removable filler material before removing portions of the resist layer, which portions are non-irradiated portions.
When the resist layer is composed of a positive resist material, the negatives of the nozzle capillaries are provided by, in the order recited, removing portions of the resist layer, which portions are irradiated portions, thereby defining nozzle capillary zones; filling the preliminary channels and the nozzle capillary zones with a removable filler material; and removing non-irradiated portions of the resist layer.
Rather than defining the nozzle capillaries within an otherwise continuous galvanic layer, the nozzle capillaries may be each defined within a tubular projection extending ~2~i857~
from the first surface of the metal plate and having an outer diameter and positioning. The method then includes the further step of subjecting second portions of the resist layer, which resist layer is composed of a negative resist material, to high energy radiation by irradiating a second time through a mask positioned adjacent to the resist layer, immediately following the step of subjecting first portions of the resist layer to high energy radiation. The mask has absorber structures which correspond in diameter and posi-tioning to the outer diameter and positioning of the tubularprojections to be subsequently provided. The non-irradiated portions of the resist layer correspond to negatives of the tubular projections, such that the step of removing the non-irradiated portions of the resist layer results in the formation of tubular cavities, which cavities expose portions of the first surface. Then, the subsequent step of electro-depositing a galvanic layer provides a discontinuous galvanic layer consisting of tubular projections.
When the resist layer is composed of a positive resist material and the plurality of nozzle capillaries are each defined within a tubular projection, the method includes the further steps of, after the step of filling the preliminary channels and the nozzle capillary zones with a removable filler material, subjecting second portions of the resist 1;~5857~
ldyer to high energy radiation by irradiating a second time through a mask positioned adjacent to the resist layer. The mask has passages which correspond in diameter and position-ing to the outer diameter and positioning of the tubular 5 projections to be subsequently provided. The irradiated second portions of the resist layer correspond to negatives of the tubular projections and when the irradiated second portions of the resist layer are removed, tubular cavities are formed. The tubular cavities expose portions of the 10 first surface so that the subsequent step of electrodeposit-ing a galvanic layer provides a discontinuous galvanic layer consisting of the tubular projections.
Spinning nozzle plates having tubular nozzle capillaries may be used with particular advantage as components of 15 spinning nozzle devices for the production of hollow fibers or multicomponent fibers. Such spinning nozzle devices are generally composed of a plurality of superposed spinning nozzle plates. Since, according to the method of the present invention, the nozzle capillaries can be manufactured with 20 extreme precision and uniformity with respect to their individual cross-sections, as well as their mutual position-ing, and the alignment of a plurality of relatively large spinning nozzle plates with respect to one another poses no major problems in the assembly of spinning nozzle devices, ~;~5857;~
the manufacture of hollow fibers or multicomponent fibers having any desired cross-section and structure is possible.
Thus, fibers for novel and unusual purposes can be produced by this method.
The metal plate provided for use in the foregoing method has a plurality of spaced-apart preliminary channels defined therethrough and may be fabricated by a variety of methods which are well known in the art, such as by routine machining methods. Particularly preferred for the present invention, however, is a method using photolithographic and electro-deposition techniques wherein a resist layer is provided on an electrode plate. Portions of the resist laver are then subjected to high energy radiation, which radiation has a direction, through a mask having passages. The passages correspond in cross-sectional size and shape and in position-ing to that of the tapered ends of the funnel-shaped prelimi-nary channels to be subsequently provided. The mask, resist layer and electrode plate form a unit, which unit is movably positioned in a plane perpendicular to the direction of the high energy radiation. During irradiation, the unit is moved with respect to the plane and the radiation direction. The negatives of the plurality of the funnel-shaped preliminary channels are provided on the electrode plate by removing portions of the resist layer to expose portions of the electrode plate. A galvanic layer is electrodeposited on the exposed portions of the electrode plate, the galvanic layer 8S7~
thereby defining a plurality of funnel-shaped preliminary channels. The galvanic layer is then planed and the nega-tives and the electrode plate are removed, whereby the metal plate is provided.
When the resist layer is composed of a negative resist material, the negativesof the funnel-shaped preliminary channels are provided on the electrode plate by removing non-irradiated portions of the resist layer. When the resist layer is composed of a positive resist material, the nega-tives of the funnel-shaped preliminary channels are provided on the elec~rode plate by, in the order recited, removing portions of the resist, which portions are irradiated portions, thereby defining preliminary channel zones; filling the preliminary channel zones with a removable filler 15 material; and removing further portions of the resist layer, which further portions are non-irradiated portions.
The movement of the unit with respect to the plane and the radiation direction during irradiation may be movement by rocking the unit abou~ the plane in at least one direction, 20 whereby the irradiated portions of the resist layer have a trapezoidal funnel shape. Alternately, the movement of the unit may be by tumbling the unit about the plane whereby the resist layer have a conical funnel shape. The high energy radiation, moreover, is preferably X-ray radiation generated by an electron synchrotron.
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The offset-free, continuous transition from preliminary channel to nozzle capillary realized by the present invention is also achievable with nozzle capillaries having a special shape. For example, star-shaped cross-sections, as well as 5 nozzle capillaries having circular cross-sections, etc., are achievable.
BRIEF DESCRIPTION OF THE DRAWING
The individual steps of the method according to the present invention will be described below with reference to 10 the drawing figures which schematically show in cross-section various stages in the production of a spinning nozzle plate:
Figure 1 shows irradiation of a resist layer through the funnel-shaped preliminary channels of a metal plate, which metal plate is functioning as a self-aligning mask in a first 15 embodiment of the method as shown in Figures 1 through 4;
Figure 2 shows the funnel-shaped preliminary channels of the metal plate of Figure 1 filled with a removable filler material, after which negatives of the nozzle capillaries are provided by removing non-irradiated portions of a resist 20 layer composed of a negative resist material;
Figures 2a, 2b and 2c show negatives of the nozzle capillaries provided by removing irradiated portions of a resist layer composed of a positive resist material to define 125857~
capillary zones (Figure 2a), filling the funnel-shaped preliminary channels and the nozzle capillary zones with a removable filler material (Figure 2b), and removing non-irradiated portions of the resist layer ~Figure 2c);
Figure 3 and 3a show electrodepositing a galvanic layer on the surface of the metal plate of Figures 2 and 2c, respectively, after providing the surface with negatives of the nozzle capillaries;
Figure 4 shows a finished spinning nozzle plate accord-10 ing to the first embodiment of the invention with an offset-free, flush transition between preliminary channel and nozzle capillary formed by planing the galvanic layer of Figures 3 and 3a and removing the filler material and the negatives of the nozzle capillaries;
Figure 5 shows irradiation of a resist layer through the funnel-shaped preliminary channels of a metal plate, which metal plate is functioning as a self-aligning mask in a second embodiment of the method as shown in Figures 5 through 9 wher~in the nozzle capillaries are defined within tubular 20 projections;
Figure 6 shows irradiation of the negative resist layer of Figure S a second time through a mask having absorber structures which correspond in diameter and positioning to that for tubular projections to be subsequently provided, 1~58~7;~ 1 so that non-irradiated portions of the resist layer cor-respond to negatives of the tubular projectionS, the prelimi- ¦
nary channels being filled with a removable filler material;
Figure 6a shows irradiation of the positive resist layer of Figure 5 a second time after removing the portions of the resist layer irradiated in Figure 5 to define nozzle capil-lary zones and after subsequently filling the nozzle capil-lary zones and the preliminary channels with a removable filler material, the second irradiation being through a mask having passages which correspond in diameter and positioning to that for tubular projections to be subsequently provided, so that irradiated portions of the rPsist layer correspond to negatives of the tubular projections;
Figures 7 and 7a show tubular cavities formed by removing the negatives of the tubular projections thereby forming tubular cavities and exposing portions of the metal plate; in Figure 7, the non-irradiated portions of the negative resist layer of Figure 6, and in Figure 7a, the irradiated portions of the positive resist layer of Figure 6a;
Figure 8 shows electrodepositing a galvanic layer, which is a discontinuous galvanic layer consisting of tubular projections, onto the portions of the metal plate exposed by the tubular cavities formed in Figures 7 and 7a;
1~5857;~
Figure 9 shows a finished spinning nozzle plate accord-ing to the second embodiment of the invention with an offset-free, flush transition between preliminary channel and nozzle capillaries formed by planing the galvanic layer of Figure 8 and removing the filler material and the negatives of the nozzle capillaries;
Figure 10 relates to a method for providing a metal plate having funnel-shaped preliminary channels and shows irradiation through a mask of a unit formed by an electrode plate provided with a resist layer composed of a negative resist material and the mask, which mask has passages, the units being movably positioned in a plane perpendicular to the direction of the irradiation and being moved about the plane during irradiation;
Figure 11 shows electrodeposition of a galvanic layer onto exposed portions of the electrode plate of Figure 10, after removing the non-irradiated portions of the resist layer to form negatives of the funnel-shaped preliminary channels on exposed portions of the electrode plates; and Figure 12 shows a finished metal plate having funnel-shaped preliminary channels after the electrode plate and the negatives of the funnel-shaped preliminary channels according to Figure 11 have been removed.
12S85~
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Figure 1 shows a metal plate 141 having funnel-shaped preliminary channels 144. The side of metal plate 141, first surface 141a, at which tapered ends 144a of the prelimi-nary channels 144 open, is provided with a resist layer 142of radiation-sensitive, negative resist material. Portions 145 of resist layer 142 are irradiated through the prelimi-nary channels 144 by irradiating the other side of plate 141, second surface 141b, with high energy radiation 143, for example with X-ray radiation 143 from an electron synchro-tron, thereby causing changes in the irradiation-sensitive, negative photoresist material which render the irradiated portions 145 substantially insolu~le in a developer (not shown). The irradiated portions 145 have a cross-sectional shape and size which corresponds to the cross-sectional shape and size of the tapered ends 144a of the preliminary channels 144 and have a volume which corresponds in size and shape to that of the nozzle capillaries.
Examples of negative resist materials useful in the present invention are polystyrene-based materials, many commercially-available variations of such formulations being available. Preferred developers for polystyrene-based negative resist materials are liquid developers useful as an immersion bath or spray and are composed of a mixture of ketones and higher alcohols. A non-irradiated resist layer of this negative type is readily soluble in the developer.
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25213-~5 A resist layer 142 may be provided on metaL plate 141 in any one of several ways. The preliminary channels 144 of the metal plate 141 may be filled with a removable filler material and the resist layer 142 coated in any one of several methods including flow coating, roller coating, dip coating, etc. A removable filler 152 is shown filling the preliminary channels 144 in Figure 2, for example. Since the removable filler material is not transmissive in a thick layer to high energy radiation, it is removed prior to the irradiation step.
Alternately, if the cross-sectional area of the tapered ends 144a of the preliminary channels 144 are suffi-ciently small in view of the viscosity, as adjusted such as with solvents and/or thickeners, of the photoresist material to be coated thereon, for example, on the order of 0.1 millimeter square or less, the resist layer may be coated by roller coat-ing, flow coating, etc., directly onto the first surface 141a of the metal plate, despite the presence of the tapered ends 144a which open at the first surface 144a.
The photoresist layers 142 may be provided by yet another method variation in which a self-supporting sheet of the photoresist materia] is prepared and is laminated onto 1~:5857;~
the first surface 141a of the metal plate 144 while tacky and~or by the application of heat and pressure, such as by rolling the outer surface of the self-supporting resist material with a heated roller under pressure. In a further variation of this alternate method, a thin adhesive layer (non shown) may be coated onto the first surface 141a of the metal plate 144 and a self-supporting photoresist material applied to the adhesi~e layer, with or without the simul-taneous application of heat and pressure.
125~357~
After irradiation of the resist layer 142 through metal plate 141, using metal plate 141 as a self-aligning mask, if the preliminary channels 144 are not already filled with removable filler material 152, they are filled with removable filler material 152 of a type which bonds or can be caused to bond to the inside walls of preliminary channels 144 as well as to the portions of the resist layer 142 at the interfaces thereof with preliminary channels 144. This removable filler material 152 is composed of, for example, a mixture of an epoxide resin and an internal separating agent. Removable filler material is preferably chemically removable by dissolution in a solvent, such as by immersing or spraying. It is necessary that the removable filler material 152 be substantially resistant to the developers used in conjunction with developing the photoresist materials after irradiation.
With reference to Figure 2, after filling prelimi-nary channels 144 with removable filler material 152, the non-irradiated portions of resist layer 142 are removed, for example, by immersing resist layer 142 in liquid developer (not shown) leaving only negatives 151 of nozzle capi-llaries on metal plate 141. Negatives 151 are shown in Figure 2 as having a column-shape, the cross-section of negatives 151, however, need not be circular, but may have virtually any shape, such as the shape of a star, a rectangle, a square, a triangle, etc.
1;~5857,t::
With reference to Figure 3, metal plate 141 serves as an electrode during the electrodeposition of a gal~anic la~er 162 onto the exposed portions of first surface 141a of the metal plate 141. The electrodeposited galvanic layer 162 5 thus surrounds and includes the negatives 151 of nozzle capillaries, however, the galvanic layer 162 has a thic~ness which does not substantially exceed the thickness of the negatives 151, since the negatives 151 are to be removed in a subsequent step.
Galvanic layer 162 is then planed to achieve a desired surface finish and thickness, which thickness preferably does not exceed that of negatives 151. Negatives 151 of nozzle capillaries are then removed in a process, such as chemically dissolving the developer-insensitive, irradiated resist 15 material which composes the negatives 151 in a commercially-available liquid stripper bath (not shown). The removable filler material 152 is preferably simultaneously removed in the same operative step as for the removal of the negatives 151, for example in the stripper bath. Alternately, filler 20 material 152 may be removed in a process such as immersing in a bath of, or spraying with, a solvent or stripper material selected on the basis of the chemical and/or physical properties of the specific removable filler material.
125857;~
252l3-65 A finished spinning nozzle plate 163 is shown in Figure 4. Spinning nozzle plate 163 has funnel-shaped pre]imi-nary channels 144 in flow communication with nozzle capillaries 161, tlle structural connection therebetween being continuous, that is, flush and without a seam, and having no offsets. In tlliS manner, the recited objects accordiny to the present invention, which uses the funnel-shaped preliminary channels l44 as a self-aligning irradiation mask during the photolitho-graphic/electrodeposition formation of nozzle capillaries, are 10 accomplished.
With reference again to Figure 1, if a radiation-sensitive, positive resist material is used to ~orm a resist layer 142, now identified as resist layer 142a, the sequence of formative steps varies somewhat as shown in Figures 2a, 2b, 2c, and 3a. After irradiation tllrough the metal plate 141, irradiated portions are removed as shown in Figure 2a, for example, with a liquid developer (not shown).
Many commercially-available positive photoresist materials are available. As an example, polymetl-ylmeth-acrylate-based resist materials may be used. Preferred developers for polymethylmethacrylate-based positive photo-resist materials are liquid developers useful as a immersion bath or spray and are composed of a mixture of diethylene glycol monobutyl ether morpholine, ethanolamine and water.
' v', 125857~
The step of removing irradiated portions shown in Figure 2a defines a nozzle capillary zone 142b. As shown in Figure 2b, nozzle capillary zones 142b and preliminary channels 144 are filled with a removable filler material 152a, which filler material 152a is substantially less soluble than the positive resist material of resist layer 142a.
The non-irradiated portions of resist layer 142a are removed to produce negatives 151a of nozzle capillaries on metal plate 141 as shown in Figure 2c. Removal of the non-irradiated portions of resist layer 142a is accomplished, for example, by immersion thereof in a solvent which selectively dissolves the non-irradiated portions of resist layer 142a without dissolving the removable filler material 152a. Selection criteria for such solvents are well known in the art. Generally, the developer for the resist material may be used.
Galvanic layer 162 is produced as previously described by electrodeposition using metal plate 141 as an electrode, as shown in Figure 3a. The galvanic layer 162 is planed to a desired surface finish and thickness and the removable f-ller material, which includes the filler material 152a in the preliminary channels and the filler material 151a which constitutes the negatives 151a, is removed. Again, a spinning nozzle plate 163 is produced as shown in Figure 4.
125~357~
The method according to the present invention can also be used for the production of spinning nozzle plates having nozzle capillaries defined within tubular projections. In this second embodiment according to the invention, a metal 5 plate 141 having funnel-shaped preliminary channels 144 defined therethrough is provided with a resist layer 142 along a first surface 141a thereof and is again employed as a self-aligning irradiation mask as shown in Figure 5. High energy radiation, that is, radiation which is actinic with respect to resist layer 142, is directed upon a second surface 141b of the metal plate 141 such that a first portion 174 of resist layer 142 is irradiated through the preliminary channels 144 of metal plate 141. If resist layer 142 is composed of a negative resist material, a mask having absorber structures 182 corresponding to the outer diameters 15 of the tubular projections to be subsequently provided is employed for irr~diation of a second portion 175 of resist layer 142 with high energy radiation 181 as shown in Figure 6. Absorber structures 182 may be spaced apart from or placed in contact with resist layer 142, and in alignment so 20 that non-irradiated portions of the resist layer 142 cor-respond to negatives 183 of the tubular projections to be subsequently provided. Thus, as shown in Figure 6, irradi-ated first and second portions 174 and 175, respectively, 1;~5~57;~ 1 surround non-irradiated portions 1~3 of resist layer 142~
Preliminary channels 144 are then filled with a removable filler material 191.
With referen~e to Figure 7, tubular cavities 192 are provided in resist layer 142 by removing non-irradiated portions, i.e., the negatives 183, for example, by chemically removing same by immersion or spraying with a liquid developer. Tubular cavities 192 extend down to the first surface 141a of the metal plate 141 exposing portions of same.
A galvanic layer or structure is shown in Figure 8 as having the form of tubular projections 202 and is provided by electrodeposition using metal plate 141 as an electrode.
The galvanic layer or structure in the form of tubular projec~ions 202 are, for example, metal structures prepared by immersion of at least the tubular cavities 192 and the exposed portions of first surface 141a of the metal plate 141 in an electrodeposition bath which may be, for example, a chloride-free nickel sulfamate bath maintained at a tempera-ture of 52C. The bath may also include additionalcomponents including boric acid, used to buffer the electro-lyte to a pH=4, and a wetting agent to prevent pore formation.
1;2S85~;~
The galvanic layer in the form of tubular projections 202 is then planed as before and the first portion 174 and second 175 of resist layer 142, as well as filler material l91 are both removed so that a spinning nozzle plate 211 is provided as shown in Figure 9. The spinning nozzle plate 211 according to the second embodiment of the invention has funnel-shaped preliminary channels 144 in flow communication with nozzle capillaries 161a, which nozzle capillaries 161a are defined by tubular projections 202.
The preferred high energy radiation 143 and/or 181 employed is X-ray radiation generated by an electron synchrotron having a characteristic wavelength ~c = 0.2 nm.
A~sorber structures 182 useful in X-ray masks are composed of, for example, about 16 microns of gold which is essentially impermeable to X-ray radiation. The gold absorber structures 182 may be carried on a mask substrate which is substantially permeable to X-ray radiation, such as a mask substrate of beryllium in sheet form and having a thickness of approximately 20 microns.
If a positive resist material is used to provide a resist layer 142a in the second embodiment of the method according to the present inven~ion, the irradiated portions of resist layer 142a ( not shown) correspond to negatives 174a (not shown) of nozzle capillaries and are provided by, 12S~5~
in the order recited, removing irradiated portions 174a by chemically removing same, for example, by immersion thereof in a bath of liquid developer, thereby defining nozzle capillary zones 161b (Figure 6a), and filling the preliminary channels 144 and the nozzle capillary zones 161b with a removable filler material l91a. Then, as shown in Figure 6a, second portions 183a of the resist layer 142a are subjected to high energy radiation 181 by irradiating a second time through a mask positioned adjacent to resist layer 142a, either in spaced apart relation thereto or in contact therewith, after the step of filling the preliminary channels 144 and the no~zle capillary zones 161b with removable filler material l91a. The mask has absorber structures 182a provided with passages 182b which are permeable to high energy radiation 181. Passages 182b have diameters and positioning which correspond to the outer diameter and positioning of the tubular projections 202 to be subsequently provided.
The irradiated second portions 183a of the resist layer 142a correspond to negatives 174a of the tubular projections 202. Irradiated second portions 183a are thus tubular and are produced between removable filler material l91a and the non-irradiated portions of positive resist material of layer 142a. Irradiated portions 183a are then removed, such as by immersion or spraying with a liquid developer or solvent ~ 2S~57~ `
therefore, so that tubular cavities 192a are formed as shown in Figure 7a. Electrodeposition, planing, and removing the filler material l91a and the remaining positive resist layer 142a are analogous to the description regarding Figure 8 for a negative resist system. Thus, the novel spinning nozzle plate 211 as shown in Figure 9 according to the second embodim~nt of the method of the present invention results and has the advantages previously described.
With reference to Figures 10, 11 and 12, metal plate 141 having funnel-shaped preliminary channels 144 can similarly be produced by photolithographic/electrodeposition methods.
The misalignment problems typical of conventional machining operations can be substantially eliminated by photolitho-graphic methods. Thus, an electrode plate 12 may be provided with a resist layer 121 composed of either a negative or a positive resist material. Plate 12 is a continuous plate and the resist layer 121 may be applied thereto by conventional coating means, such as by roller or dip coating. A mask 122 is disposed a short distance away from the surface of resist layer 121 as shown in Figure 10. Mask 122 is comprised of absorber structures having passages 125 defined therein.
Passages 125 permit the passage of high energy radiation therethrough and have a cross-sectional size and shape and positioning corresponding to that of the tapered ends 144a of the funnel-shaped preliminary channels 144 to be sub-sequently provided.
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Preferably, high energy radiation 123 is parallel X-ray radiation 123 from an electron synchrotron. As shown in Figure 10, mask 122, resist layer 121 and electrode plate 12 form a unit 122, 121, 12 which is movably positioned in a plane perpendicular to the direction of the high energy radiation 1~3. The unit 122, 121, 12 is shown as occupying the plane and is moved with respect to the plane and the radiation direction during irradiation of the resist layer 121. When trapezoidal funnel-shaped preliminary channels 144 are desired, the unit is moved during irradiation by rocking the unit about the plane in at least one direction, the rocking motion being indicated in Figure 10 by arrows A.
Rocking may take place in two mutually perpendicular direc-tions, so that rocking of the unit takes place about an imaginary fulcrum, first in a direction parallel to the plane of the paper and second in a direction perpendicular to the plane of the paper. When conical funnel-shaped preliminary channels 144 are desired, the unit is moved during irradia-tion by rolling the unit about the plane symmetrically and conically as indicated in Figure ll by arrows B. Funnel-shaped preliminary channels 144 having other shapes are possible by varying the nature of the movement of the unit during irradiation.
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If the precision of the preliminary channels 144 need not be great, irradiation from a highly divergent, planar radiation source may take the place of rolling the unit during irradiation. Other variations will be immediately obvious to the artisan.
When the resist layer 121 is composed of a negative resist material, negatives 131 of the funnel-shaped preliminary channels 144 are provided on the electrode plate 12 by removing non-irradiated portions of the resist layer 121, by means of, for example, a liquid developer tnot shown). The irradiated portions 124 of resist layer 121 are rendered soluble only with greater difficulty by the irradia-tion step compared to the non-irradiated portions of the resist layer 121.
Alternately, when the resist layer 121 is composed of a positive resist material, negatives 131 of funnel-shaped preliminary channels 144 are provided on the electrode plate 12 ~y process steps analogous to those shown in Figures 2a, 2b and 2c. Thus, in the order recited, irradiated portions ~0 124 of the resist layer 121 are removed thereby defining preliminary channel zones 124, the preliminary channel zones 124 are filled with a removable filler material, and the non-irradiated portions of resist layer 121 are removed.
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252]3-65 As shown in Yigure 11, whether generated using a positive resist material or a negative resist material, a gal-vanic l.ayer 141 is electrodeposited onto the exposed surfaces of electrode plate 12. The galvanic layer 141 is planed and negatives 131 and electrode plate 12 are removed so that a metal plate 141 having funnel-shaped preliminary channels 144 is provided as shown in Fiqure 12.
It will be understood that the above description of the present invention is susceptible to various modifications, chanqes and adaptations, and the same are intended to be comprehended within the meaning and range of equivalents of the appended claims.
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When fibers oE organic or inorganic material are produced in large-scale industrial systems, the starting material is pressed, in a flowable state, tl)rougll spinning nozzle plates which are equipped witll a plurality of spinning nozzle channels. In most cases, the spinning nozzle channels are composed oE preliminary channels into which the material to be spun is fed and nozzle capillaries tllrough which the material is discharged in the form of fibers, the nozzle capil-laries being in flow communication with the substantially wider preliminary c)lannels. The preliminary cl-annels 125857;~
frequently have the shape of funnels which become narrower toward the nozzle capillaries with which they structurally communicate.
When preliminary channels and nozzle capillaries are produced separately, such as in the separate lithographic-a~ o ~
~' electrolytic deposition steps according to/~. Patent ~ ,3~f~
Application Serial No. ~t~61~9, an undesirable offset frequently occurs at the point of transition from the narrow end of the funnel-shaped preliminary channel to the nozzle capillary. These offsets are typically caused by photo-lithographic mask misalignments and/or distortions and produce undesirable perturbations in the flow of the material to be spun. The resulting spun fiber thickness and/or thickness continuity may vary unacceptably from product specifications, and a sharp offset edge can cause a non-uniform disruption in the continuity of the fiber as well.
SUMMARY OF THE INVENTION
Based on this state of the art, it is an object of the present invention to provide a method for the production of spinning nozzle plates which assures a continuous, offset-free transition from the preliminary channels to the nozzle capillaries.
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This and other objects are attained by a method which uses the funnel-shaped preliminary channels as a self-aligning irradiation mask for producing the nozzle capillaries by photolithographic techniques. An offset-free, flush transition from each preliminary channel to a nozzle capillary is realized by providing a method wherein a metal plate having opposing first and second surfaces and having a plurality of spaced-apart preliminary channels defined therethrough are provided, each preliminary channel having a funnel-shape including a tapered end which opens at the first surface of the metal plate. A resist layer is provided on the first surface of the metal plate, which resist layer comprises a radiation-sensitive material. First portions of the resis~ layer are subjected to high energy radiation by irradiating the second surface of the metal plate whereby radiation is directed through the preliminary channels of the metal plate onto the resist layer, the metal plate thereby functioning as a self-aligning mask. Negatives of a plurality of nozzle capillaries are provided on the first surface of the metal plate by removing portions of the resist layer to expose portions of the first surface of the metal plate and, either before or after the removing step, depending on whether the resist layer is composed of a negative resist material or a positive resist material, ~2S85~
filling at least the preliminary channels with a removable filler material. A galvanic layer is electrodeposited on the exposed portions of the first surface of the metal plate using the metal plate as an electrode, the galvanic layer thereby defining a plurality of nozzle capillaries. The galvanic layer is planed and the removable filler material and the negatives of the plurality of nozzle capillaries are removed, whereby the fiber spinning nozzle plate is produced.
When the resist layer is composed of a negative resist material, the negatives of the nozzle capillaries are provided by filling the preliminary channels with the removable filler material before removing portions of the resist layer, which portions are non-irradiated portions.
When the resist layer is composed of a positive resist material, the negatives of the nozzle capillaries are provided by, in the order recited, removing portions of the resist layer, which portions are irradiated portions, thereby defining nozzle capillary zones; filling the preliminary channels and the nozzle capillary zones with a removable filler material; and removing non-irradiated portions of the resist layer.
Rather than defining the nozzle capillaries within an otherwise continuous galvanic layer, the nozzle capillaries may be each defined within a tubular projection extending ~2~i857~
from the first surface of the metal plate and having an outer diameter and positioning. The method then includes the further step of subjecting second portions of the resist layer, which resist layer is composed of a negative resist material, to high energy radiation by irradiating a second time through a mask positioned adjacent to the resist layer, immediately following the step of subjecting first portions of the resist layer to high energy radiation. The mask has absorber structures which correspond in diameter and posi-tioning to the outer diameter and positioning of the tubularprojections to be subsequently provided. The non-irradiated portions of the resist layer correspond to negatives of the tubular projections, such that the step of removing the non-irradiated portions of the resist layer results in the formation of tubular cavities, which cavities expose portions of the first surface. Then, the subsequent step of electro-depositing a galvanic layer provides a discontinuous galvanic layer consisting of tubular projections.
When the resist layer is composed of a positive resist material and the plurality of nozzle capillaries are each defined within a tubular projection, the method includes the further steps of, after the step of filling the preliminary channels and the nozzle capillary zones with a removable filler material, subjecting second portions of the resist 1;~5857~
ldyer to high energy radiation by irradiating a second time through a mask positioned adjacent to the resist layer. The mask has passages which correspond in diameter and position-ing to the outer diameter and positioning of the tubular 5 projections to be subsequently provided. The irradiated second portions of the resist layer correspond to negatives of the tubular projections and when the irradiated second portions of the resist layer are removed, tubular cavities are formed. The tubular cavities expose portions of the 10 first surface so that the subsequent step of electrodeposit-ing a galvanic layer provides a discontinuous galvanic layer consisting of the tubular projections.
Spinning nozzle plates having tubular nozzle capillaries may be used with particular advantage as components of 15 spinning nozzle devices for the production of hollow fibers or multicomponent fibers. Such spinning nozzle devices are generally composed of a plurality of superposed spinning nozzle plates. Since, according to the method of the present invention, the nozzle capillaries can be manufactured with 20 extreme precision and uniformity with respect to their individual cross-sections, as well as their mutual position-ing, and the alignment of a plurality of relatively large spinning nozzle plates with respect to one another poses no major problems in the assembly of spinning nozzle devices, ~;~5857;~
the manufacture of hollow fibers or multicomponent fibers having any desired cross-section and structure is possible.
Thus, fibers for novel and unusual purposes can be produced by this method.
The metal plate provided for use in the foregoing method has a plurality of spaced-apart preliminary channels defined therethrough and may be fabricated by a variety of methods which are well known in the art, such as by routine machining methods. Particularly preferred for the present invention, however, is a method using photolithographic and electro-deposition techniques wherein a resist layer is provided on an electrode plate. Portions of the resist laver are then subjected to high energy radiation, which radiation has a direction, through a mask having passages. The passages correspond in cross-sectional size and shape and in position-ing to that of the tapered ends of the funnel-shaped prelimi-nary channels to be subsequently provided. The mask, resist layer and electrode plate form a unit, which unit is movably positioned in a plane perpendicular to the direction of the high energy radiation. During irradiation, the unit is moved with respect to the plane and the radiation direction. The negatives of the plurality of the funnel-shaped preliminary channels are provided on the electrode plate by removing portions of the resist layer to expose portions of the electrode plate. A galvanic layer is electrodeposited on the exposed portions of the electrode plate, the galvanic layer 8S7~
thereby defining a plurality of funnel-shaped preliminary channels. The galvanic layer is then planed and the nega-tives and the electrode plate are removed, whereby the metal plate is provided.
When the resist layer is composed of a negative resist material, the negativesof the funnel-shaped preliminary channels are provided on the electrode plate by removing non-irradiated portions of the resist layer. When the resist layer is composed of a positive resist material, the nega-tives of the funnel-shaped preliminary channels are provided on the elec~rode plate by, in the order recited, removing portions of the resist, which portions are irradiated portions, thereby defining preliminary channel zones; filling the preliminary channel zones with a removable filler 15 material; and removing further portions of the resist layer, which further portions are non-irradiated portions.
The movement of the unit with respect to the plane and the radiation direction during irradiation may be movement by rocking the unit abou~ the plane in at least one direction, 20 whereby the irradiated portions of the resist layer have a trapezoidal funnel shape. Alternately, the movement of the unit may be by tumbling the unit about the plane whereby the resist layer have a conical funnel shape. The high energy radiation, moreover, is preferably X-ray radiation generated by an electron synchrotron.
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The offset-free, continuous transition from preliminary channel to nozzle capillary realized by the present invention is also achievable with nozzle capillaries having a special shape. For example, star-shaped cross-sections, as well as 5 nozzle capillaries having circular cross-sections, etc., are achievable.
BRIEF DESCRIPTION OF THE DRAWING
The individual steps of the method according to the present invention will be described below with reference to 10 the drawing figures which schematically show in cross-section various stages in the production of a spinning nozzle plate:
Figure 1 shows irradiation of a resist layer through the funnel-shaped preliminary channels of a metal plate, which metal plate is functioning as a self-aligning mask in a first 15 embodiment of the method as shown in Figures 1 through 4;
Figure 2 shows the funnel-shaped preliminary channels of the metal plate of Figure 1 filled with a removable filler material, after which negatives of the nozzle capillaries are provided by removing non-irradiated portions of a resist 20 layer composed of a negative resist material;
Figures 2a, 2b and 2c show negatives of the nozzle capillaries provided by removing irradiated portions of a resist layer composed of a positive resist material to define 125857~
capillary zones (Figure 2a), filling the funnel-shaped preliminary channels and the nozzle capillary zones with a removable filler material (Figure 2b), and removing non-irradiated portions of the resist layer ~Figure 2c);
Figure 3 and 3a show electrodepositing a galvanic layer on the surface of the metal plate of Figures 2 and 2c, respectively, after providing the surface with negatives of the nozzle capillaries;
Figure 4 shows a finished spinning nozzle plate accord-10 ing to the first embodiment of the invention with an offset-free, flush transition between preliminary channel and nozzle capillary formed by planing the galvanic layer of Figures 3 and 3a and removing the filler material and the negatives of the nozzle capillaries;
Figure 5 shows irradiation of a resist layer through the funnel-shaped preliminary channels of a metal plate, which metal plate is functioning as a self-aligning mask in a second embodiment of the method as shown in Figures 5 through 9 wher~in the nozzle capillaries are defined within tubular 20 projections;
Figure 6 shows irradiation of the negative resist layer of Figure S a second time through a mask having absorber structures which correspond in diameter and positioning to that for tubular projections to be subsequently provided, 1~58~7;~ 1 so that non-irradiated portions of the resist layer cor-respond to negatives of the tubular projectionS, the prelimi- ¦
nary channels being filled with a removable filler material;
Figure 6a shows irradiation of the positive resist layer of Figure 5 a second time after removing the portions of the resist layer irradiated in Figure 5 to define nozzle capil-lary zones and after subsequently filling the nozzle capil-lary zones and the preliminary channels with a removable filler material, the second irradiation being through a mask having passages which correspond in diameter and positioning to that for tubular projections to be subsequently provided, so that irradiated portions of the rPsist layer correspond to negatives of the tubular projections;
Figures 7 and 7a show tubular cavities formed by removing the negatives of the tubular projections thereby forming tubular cavities and exposing portions of the metal plate; in Figure 7, the non-irradiated portions of the negative resist layer of Figure 6, and in Figure 7a, the irradiated portions of the positive resist layer of Figure 6a;
Figure 8 shows electrodepositing a galvanic layer, which is a discontinuous galvanic layer consisting of tubular projections, onto the portions of the metal plate exposed by the tubular cavities formed in Figures 7 and 7a;
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Figure 9 shows a finished spinning nozzle plate accord-ing to the second embodiment of the invention with an offset-free, flush transition between preliminary channel and nozzle capillaries formed by planing the galvanic layer of Figure 8 and removing the filler material and the negatives of the nozzle capillaries;
Figure 10 relates to a method for providing a metal plate having funnel-shaped preliminary channels and shows irradiation through a mask of a unit formed by an electrode plate provided with a resist layer composed of a negative resist material and the mask, which mask has passages, the units being movably positioned in a plane perpendicular to the direction of the irradiation and being moved about the plane during irradiation;
Figure 11 shows electrodeposition of a galvanic layer onto exposed portions of the electrode plate of Figure 10, after removing the non-irradiated portions of the resist layer to form negatives of the funnel-shaped preliminary channels on exposed portions of the electrode plates; and Figure 12 shows a finished metal plate having funnel-shaped preliminary channels after the electrode plate and the negatives of the funnel-shaped preliminary channels according to Figure 11 have been removed.
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DESCRIPTION OF THE PREFERRED EMBODIMENTS
Figure 1 shows a metal plate 141 having funnel-shaped preliminary channels 144. The side of metal plate 141, first surface 141a, at which tapered ends 144a of the prelimi-nary channels 144 open, is provided with a resist layer 142of radiation-sensitive, negative resist material. Portions 145 of resist layer 142 are irradiated through the prelimi-nary channels 144 by irradiating the other side of plate 141, second surface 141b, with high energy radiation 143, for example with X-ray radiation 143 from an electron synchro-tron, thereby causing changes in the irradiation-sensitive, negative photoresist material which render the irradiated portions 145 substantially insolu~le in a developer (not shown). The irradiated portions 145 have a cross-sectional shape and size which corresponds to the cross-sectional shape and size of the tapered ends 144a of the preliminary channels 144 and have a volume which corresponds in size and shape to that of the nozzle capillaries.
Examples of negative resist materials useful in the present invention are polystyrene-based materials, many commercially-available variations of such formulations being available. Preferred developers for polystyrene-based negative resist materials are liquid developers useful as an immersion bath or spray and are composed of a mixture of ketones and higher alcohols. A non-irradiated resist layer of this negative type is readily soluble in the developer.
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25213-~5 A resist layer 142 may be provided on metaL plate 141 in any one of several ways. The preliminary channels 144 of the metal plate 141 may be filled with a removable filler material and the resist layer 142 coated in any one of several methods including flow coating, roller coating, dip coating, etc. A removable filler 152 is shown filling the preliminary channels 144 in Figure 2, for example. Since the removable filler material is not transmissive in a thick layer to high energy radiation, it is removed prior to the irradiation step.
Alternately, if the cross-sectional area of the tapered ends 144a of the preliminary channels 144 are suffi-ciently small in view of the viscosity, as adjusted such as with solvents and/or thickeners, of the photoresist material to be coated thereon, for example, on the order of 0.1 millimeter square or less, the resist layer may be coated by roller coat-ing, flow coating, etc., directly onto the first surface 141a of the metal plate, despite the presence of the tapered ends 144a which open at the first surface 144a.
The photoresist layers 142 may be provided by yet another method variation in which a self-supporting sheet of the photoresist materia] is prepared and is laminated onto 1~:5857;~
the first surface 141a of the metal plate 144 while tacky and~or by the application of heat and pressure, such as by rolling the outer surface of the self-supporting resist material with a heated roller under pressure. In a further variation of this alternate method, a thin adhesive layer (non shown) may be coated onto the first surface 141a of the metal plate 144 and a self-supporting photoresist material applied to the adhesi~e layer, with or without the simul-taneous application of heat and pressure.
125~357~
After irradiation of the resist layer 142 through metal plate 141, using metal plate 141 as a self-aligning mask, if the preliminary channels 144 are not already filled with removable filler material 152, they are filled with removable filler material 152 of a type which bonds or can be caused to bond to the inside walls of preliminary channels 144 as well as to the portions of the resist layer 142 at the interfaces thereof with preliminary channels 144. This removable filler material 152 is composed of, for example, a mixture of an epoxide resin and an internal separating agent. Removable filler material is preferably chemically removable by dissolution in a solvent, such as by immersing or spraying. It is necessary that the removable filler material 152 be substantially resistant to the developers used in conjunction with developing the photoresist materials after irradiation.
With reference to Figure 2, after filling prelimi-nary channels 144 with removable filler material 152, the non-irradiated portions of resist layer 142 are removed, for example, by immersing resist layer 142 in liquid developer (not shown) leaving only negatives 151 of nozzle capi-llaries on metal plate 141. Negatives 151 are shown in Figure 2 as having a column-shape, the cross-section of negatives 151, however, need not be circular, but may have virtually any shape, such as the shape of a star, a rectangle, a square, a triangle, etc.
1;~5857,t::
With reference to Figure 3, metal plate 141 serves as an electrode during the electrodeposition of a gal~anic la~er 162 onto the exposed portions of first surface 141a of the metal plate 141. The electrodeposited galvanic layer 162 5 thus surrounds and includes the negatives 151 of nozzle capillaries, however, the galvanic layer 162 has a thic~ness which does not substantially exceed the thickness of the negatives 151, since the negatives 151 are to be removed in a subsequent step.
Galvanic layer 162 is then planed to achieve a desired surface finish and thickness, which thickness preferably does not exceed that of negatives 151. Negatives 151 of nozzle capillaries are then removed in a process, such as chemically dissolving the developer-insensitive, irradiated resist 15 material which composes the negatives 151 in a commercially-available liquid stripper bath (not shown). The removable filler material 152 is preferably simultaneously removed in the same operative step as for the removal of the negatives 151, for example in the stripper bath. Alternately, filler 20 material 152 may be removed in a process such as immersing in a bath of, or spraying with, a solvent or stripper material selected on the basis of the chemical and/or physical properties of the specific removable filler material.
125857;~
252l3-65 A finished spinning nozzle plate 163 is shown in Figure 4. Spinning nozzle plate 163 has funnel-shaped pre]imi-nary channels 144 in flow communication with nozzle capillaries 161, tlle structural connection therebetween being continuous, that is, flush and without a seam, and having no offsets. In tlliS manner, the recited objects accordiny to the present invention, which uses the funnel-shaped preliminary channels l44 as a self-aligning irradiation mask during the photolitho-graphic/electrodeposition formation of nozzle capillaries, are 10 accomplished.
With reference again to Figure 1, if a radiation-sensitive, positive resist material is used to ~orm a resist layer 142, now identified as resist layer 142a, the sequence of formative steps varies somewhat as shown in Figures 2a, 2b, 2c, and 3a. After irradiation tllrough the metal plate 141, irradiated portions are removed as shown in Figure 2a, for example, with a liquid developer (not shown).
Many commercially-available positive photoresist materials are available. As an example, polymetl-ylmeth-acrylate-based resist materials may be used. Preferred developers for polymethylmethacrylate-based positive photo-resist materials are liquid developers useful as a immersion bath or spray and are composed of a mixture of diethylene glycol monobutyl ether morpholine, ethanolamine and water.
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The step of removing irradiated portions shown in Figure 2a defines a nozzle capillary zone 142b. As shown in Figure 2b, nozzle capillary zones 142b and preliminary channels 144 are filled with a removable filler material 152a, which filler material 152a is substantially less soluble than the positive resist material of resist layer 142a.
The non-irradiated portions of resist layer 142a are removed to produce negatives 151a of nozzle capillaries on metal plate 141 as shown in Figure 2c. Removal of the non-irradiated portions of resist layer 142a is accomplished, for example, by immersion thereof in a solvent which selectively dissolves the non-irradiated portions of resist layer 142a without dissolving the removable filler material 152a. Selection criteria for such solvents are well known in the art. Generally, the developer for the resist material may be used.
Galvanic layer 162 is produced as previously described by electrodeposition using metal plate 141 as an electrode, as shown in Figure 3a. The galvanic layer 162 is planed to a desired surface finish and thickness and the removable f-ller material, which includes the filler material 152a in the preliminary channels and the filler material 151a which constitutes the negatives 151a, is removed. Again, a spinning nozzle plate 163 is produced as shown in Figure 4.
125~357~
The method according to the present invention can also be used for the production of spinning nozzle plates having nozzle capillaries defined within tubular projections. In this second embodiment according to the invention, a metal 5 plate 141 having funnel-shaped preliminary channels 144 defined therethrough is provided with a resist layer 142 along a first surface 141a thereof and is again employed as a self-aligning irradiation mask as shown in Figure 5. High energy radiation, that is, radiation which is actinic with respect to resist layer 142, is directed upon a second surface 141b of the metal plate 141 such that a first portion 174 of resist layer 142 is irradiated through the preliminary channels 144 of metal plate 141. If resist layer 142 is composed of a negative resist material, a mask having absorber structures 182 corresponding to the outer diameters 15 of the tubular projections to be subsequently provided is employed for irr~diation of a second portion 175 of resist layer 142 with high energy radiation 181 as shown in Figure 6. Absorber structures 182 may be spaced apart from or placed in contact with resist layer 142, and in alignment so 20 that non-irradiated portions of the resist layer 142 cor-respond to negatives 183 of the tubular projections to be subsequently provided. Thus, as shown in Figure 6, irradi-ated first and second portions 174 and 175, respectively, 1;~5~57;~ 1 surround non-irradiated portions 1~3 of resist layer 142~
Preliminary channels 144 are then filled with a removable filler material 191.
With referen~e to Figure 7, tubular cavities 192 are provided in resist layer 142 by removing non-irradiated portions, i.e., the negatives 183, for example, by chemically removing same by immersion or spraying with a liquid developer. Tubular cavities 192 extend down to the first surface 141a of the metal plate 141 exposing portions of same.
A galvanic layer or structure is shown in Figure 8 as having the form of tubular projections 202 and is provided by electrodeposition using metal plate 141 as an electrode.
The galvanic layer or structure in the form of tubular projec~ions 202 are, for example, metal structures prepared by immersion of at least the tubular cavities 192 and the exposed portions of first surface 141a of the metal plate 141 in an electrodeposition bath which may be, for example, a chloride-free nickel sulfamate bath maintained at a tempera-ture of 52C. The bath may also include additionalcomponents including boric acid, used to buffer the electro-lyte to a pH=4, and a wetting agent to prevent pore formation.
1;2S85~;~
The galvanic layer in the form of tubular projections 202 is then planed as before and the first portion 174 and second 175 of resist layer 142, as well as filler material l91 are both removed so that a spinning nozzle plate 211 is provided as shown in Figure 9. The spinning nozzle plate 211 according to the second embodiment of the invention has funnel-shaped preliminary channels 144 in flow communication with nozzle capillaries 161a, which nozzle capillaries 161a are defined by tubular projections 202.
The preferred high energy radiation 143 and/or 181 employed is X-ray radiation generated by an electron synchrotron having a characteristic wavelength ~c = 0.2 nm.
A~sorber structures 182 useful in X-ray masks are composed of, for example, about 16 microns of gold which is essentially impermeable to X-ray radiation. The gold absorber structures 182 may be carried on a mask substrate which is substantially permeable to X-ray radiation, such as a mask substrate of beryllium in sheet form and having a thickness of approximately 20 microns.
If a positive resist material is used to provide a resist layer 142a in the second embodiment of the method according to the present inven~ion, the irradiated portions of resist layer 142a ( not shown) correspond to negatives 174a (not shown) of nozzle capillaries and are provided by, 12S~5~
in the order recited, removing irradiated portions 174a by chemically removing same, for example, by immersion thereof in a bath of liquid developer, thereby defining nozzle capillary zones 161b (Figure 6a), and filling the preliminary channels 144 and the nozzle capillary zones 161b with a removable filler material l91a. Then, as shown in Figure 6a, second portions 183a of the resist layer 142a are subjected to high energy radiation 181 by irradiating a second time through a mask positioned adjacent to resist layer 142a, either in spaced apart relation thereto or in contact therewith, after the step of filling the preliminary channels 144 and the no~zle capillary zones 161b with removable filler material l91a. The mask has absorber structures 182a provided with passages 182b which are permeable to high energy radiation 181. Passages 182b have diameters and positioning which correspond to the outer diameter and positioning of the tubular projections 202 to be subsequently provided.
The irradiated second portions 183a of the resist layer 142a correspond to negatives 174a of the tubular projections 202. Irradiated second portions 183a are thus tubular and are produced between removable filler material l91a and the non-irradiated portions of positive resist material of layer 142a. Irradiated portions 183a are then removed, such as by immersion or spraying with a liquid developer or solvent ~ 2S~57~ `
therefore, so that tubular cavities 192a are formed as shown in Figure 7a. Electrodeposition, planing, and removing the filler material l91a and the remaining positive resist layer 142a are analogous to the description regarding Figure 8 for a negative resist system. Thus, the novel spinning nozzle plate 211 as shown in Figure 9 according to the second embodim~nt of the method of the present invention results and has the advantages previously described.
With reference to Figures 10, 11 and 12, metal plate 141 having funnel-shaped preliminary channels 144 can similarly be produced by photolithographic/electrodeposition methods.
The misalignment problems typical of conventional machining operations can be substantially eliminated by photolitho-graphic methods. Thus, an electrode plate 12 may be provided with a resist layer 121 composed of either a negative or a positive resist material. Plate 12 is a continuous plate and the resist layer 121 may be applied thereto by conventional coating means, such as by roller or dip coating. A mask 122 is disposed a short distance away from the surface of resist layer 121 as shown in Figure 10. Mask 122 is comprised of absorber structures having passages 125 defined therein.
Passages 125 permit the passage of high energy radiation therethrough and have a cross-sectional size and shape and positioning corresponding to that of the tapered ends 144a of the funnel-shaped preliminary channels 144 to be sub-sequently provided.
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Preferably, high energy radiation 123 is parallel X-ray radiation 123 from an electron synchrotron. As shown in Figure 10, mask 122, resist layer 121 and electrode plate 12 form a unit 122, 121, 12 which is movably positioned in a plane perpendicular to the direction of the high energy radiation 1~3. The unit 122, 121, 12 is shown as occupying the plane and is moved with respect to the plane and the radiation direction during irradiation of the resist layer 121. When trapezoidal funnel-shaped preliminary channels 144 are desired, the unit is moved during irradiation by rocking the unit about the plane in at least one direction, the rocking motion being indicated in Figure 10 by arrows A.
Rocking may take place in two mutually perpendicular direc-tions, so that rocking of the unit takes place about an imaginary fulcrum, first in a direction parallel to the plane of the paper and second in a direction perpendicular to the plane of the paper. When conical funnel-shaped preliminary channels 144 are desired, the unit is moved during irradia-tion by rolling the unit about the plane symmetrically and conically as indicated in Figure ll by arrows B. Funnel-shaped preliminary channels 144 having other shapes are possible by varying the nature of the movement of the unit during irradiation.
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If the precision of the preliminary channels 144 need not be great, irradiation from a highly divergent, planar radiation source may take the place of rolling the unit during irradiation. Other variations will be immediately obvious to the artisan.
When the resist layer 121 is composed of a negative resist material, negatives 131 of the funnel-shaped preliminary channels 144 are provided on the electrode plate 12 by removing non-irradiated portions of the resist layer 121, by means of, for example, a liquid developer tnot shown). The irradiated portions 124 of resist layer 121 are rendered soluble only with greater difficulty by the irradia-tion step compared to the non-irradiated portions of the resist layer 121.
Alternately, when the resist layer 121 is composed of a positive resist material, negatives 131 of funnel-shaped preliminary channels 144 are provided on the electrode plate 12 ~y process steps analogous to those shown in Figures 2a, 2b and 2c. Thus, in the order recited, irradiated portions ~0 124 of the resist layer 121 are removed thereby defining preliminary channel zones 124, the preliminary channel zones 124 are filled with a removable filler material, and the non-irradiated portions of resist layer 121 are removed.
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252]3-65 As shown in Yigure 11, whether generated using a positive resist material or a negative resist material, a gal-vanic l.ayer 141 is electrodeposited onto the exposed surfaces of electrode plate 12. The galvanic layer 141 is planed and negatives 131 and electrode plate 12 are removed so that a metal plate 141 having funnel-shaped preliminary channels 144 is provided as shown in Fiqure 12.
It will be understood that the above description of the present invention is susceptible to various modifications, chanqes and adaptations, and the same are intended to be comprehended within the meaning and range of equivalents of the appended claims.
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Claims (21)
1. A method for producing a spinning nozzle plate having funnel-shaped preliminary channels in flow communica-tion with nozzle capillaries, the method comprising the steps of:
a. providing a metal plate having opposing first and second surfaces and having a plurality of spaced-apart preliminary channels defined therethrough, each preliminary channel having a funnel-shape including a tapered end which opens at the first surface of the metal plate;
b. providing a resist layer on the first surface of the metal plate, which resist layer comprises a radiation-sensitive material;
c. subjecting first portions of the resist layer to high energy radiation by irradiating the second surface of the metal plate whereby radiation is directed through the preliminary channels of the metal plate onto the resist layer, the metal plate thereby functioning as a self-aligning mask;
d. providing negatives of a plurality of nozzle capillaries on the first surface of the metal plate by removing portions of the resist layer to expose portions of the first surface of the metal plate and filling at least the preliminary channels with a removable filler material, e. electrodepositing a galvanic layer on the exposed portions of the first surface of the metal plate using the metal plate as an electrode, the galvanic layer thereby defining a plurality of nozzle capillaries;
f. planing the galvanic layer; and g. removing the removable filler material and the negatives of the plurality of nozzle capillaries.
a. providing a metal plate having opposing first and second surfaces and having a plurality of spaced-apart preliminary channels defined therethrough, each preliminary channel having a funnel-shape including a tapered end which opens at the first surface of the metal plate;
b. providing a resist layer on the first surface of the metal plate, which resist layer comprises a radiation-sensitive material;
c. subjecting first portions of the resist layer to high energy radiation by irradiating the second surface of the metal plate whereby radiation is directed through the preliminary channels of the metal plate onto the resist layer, the metal plate thereby functioning as a self-aligning mask;
d. providing negatives of a plurality of nozzle capillaries on the first surface of the metal plate by removing portions of the resist layer to expose portions of the first surface of the metal plate and filling at least the preliminary channels with a removable filler material, e. electrodepositing a galvanic layer on the exposed portions of the first surface of the metal plate using the metal plate as an electrode, the galvanic layer thereby defining a plurality of nozzle capillaries;
f. planing the galvanic layer; and g. removing the removable filler material and the negatives of the plurality of nozzle capillaries.
2. The method according to claim 1, wherein the resist layer is composed of a negative resist material, and wherein the negatives of the plurality of nozzle capillaries are provided by filling the preliminary channels with the removable filler material before removing portions of the resist layer, which portions are non-irradiated portions.
3. The method according to claim 2, wherein the plurality of nozzle capillaries are each defined within a tubular projection extending from the first surface of the metal plate and having an outer diameter and positioning, wherein the method includes the further step of subjecting second portions of the resist layer to high energy radiation by irradiating a second time through a mask positioned adjacent to the resist layer, immediately following the step of subjecting first portions of the resist layer to high energy radiation, the mask having absorber structures which correspond in diameter and positioning to the outer diameter and positioning of the tubular projections to be subsequently provided, the non-irradiated portions of the resist layer corresponding to negatives of the tubular projections, and wherein the step of removing the non-irradiated portions of the resist layer results in the formation of tubular cavities, which cavities expose portions of the first surface, and the subsequent step of electrodepositing a galvanic layer provides a discontinuous galvanic layer consisting of said tubular projections.
4. The method according to claim 3, wherein the metal plate having a plurality of spaced-apart preliminary channels defined therethrough is provided by a method including the steps of:
a. providing a resist layer on an electrode plate;
b. subjecting portions of the resist layer to high energy radiation, which radiation has a direction, through a mask having passages, which passages correspond in cross-sectional size and shape and in positioning to that of the tapered ends of the funnel-shaped preliminary channels to be subsequently provided, the mask, resist layer and electrode plate forming a unit, which unit is movably positioned in a plane perpendicular to the direction of the high energy radiation and is moved with respect to said plane and said radiation direction during irradiation;
c. providing negatives of the plurality of funnel-shaped preliminary channels on the electrode plate by removing portions of the resist layer to expose portions of the electrode plate;
d. electrodepositing a galvanic layer on the exposed portions of the electrode plate, the galvanic layer thereby defining a plurality of funnel-shaped preliminary channels;
e. planing the galvanic layer; and f. removing the negatives and the electrode plate.
a. providing a resist layer on an electrode plate;
b. subjecting portions of the resist layer to high energy radiation, which radiation has a direction, through a mask having passages, which passages correspond in cross-sectional size and shape and in positioning to that of the tapered ends of the funnel-shaped preliminary channels to be subsequently provided, the mask, resist layer and electrode plate forming a unit, which unit is movably positioned in a plane perpendicular to the direction of the high energy radiation and is moved with respect to said plane and said radiation direction during irradiation;
c. providing negatives of the plurality of funnel-shaped preliminary channels on the electrode plate by removing portions of the resist layer to expose portions of the electrode plate;
d. electrodepositing a galvanic layer on the exposed portions of the electrode plate, the galvanic layer thereby defining a plurality of funnel-shaped preliminary channels;
e. planing the galvanic layer; and f. removing the negatives and the electrode plate.
5. The method according to claim 4, wherein the resist layer is composed of a negative resist material and wherein negatives of the funnel-shaped preliminary channels are provided on the electrode plate by removing non-irradiated portions of the resist layer.
6. The method according to claim 4, wherein the resist layer is composed of a positive resist material and wherein negatives of the funnel-shaped preliminary channels are provided on the electrode plate by, in the order recited, removing portions of the resist layer, which portions are irradiated portions, thereby defining preliminary channel zones; filling the preliminary channel zones with a removable filler material; and removing further portions of the resist layer, which further portions are non-irradiated portions.
7. The method according to claim 4, wherein the unit is moved during irradiation by rocking the unit about the plane in at least one direction, whereby the irradiated portions of the resist layer have a trapezoidal funnel shape.
8. The method according to claim 4, wherein the unit is moved during irradiation by tumbling the unit about the plane, whereby the irradiated portions of the resist layer have a conical funnel shape.
9. The method according to claim 1, wherein the resist layer is composed of a positive resist material, and wherein the negatives of the nozzle capillaries are provided by, in the order recited, removing portions of the resist layer, which portions are irradiated portions, thereby defining nozzle capillary zones; filling the preliminary channels and the nozzle capillary zones with a removable filler material;
and removing further portions of the resist layer, which further portions are non-irradiated portions.
and removing further portions of the resist layer, which further portions are non-irradiated portions.
10. The method according to claim 9, wherein the plurality of nozzle capillaries are each defined within a tubular projection extending from the first surface of the metal plate and having an outer diameter and positioning, wherein the method includes the further steps of, after the step of filling the preliminary channels and the nozzle capillary zones with a removable filler material, subjecting second portions of the resist layer to high energy radiation by irradiating a second time through a mask positioned adjacent to the resist layer, the mask having passages which correspond in diameter and positioning to the outer diameter and positioning of the tubular projections to be subsequently provided, the irradiated second portions of the resist layer corresponding to negatives of the tubular projections; and removing irradiated second portions of the resist layer to form tubular cavities, which cavities expose portions of the first surface so that the subsequent step of electrodeposit-ing a galvanic layer provides a discontinuous galvanic layer consisting of said tubular projections.
11. The method according to claim 10, wherein the metal plate having a plurality of spaced-apart preliminary channels defined therethrough is provided by a method including the steps of:
a. providing a resist layer on an electrode plate;
b. subjecting portions of the resist layer to high energy radiation, which radiation has a direction, through a mask having passages, which passages correspond in cross-sectional size and shape and in positioning to that of the tapered ends of the funnel-shaped preliminary channels to be subsequently provided, the mask, resist layer and electrode plate forming a unit, which unit is movably positioned in a plane perpendicular to the direction of the high energy radiation and is moved with respect to said plane and said radiation direction during irradiation;
c. providing negatives of the plurality of funnel-shaped preliminary channels on the electrode plate by removing portions of the resist layer to expose portions of the electrode plate;
d. electrodepositing a galvanic layer on the exposed portions of the electrode plate, the galvanic layer thereby defining a plurality of funnel-shaped preliminary channels;
e. planing the galvanic layer; and f. removing the negatives and the electrode plate.
a. providing a resist layer on an electrode plate;
b. subjecting portions of the resist layer to high energy radiation, which radiation has a direction, through a mask having passages, which passages correspond in cross-sectional size and shape and in positioning to that of the tapered ends of the funnel-shaped preliminary channels to be subsequently provided, the mask, resist layer and electrode plate forming a unit, which unit is movably positioned in a plane perpendicular to the direction of the high energy radiation and is moved with respect to said plane and said radiation direction during irradiation;
c. providing negatives of the plurality of funnel-shaped preliminary channels on the electrode plate by removing portions of the resist layer to expose portions of the electrode plate;
d. electrodepositing a galvanic layer on the exposed portions of the electrode plate, the galvanic layer thereby defining a plurality of funnel-shaped preliminary channels;
e. planing the galvanic layer; and f. removing the negatives and the electrode plate.
12. The method according to claim 11, wherein the resist layer is composed of a negative resist material and wherein negatives of the funnel-shaped preliminary channels are provided on the electrode plate by removing non-irradiated portions of the resist layer.
13. The method according to claim 11, wherein the resist layer is composed of a positive resist material and wherein negatives of the funnel-shaped preliminary channels are provided on the electrode plate by, in the order recited, removing portions of the resist layer, which portions are irradiated portions, thereby defining preliminary channel zones; filling the preliminary channel zones with a removable filler material; and removing further portions of the resist layer, which further portions are non-irradiated portions.
14. The method according to claim 11, wherein the unit is moved during irradiation by rocking the unit about the plane in at least one direction, whereby the irradiated portions of the resist layer have a trapezoidal funnel shape.
15. The method according to claim 11, wherein the unit is moved during irradiation by tumbling the unit about the plane whereby the irradiated portions of the resist layer have a conical funnel shape.
16. The method according to claim 1, wherein the metal plate having a plurality of spaced-apart preliminary channels defined therethrough is provided by a method including the steps of:
a. providing a resist layer on an electrode plate;
b. subjecting portions of the resist layer to high energy radiation, which radiation has a direction, through a mask having passages, which passages correspond in cross-sectional size and shape and in positioning to that of the tapered ends of the funnel-shaped preliminary channels to be subsequently provided, the mask, resist layer and electrode plate forming a unit, which unit is movably positioned in a plane perpendicular to the direction of the high energy radiation and is moved with respect to said plane and said radiation direction during irradiation;
c. providing negatives of the plurality of funnel-shaped preliminary channels on the electrode plate by removing portions of the resist layer to expose portions of the electrode plate;
d. electrodepositing a galvanic layer on the exposed portions of the electrode plate, the galvanic layer thereby defining a plurality of funnel-shaped preliminary channels;
e. planing the galvanic layer; and f. removing the negatives and the electrode plate.
a. providing a resist layer on an electrode plate;
b. subjecting portions of the resist layer to high energy radiation, which radiation has a direction, through a mask having passages, which passages correspond in cross-sectional size and shape and in positioning to that of the tapered ends of the funnel-shaped preliminary channels to be subsequently provided, the mask, resist layer and electrode plate forming a unit, which unit is movably positioned in a plane perpendicular to the direction of the high energy radiation and is moved with respect to said plane and said radiation direction during irradiation;
c. providing negatives of the plurality of funnel-shaped preliminary channels on the electrode plate by removing portions of the resist layer to expose portions of the electrode plate;
d. electrodepositing a galvanic layer on the exposed portions of the electrode plate, the galvanic layer thereby defining a plurality of funnel-shaped preliminary channels;
e. planing the galvanic layer; and f. removing the negatives and the electrode plate.
17. The method according to claim 16, wherein the resist layer is composed of a negative resist material and wherein negatives of the funnel-shaped preliminary channels are provided on the electrode plate by removing non-irradiated portions of the resist layer.
18. The method according to claim 16, wherein the resist layer is composed of a positive resist material and wherein negatives of the funnel-shaped preliminary channels are provided on the electrode plate by, in the order recited, removing portions of the resist layer, which portions are irradiated portions, thereby defining preliminary channel zones; filling the preliminary channel zones with a removable filler material; and removing further portions of the resist layer, which further portions are non-irradiated portions.
19. The method according to claim 16, wherein the unit is moved during irradiation by rocking the unit about the plane in at least one direction, whereby the irradiated portions of the resist layer have a trapezoidal funnel shape.
20. The method according to claim 16, wherein the unit is moved during irradiation by tumbling the unit about the plane, whereby the irradiated portions of the resist layer have a conical funnel shape.
21. The method according to claim 1, wherein the high energy radiation is X-ray radiation generated by an electron synchrotron.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853524411 DE3524411A1 (en) | 1985-07-09 | 1985-07-09 | METHOD FOR PRODUCING SPINNING NOZZLE PLATES |
| DEP3524411.9 | 1985-07-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1258572A true CA1258572A (en) | 1989-08-22 |
Family
ID=6275266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000513271A Expired CA1258572A (en) | 1985-07-09 | 1986-07-08 | Method for producing a spinning nozzle plate |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4694548A (en) |
| EP (1) | EP0209651B1 (en) |
| JP (1) | JPH0747249B2 (en) |
| AT (1) | ATE66254T1 (en) |
| AU (1) | AU585624B2 (en) |
| BR (1) | BR8603196A (en) |
| CA (1) | CA1258572A (en) |
| DE (2) | DE3524411A1 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5189437A (en) * | 1987-09-19 | 1993-02-23 | Xaar Limited | Manufacture of nozzles for ink jet printers |
| DE3841621A1 (en) * | 1988-12-10 | 1990-07-12 | Draegerwerk Ag | ELECTROCHEMICAL MEASURING CELL WITH MICROSTRUCTURED CAPILLARY OPENINGS IN THE MEASURING ELECTRODE |
| US5119550A (en) * | 1989-07-03 | 1992-06-09 | Eastman Kodak Company | Method of making transfer apparatus having vacuum holes |
| US5189777A (en) * | 1990-12-07 | 1993-03-02 | Wisconsin Alumni Research Foundation | Method of producing micromachined differential pressure transducers |
| DE4042125A1 (en) * | 1990-12-28 | 1992-07-02 | Maxs Ag | METHOD FOR PRODUCING A REINFORCED FLAT OBJECT HAVING MICRO-OPENINGS |
| US5206983A (en) * | 1991-06-24 | 1993-05-04 | Wisconsin Alumni Research Foundation | Method of manufacturing micromechanical devices |
| US5190637A (en) * | 1992-04-24 | 1993-03-02 | Wisconsin Alumni Research Foundation | Formation of microstructures by multiple level deep X-ray lithography with sacrificial metal layers |
| US5378583A (en) * | 1992-12-22 | 1995-01-03 | Wisconsin Alumni Research Foundation | Formation of microstructures using a preformed photoresist sheet |
| US5412265A (en) * | 1993-04-05 | 1995-05-02 | Ford Motor Company | Planar micro-motor and method of fabrication |
| US5413668A (en) * | 1993-10-25 | 1995-05-09 | Ford Motor Company | Method for making mechanical and micro-electromechanical devices |
| DE19530193A1 (en) * | 1995-08-17 | 1997-02-20 | Bosch Gmbh Robert | Nozzle plate, in particular for fuel injection valves, and method for producing a nozzle plate |
| AU7163596A (en) * | 1995-10-30 | 1997-05-22 | Kimberly-Clark Corporation | Fiber spin pack |
| GB9623185D0 (en) * | 1996-11-09 | 1997-01-08 | Epigem Limited | Improved micro relief element and preparation thereof |
| CZ299554B6 (en) * | 1997-09-15 | 2008-09-03 | The Procter & Gamble Company | Compound with quinolone structure, pharmaceutical composition containing thereof and use of such compound |
| US6272275B1 (en) | 1999-06-25 | 2001-08-07 | Corning Incorporated | Print-molding for process for planar waveguides |
| DE10305425B4 (en) * | 2003-02-03 | 2006-04-27 | Siemens Ag | Production method for a perforated disk for ejecting a fluid |
| DE10305427B4 (en) * | 2003-02-03 | 2006-05-24 | Siemens Ag | Production method for a perforated disk for ejecting a fluid |
| CN111702323B (en) * | 2020-06-30 | 2022-05-10 | 苏州锐涛光电科技有限公司 | Processing method of spinneret orifice of melt-blown plate die |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3192136A (en) * | 1962-09-14 | 1965-06-29 | Sperry Rand Corp | Method of preparing precision screens |
| US3512247A (en) * | 1966-11-16 | 1970-05-19 | Celanese Corp | Process for producing spinnerettes |
| US3449221A (en) * | 1966-12-08 | 1969-06-10 | Dynamics Res Corp | Method of making a monometallic mask |
| US4246076A (en) * | 1979-12-06 | 1981-01-20 | Xerox Corporation | Method for producing nozzles for ink jet printers |
| US4430784A (en) * | 1980-02-22 | 1984-02-14 | Celanese Corporation | Manufacturing process for orifice nozzle devices for ink jet printing apparati |
| DE3042483A1 (en) * | 1980-11-11 | 1982-06-16 | Philips Patentverwaltung Gmbh, 2000 Hamburg | METHOD AND ARRANGEMENT FOR PRODUCING A NOZZLE PLATE FOR INK JET WRITER |
| DE3206820C2 (en) * | 1982-02-26 | 1984-02-09 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | Process for making separation nozzle elements |
| NL8203521A (en) * | 1982-09-10 | 1984-04-02 | Philips Nv | METHOD FOR MANUFACTURING AN APPARATUS |
| US4552831A (en) * | 1984-02-06 | 1985-11-12 | International Business Machines Corporation | Fabrication method for controlled via hole process |
-
1985
- 1985-07-09 DE DE19853524411 patent/DE3524411A1/en active Granted
-
1986
- 1986-04-30 DE DE8686105992T patent/DE3680837D1/en not_active Expired - Fee Related
- 1986-04-30 AT AT86105992T patent/ATE66254T1/en not_active IP Right Cessation
- 1986-04-30 EP EP86105992A patent/EP0209651B1/en not_active Expired - Lifetime
- 1986-07-08 JP JP61158898A patent/JPH0747249B2/en not_active Expired - Lifetime
- 1986-07-08 BR BR8603196A patent/BR8603196A/en not_active IP Right Cessation
- 1986-07-08 CA CA000513271A patent/CA1258572A/en not_active Expired
- 1986-07-09 AU AU59888/86A patent/AU585624B2/en not_active Ceased
- 1986-07-09 US US06/883,633 patent/US4694548A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0209651B1 (en) | 1991-08-14 |
| JPH0747249B2 (en) | 1995-05-24 |
| AU5988886A (en) | 1987-01-15 |
| EP0209651A2 (en) | 1987-01-28 |
| JPS6244322A (en) | 1987-02-26 |
| ATE66254T1 (en) | 1991-08-15 |
| BR8603196A (en) | 1987-02-24 |
| DE3524411C2 (en) | 1989-05-03 |
| DE3524411A1 (en) | 1987-01-15 |
| EP0209651A3 (en) | 1988-09-14 |
| AU585624B2 (en) | 1989-06-22 |
| DE3680837D1 (en) | 1991-09-19 |
| US4694548A (en) | 1987-09-22 |
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| MKEX | Expiry |