EP0816095B1 - Tête d'impression par jet d'encre à base de composés organosiliciques - Google Patents

Tête d'impression par jet d'encre à base de composés organosiliciques Download PDF

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Publication number
EP0816095B1
EP0816095B1 EP97110589A EP97110589A EP0816095B1 EP 0816095 B1 EP0816095 B1 EP 0816095B1 EP 97110589 A EP97110589 A EP 97110589A EP 97110589 A EP97110589 A EP 97110589A EP 0816095 B1 EP0816095 B1 EP 0816095B1
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EP
European Patent Office
Prior art keywords
compound
group
lacquer
produced
ink jet
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 - Lifetime
Application number
EP97110589A
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German (de)
English (en)
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EP0816095A1 (fr
Inventor
Jürgen Dr. Kappel
Michael Dr. Popall
Jochen Dr. Schulz
Adelheid Martin
Birke-E. Olsowski
Karl Bühler
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP0816095A1 publication Critical patent/EP0816095A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/1631—Manufacturing processes photolithography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1601—Production of bubble jet print heads

Definitions

  • the present invention relates to ink jet printheads which consist at least in part of a polymeric material that is produced using organosilicon compounds with polycondensable and polymerizable groups.
  • Inkjet printheads now have to be sold in increasing numbers to be produced. This printing technology is now one time enormously widespread, on the other hand it is desirable to have one To develop "cheap printhead", each together with the Ink cartridge can be replaced.
  • Inkjet printheads exist next to the actuator (heating element, Piezo element, electrodynamic transducer, etc.) made of structures for liquid management (channel walls, covers, nozzle walls, -covers, ink supply), ink filters and one not wetting nozzle outlet side (e.g. nozzle plate).
  • Modern Ink printheads have the planar structure in common that with the means of semiconductor manufacturing a relatively inexpensive Manufacture with high accuracy in large numbers enables. There are differences in the structure: “Edge shooter arrangement” the droplet is ejected tangentially to the heating element surface, while the so-called “Side shooter arrangement” of the drops normal to the heating element surface is delivered.
  • the layered structure of the "edge shooter variant” (substrate, Thin film structure, channel structure, channel cover, glass tub with Ink reservoir) requires nozzles that come from different Materials with different wetting properties be formed (thin film layer, photoresist channel wall, Photoresist adhesive layer, channel cover). This different wetting properties can be negative affect drop formation. Therefore, with “edge shooter arrangements” additionally the coating on the nozzle outlet side with a hydrophobic material.
  • the nozzle outlet of the side shooter arrangement nozzle plate is made but from only one material. Thereby lie in the nozzle area same wetting properties.
  • an additional one only Coating (anti-slide coating) required, if the hydrophobic properties of the material are not suffice.
  • the channel structures of today's printheads are usually made Acrylic-based photoresists through photolithographic Processes generated.
  • photo glass is used that structured after the exposure of the mask can be etched.
  • EP 658 430 A1 also describes an ink jet head Channel walls formed from an epoxy resin composition which have an epoxy resin with a diepoxy structure contains a siloxane bond.
  • the resin is used in the manufacture of the inkjet printhead to the positive of the future Ink channels applied, which consist of photoresist. This are then extracted so that the corresponding Channel structures arise. This process is complex because must be worked with different materials and many individual steps are required.
  • the object of the present invention is a universally applicable To provide material for inkjet printheads, with the channel structures, substrates, nozzle plates, nozzles, ink reservoirs, Ink filters and the like for color and mono ink jet print heads can be completely manufactured, and whose hydrophobic properties are sufficient to respond to the To be able to dispense with an anti-triel coating.
  • the Material should be inexpensive, and structuring should with little effort and / or with high precision can.
  • Polymer materials of the type used according to the invention belong to the material class of the so-called ORMOCERE (ORganically MOdified CERamics). You can choose between inorganic and organic polymers are classified. The production is based on alkoxides of silicon and, if necessary, in addition other metals wholly or partly through organic polymerizable substituents are modified. By hydrolysis and condensation becomes the inorganic part of the network built up by polymerization, polyaddition or others organic coupling reactions the organic part from reactive organic substituents.
  • ORMOCERE ORganically MOdified CERamics
  • Layers to be structured can be according to the invention are manufactured as follows:
  • a pre-condensate (here mostly with "lacquer” designated) prepared from the selected starting materials, which depending on the chemical compounds used is usually stable for a few months.
  • the paint can be varied in its solids content, for example by Removal of solvent or water or by addition an additional solvent. By diving, spinning or spraying or the like.
  • the paint is then on the desired substrate material applied as a layer, the Substrate not only from foreign material such as glass, ceramic, metal or foreign polymer, but also from the same material can exist.
  • the polymeric material both photopolymerizable groups as well as thermally cross-linkable Contains groups. Furthermore, it is of course preferred a photoinitiator and possibly an accelerator, for example based on amine added.
  • FIG. 1 The formation of a polymeric "ORMOCER" hybrid material is shown by way of example in FIG. 1 : first, the inorganic oxide network is built up by polycondensation of alkoxysilanes, in a subsequent step the methacrylic groups of 3-methacryloxypropyltrimethoxysilane (MEMO) are photochemically crosslinked and finally the Epoxy groups of 3-glycidoxypropyltrimethoxysilane (GLYMO) thermally polymerized, so that an organic network value is also created.
  • MEMO methacrylic groups of 3-methacryloxypropyltrimethoxysilane
  • GLYMO Epoxy groups of 3-glycidoxypropyltrimethoxysilane
  • photochemical radical initiator for example Quantacure ITX from Shell Chemie, Irgacure 184 from Ciba-Geigy or Darocur 4263 from Merck.
  • photochemical crosslinking is suitable for N-methyldiethanolamine or diethylenetriamine, the latter also can act as an epoxy hardener. Mixtures can also be used of which are used.
  • the use of the GMP2T system is very particularly preferred.
  • the paint is preferably made by first the desired silanes, if necessary with further additives (e.g. Network formers or modifying substances), mixed and, if necessary under heat, hydrolyzed by adding water.
  • further additives e.g. Network formers or modifying substances
  • the Water addition can be done slowly, so the system first substoichiometric amounts are supplied.
  • the liquid lacquer produced as described above becomes possibly brought to a desired solids content, what preferably by spinning in or distilling off Solvent or water happens. If necessary, additional or alternatively diluted with a suitable solvent (e.g. with ethanol, acetone, propyl acetate or the like). On Solids content in the range from 50% to 85%, especially from about 75% is desirable. However, it should be clear that depending on the type of order and the one you want Structure height also worked with other solids contents can be.
  • a suitable solvent e.g. with ethanol, acetone, propyl acetate or the like.
  • the varnish can then be applied as a layer on one or different Substrate (s) are applied.
  • the substrate or substrates can it be made of another material like glass, Ceramic, metal, silicon or polymer or the like. Act it can also be an order on the used according to the invention Material take place, which should then already be hardened.
  • the varnish can be applied by spin-on application (for example at a rotation speed of about 300 to 800 rpm and a period of about 30 to 80 seconds).
  • spin-on application for example at a rotation speed of about 300 to 800 rpm and a period of about 30 to 80 seconds.
  • Doctor blade dipping, spraying, embossing or similar
  • the paint is used to create channels or comparable structures subjected to structuring. This can in principle be done by any method, whereby however, the ones described below are preferred:
  • photo structuring takes place with the help of Exposing the desired parts of the paint
  • the Exposure is carried out with a flat light source.
  • the parts of the lacquer, which should not be exposed, are included Protected from radiation by using a mask. It can the mask e.g. be placed in front of the light source. Alternatively, you can work with a mask aligner, where under certain circumstances a simultaneous mechanical embossing of the lacquer using the mask can. However, this is reserved for special cases, as it is common a contact exposure to bond mask and Paint could result. Is exposed with a wavelength which initiates the photochemical reactions in the paint.
  • the GMP2T system is a composition of the polymer material that is suitable for photolithography.
  • a varnish made of this material which was essentially freed from volatile constituents (alcohols, water) that were formed during the implementation of the components and was diluted to the desired solids content with propyl acetate, can be layer thicknesses of more than 10 ⁇ m and even in the range of Achieve ⁇ 40 ⁇ m.
  • GMDT has proven to be particularly suitable, particularly with regard to its adhesive properties.
  • GMP2D and especially GMD have a higher elasticity due to their high proportion of units that can only be crosslinked in two ways, which means that larger structural heights can be realized without cracks.
  • the incorporation of fillers is possible. It should be noted that an increasing proportion of filler can reduce the adhesion to the substrate.
  • a solvent are suitable polar substances such as aqueous alkali solutions, Alcohol and the like, but also non-polar solvents such as Toluene and the like, if they are able to do so to remove unpolymerized condensate from the layer.
  • suitable polar substances such as aqueous alkali solutions, Alcohol and the like, but also non-polar solvents such as Toluene and the like, if they are able to do so to remove unpolymerized condensate from the layer.
  • non-polar solvents such as Toluene and the like
  • the structures obtained become thermal post-hardened. This can occur, for example, in the hour range a temperature between 100 ° C and 170 ° C.
  • the coating of the substrates, the development of the structures and the thermal post-curing takes place in direct laser writing as in photolithography.
  • a narrowly focused laser beam is chosen for direct exposure of the lacquer.
  • the laser beam is focused to the desired width, for example 3 to 50 ⁇ m and in particular 10 to 20 ⁇ m for the channel structures described.
  • writing takes place at a speed of 0.1 to 10 mm / sec. In particular, a speed of approximately 1 mm / sec. is preferred in order to achieve crack-free, uniform structures. Even with the laser direct writing structure heights can be achieved up to 40 ⁇ m.
  • the lacquer is preferably thermally or photochemically pre-crosslinked in order to avoid sticking to the embossing mask.
  • a thermal pretreatment of a few minutes at around 80 ° C - 120 ° C is beneficial. Higher temperatures lead to strong pre-crosslinking (which makes it more difficult for the embossing mask to penetrate), while shorter thermal pre-treatments do not prevent the mask and layer from sticking together. Structured glass or Si masks or nickel sheets with structure heights in the range of 40 ⁇ m can be used as masks.
  • Embossing machines in the manner of a mask aligner are possible. Exposure or thermal treatment at temperatures up to 170 ° C. is preferably carried out simultaneously with the pressing of the mask. The pressure is then relaxed again, the mask is removed and the structure obtained is thermally hardened.
  • ink printhead components can be such as channel walls, channel covers, nozzle walls, Nozzle covers, passivation layers, nozzle plates, ink reservoirs, Generate ink filters and the like.
  • coated substrates to produce the desired ones Channels stacked (base-base, head-to-head).
  • Base a uniform material generate, with the exception of the actuators for generating drops (Heating element, piezo element, electrodynamic converter Etc.).
  • the production of planar ink printheads is particularly favorable according to the invention.
  • the components 1. to 4. are submitted and at Room temperature stirred for 18 h. Then within The suspension was heated to about 70 ° C. for 90 minutes. after the Suspension has become clear, is 1/4 of the amount of water Maintenance of heating added. At intervals of approx. The remaining amount of water is added for 20 min 1/4). After all of the water has been added, the mixture is stirred at 70 ° C. for 1 h continued stirring. Then the heater is removed, and after the paint is ready to use after cooling.
  • the system GMP2T is used for the generation of channel structures, which has very good adhesion to the various substrate materials, even after ink storage.
  • the solvent is distilled off until a solids content of 75% is reached.
  • 1.5% by mass of photoinitiator (Quantacure ITX, Shell Chemie) and 1.5% by mass of accelerator (N-methyldiethanolamine and diethylenetriamine, ratio 1: 1) are dissolved in the lacquer and this system is carried out on substrates (glass, Si) Spin-on application applied (600 rpm for 60 sec.).
  • the photostructuring is carried out using a mask aligner (Karl-Süss MA 45) at a wavelength of 360 nm and an exposure intensity of 14 mW / cm 2 . Exposure times of approximately 10 seconds have proven to be optimal under these conditions.
  • the exposed structures are developed by spraying with ethanol (duration: 10 seconds).
  • the structures obtained are cured at 120 ° C. for 10 h. These structures are characterized in FIGS. 2 to 4 (SEM and profilometer measurements). With the described method crack-free structure heights can be realized in one step up to 30 ⁇ m.
  • These structures have a high edge steepness, have good substrate adhesion and the required ink storage stability. For this reason and due to their temperature stability up to 270 ° C (thermogravimetric determination in air) they are very well suited for use as channel structures for inkjet printheads.
  • the coating of the substrates, the development of the structures and the thermal post-curing for direct laser writing is carried out as described in Example 2.
  • the system GMP2T is again selected as the material, the concentration of photoinitiator is 0.05% by weight (Irgacure 184, company Ciba-Geigy or Quantacure ITX), the laser wavelength is 360 nm, the laser power before focusing is 1, 41-2.28 mW (variable; 1 mm beam diameter).
  • the laser beam is focused on approx. 10 - 15 ⁇ m .
  • Writing takes place at a speed of 1 mm / sec.
  • Such a laser-written structuring and the associated profilometer measurement are shown in FIGS. 5 and 6.
  • the thickening at the corners can be traced back to the persistence of the laser beam when changing direction.
  • the structure height is 20 ⁇ m .
  • the GMP2T system is also used for embossing channel structures (see example 2).
  • Application conditions glass substrates
  • curing photochemical and thermal post-curing
  • the embossing process requires thermal pretreatment of the applied coating.
  • the most favorable pre-curing conditions are thermal pre-treatments at approx. 80 ° C (5 min). Increasing the temperature leads to strong pre-crosslinking (bad penetration of the embossing mask as a result), while shorter thermal pre-treatment leads to the mask and layer sticking together.
  • Structured glass or Si masks with structure heights of up to 40 ⁇ m are used. After the pre-hardening of the layer, these masks are placed on the layer and pressed with a pressure of approx. 1 kg / cm 2 , exposure being carried out (approx. 10 sec, 14 mW / cm 2 at 360 nm). Then the pressure is released again, the mask is removed and the structure obtained is post-cured at 120 ° C. for 10 hours.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Particle Formation And Scattering Control In Inkjet Printers (AREA)
  • Paints Or Removers (AREA)

Claims (14)

  1. Tête d'impression par jet d'encre ayant un ou plusieurs composants en polymère fabriqués à partir ou essentiellement en utilisant au moins une combinaison (I) : XaRbSiR' (4-a-b) avec
    X
    = groupe hydrolysable
    R
    = groupe alkyle, aryle, alkényle, alkylaryle ou arylalkyle, le cas échéant substitué,
    R'
    = radical organique avec au moins un groupe polymérisable,
    a
    = 1 à 3,
    b
    = 0 à 2,
    caractérisée en ce qu'
    on fabrique la matière en utilisant la combinaison (I) avec un groupe accessible à la photopolymérisation et une combinaison (I) avec un groupe réticulable thermiquement, ou une combinaison (I) avec à la fois un groupe accessible à la polymérisation et un groupe réticulable par voie thermique.
  2. Tête d'impression par jet d'encre selon la revendication 1,
    caractérisée en ce qu'
    on sélectionne les composants pour former les structures de canal, les substrats, les plaques à buses, les buses, les réservoirs d'encre et les filtres à encre.
  3. Tête d'impression par jet d'encre selon l'une quelconque des revendications 1 ou 2,
    caractérisée en ce qu'
    on utilise une combinaison avec le cas échéant des groupes vinyloxyalkyle substitués et une combinaison (I) avec un groupe alkylénoxyde-oxyalkyle, le cas échéant substitué pour la fabrication.
  4. Tête d'impression par jet d'encre selon la revendication 1,
    caractérisée en ce qu'
    on fabrique les polymères en utilisant le glycidoxypropyltriméthoxysilane, le méthacryloxypropyltriméthoxysilane, le diphénylsilanediol et le tétraéthoxysilane.
  5. Procédé de fabrication d'une tête d'impression par jet d'encre,
    caractérisé en ce qu'
    on fabrique un ou plusieurs composants de la tête en un polymère obtenu en utilisant au moins une combinaison (I) : XaRbSiR' (4-a-b) avec
    X
    = groupe hydrolysable,
    R
    = groupe alkyle, aryle, alkényle, alkylaryle ou arylalkyle, le cas échéant substitué,
    R'
    = radical organique avec au moins un groupe polymérisable,
    a
    = 1 à 3,
    b
    = 0 à 2.
    ou au moins essentiellement une combinaison (I), avec l'indication que la fabrication de la matière a été faite en utilisant une combinaison (I) avec un groupe accessible à la photopolymérisation et une combinaison (I) avec un groupe réticulable thermiquement, ou une combinaison (I) contenant à la fois un groupe accessible à la photopolymérisation et un autre réticulable par voie thermique.
  6. Procédé selon la revendication 5,
    caractérisé en ce qu'
    on forme les composants en mélangeant un vernis de combinaison de départ précondensé avec addition d'eau, en mélangeant un photoinitiateur et le cas échéant un accélérateur et en l'appliquant sur les substrats, et après éventuellement un prétraitement, on met le vernis en structure et enfin on assemble le cas échéant les substrats pour obtenir une structure tridimensionnelle.
  7. Procédé selon la revendication 6,
    caractérisé en ce qu'
    avant l'application sur les substrats, on réalise le vernis avec une teneur en matières solides d'au moins 50 % en poids.
  8. Procédé selon l'une des revendications 6 à 7,
    caractérisé en ce qu'
    on applique le vernis sur les substrats par un procédé d'application en rotation.
  9. Procédé selon l'une quelconque des revendications 6 à 7,
    caractérisé en ce qu'
    on structure le vernis par application des étapes suivantes :
    exposition des parties souhaitées du vernis à la lumière,
    rinçage des parties non exposées du vernis avec un solvant,
    traitement thermique ultérieur des structures formées pour obtenir des polymères.
  10. Procédé selon la revendication 9,
    caractérisé en ce que
    l'exposition à la lumière se fait à l'aide d'une source lumineuse surfacique et les parties du vernis qui ne doivent être exposées sont protégées contre l'insolation par un masque.
  11. Procédé selon la revendication 9,
    caractérisé en ce que
    l'exposition se fait par inscription directe au laser avec un faisceau laser focalisé.
  12. Procédé selon l'une quelconque des revendications 6 à 8,
    caractérisé en ce qu'
    on met le vernis en structure en appliquant les étapes suivantes :
    le cas échéant, on effectue un prétraitement thermique ou photochimique,
    on enfonce mécaniquement les structures souhaitées dans le vernis,
    on éclaire au moins les parties non creusées du vernis, on effectue une réticulation thermique des structures formées.
  13. Application d'un polymère fabriqué à partir principalement ou avec l'utilisation d'au moins une combinaison (I) : XaRbSiR'(4-a-b) avec
    X
    = groupe hydrolysable
    R
    = groupe alkyle, aryle, alkényle, alkylaryle ou arylalkyle, le cas échéant substitué,
    R'
    = radical organique avec au moins un groupe polymérisable,
    a
    = 1 à 3,
    b
    = 0 à 2.
    comme matière pour les têtes d'impression par jet de laser ou des composants de telles têtes, en indiquant que la fabrication de la matière se fait sous l'utilisation de la combinaison (I) et d'un groupe polymérisable et d'une combinaison (I) avec un groupe réticulable par voie thermique, ou une combinaison (I) contenant à la fois un groupe pour la photopolymérisation et un groupe à reticuletion thermique.
  14. Application selon la revendication 13,
    caractérisée en ce que
    les composants de la tête d'impression par jet d'encre sont choisis dans le groupe formé par les parois de canal, les recouvrement de canal, les parois de buse, les recouvrements de buse, les couches de passivation, les plaques de buses, les réservoirs d'encre et les filtres à encre.
EP97110589A 1996-06-28 1997-06-27 Tête d'impression par jet d'encre à base de composés organosiliciques Expired - Lifetime EP0816095B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19626053 1996-06-28
DE19626053 1996-06-28
PCT/DE1997/001340 WO1998000296A1 (fr) 1996-06-28 1997-06-26 Tete d'impression a jet d'encre avec des elements constitues de composes organosiliciques
WOPCT/DE97/01340 1997-06-26

Publications (2)

Publication Number Publication Date
EP0816095A1 EP0816095A1 (fr) 1998-01-07
EP0816095B1 true EP0816095B1 (fr) 2001-05-16

Family

ID=7798351

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97110589A Expired - Lifetime EP0816095B1 (fr) 1996-06-28 1997-06-27 Tête d'impression par jet d'encre à base de composés organosiliciques

Country Status (4)

Country Link
EP (1) EP0816095B1 (fr)
CA (1) CA2230636A1 (fr)
DE (1) DE59703535D1 (fr)
WO (1) WO1998000296A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451420B1 (en) 2000-03-17 2002-09-17 Nanofilm, Ltd. Organic-inorganic hybrid polymer and method of making same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58224761A (ja) * 1982-06-25 1983-12-27 Canon Inc インクジエツト記録ヘツド
JP3397478B2 (ja) * 1993-11-26 2003-04-14 キヤノン株式会社 インクジェットヘッド及び該インクジェットヘッドの製造方法及びインクジェット装置
DE4400315C1 (de) * 1994-01-07 1995-01-12 Kernforschungsz Karlsruhe Verfahren zum stufenweisen Aufbau von Mikrostrukturkörpern und damit hergestellter Mikrostrukturkörper
JPH08174845A (ja) * 1994-12-26 1996-07-09 Canon Inc 液流路形成用樹脂材料、これを用いた液体噴射記録ヘッド、及びその製造方法
US6461798B1 (en) * 1995-03-31 2002-10-08 Canon Kabushiki Kaisha Process for the production of an ink jet head
DE19613650C1 (de) * 1996-04-04 1997-04-10 Fraunhofer Ges Forschung Hydrolisierbare, fluorierte Silane, Verfahren zu deren Herstellung und deren Verwendung zur Herstellung von Kieselsäurepolykondensaten und Kieselsäureheteropolykondensaten

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Publication number Publication date
WO1998000296A1 (fr) 1998-01-08
DE59703535D1 (de) 2001-06-21
CA2230636A1 (fr) 1998-01-08
EP0816095A1 (fr) 1998-01-07

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