EP2963500A1 - Particule polymere - Google Patents

Particule polymere Download PDF

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Publication number
EP2963500A1
EP2963500A1 EP15176385.1A EP15176385A EP2963500A1 EP 2963500 A1 EP2963500 A1 EP 2963500A1 EP 15176385 A EP15176385 A EP 15176385A EP 2963500 A1 EP2963500 A1 EP 2963500A1
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EP
European Patent Office
Prior art keywords
group
functional group
polymer
polymer particles
functional
Prior art date
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EP15176385.1A
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German (de)
English (en)
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EP2963500B1 (fr
Inventor
Thomas Hirth
Achim Weber
Kirsten Borchers
Stefan GÜTTLER
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Universitaet Stuttgart
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP2963500A1 publication Critical patent/EP2963500A1/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/20—Fixing, e.g. by using heat
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/22—Apparatus for electrographic processes using a charge pattern involving the combination of more than one step according to groups G03G13/02 - G03G13/20
    • G03G15/221—Machines other than electrographic copiers, e.g. electrophotographic cameras, electrostatic typewriters
    • G03G15/224—Machines for forming tactile or three dimensional images by electrographic means, e.g. braille, 3d printing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0825—Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08706—Polymers of alkenyl-aromatic compounds
    • G03G9/08708—Copolymers of styrene
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08724—Polyvinylesters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08726—Polymers of unsaturated acids or derivatives thereof
    • G03G9/08728—Polymers of esters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08753—Epoxyresins
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08755—Polyesters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08759—Polyethers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08771—Polymers having sulfur in the main chain, with or without oxygen, nitrogen or carbon only
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08791—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by the presence of specified groups or side chains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08793—Crosslinked polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/093—Encapsulated toner particles
    • G03G9/09307—Encapsulated toner particles specified by the shell material
    • G03G9/09342—Inorganic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/093—Encapsulated toner particles
    • G03G9/0935—Encapsulated toner particles specified by the core material
    • G03G9/09357—Macromolecular compounds
    • G03G9/09364—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09708—Inorganic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09708—Inorganic compounds
    • G03G9/09725—Silicon-oxides; Silicates
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material

Definitions

  • the present invention relates to polymer particles which are particularly suitable as toner particles for electrophotographic processes, to electrophotographic processes for producing three-dimensional structures on a support structure and to the three-dimensional structures produced by means of these processes.
  • the melting of toner or polymer particles by means of electromagnetic radiation is known by the term "non-contact fusing".
  • the electromagnetic radiation is used as a heat source for the melting of the polymer.
  • a chemical fixation of the toner particles on each other is not achieved ( JP 002000035689 . JP 002004177660 . US 000004435069 A . DE 000010064563 A1 ).
  • Electrophotography (“laser printing”) has proven in recent decades to be a reliable method for two-dimensional typeface printing with comparatively high resolution (1200 dpi, resolution ⁇ 50 ⁇ m). Accordingly, electrophotography represents a widespread printing technique with which technical surfaces, usually in the form of paper or film surfaces, can be printed with substances present in powder form.
  • a rotating photo-roll which is coated with a photo semiconductor material, electrostatically charged, for example by means of a Vorladungswalze or a corona, and then exposed by means of a laser array or an LED array at local locations, whereby they at these exposed areas at least partially discharged electrically.
  • All other, unexposed areas of the photo-roll remain electrically charged and correspond to the negative image of the two-dimensional structures to be printed, for example in the form of texts, images etc.
  • Powdered toner is transferred to the exposed photo-roll in a subsequent step, the toner being rubbed in the printing unit is electrostatically charged and therefore able to adhere only to the discharged areas of the photo-roll.
  • To influence the electrostatic charge of the toner today's commercially available toner contain about 2 to 4 vol.% Charge control additives.
  • the majority of the toner ie about 80 to 90 vol.% Usually consists of a dry solvent, the so-called matrix, which typically consists of a mixture of resin and wax.
  • About 5 to 18% by volume of the toner contains a dye fraction, for example in the form of carbon black.
  • electrophotographic processes with which multilayer objects can be printed from metal powder
  • metal powder van der Eijk et al., Metal Printing Process: A Rapid Manufacturing Process Based on Xerography using Metal Powders Materials, Science & Technology, 2005
  • electrophotographic generated surfaces were structured three-dimensionally by means of foaming agents ( JP 002005004142 AA ).
  • foaming agents JP 002005004142 AA
  • the resolution can not be controlled sufficiently and is limited to the toner layer located on the support structure. This method therefore does not offer the possibility of generating a three-dimensional object in layers.
  • Electrophotographic processes are also known in which the adhesion of the toner to the support structure is increased by means of curing reactive groups ( US 5,888,689 ) and / or by postcrosslinking the particles by the addition of photoinitiators ( WO 2006/027264 A1 . EP 0 667 381 B1 . EP 0 952 498 A1 ). Also known is a process for producing toner materials containing UV-polymerizable additives ( US 000005212526 A ). However, these methods alone provide improved adhesion to the support surface and do not ensure the controlled three-dimensional construction of polymer layers.
  • the technical problem underlying the present invention is to provide methods and means which overcome the aforementioned disadvantages, in particular to provide methods and means by means of which high-resolution three-dimensional structures, in particular in the micron and / or mm range, can be produced, in particular a fast and cost-effective method and wherein the products produced may also be biocompatible and biofunctional.
  • the present invention is based on the technical problem of providing high-resolution three-dimensional structures of the aforementioned type which can be used, for example, as transplants, in tissue engineering methods or products, as tube structures or the like.
  • the present invention solves the underlying technical problem by providing polymer particles according to the main claim and from these polymer particles, in particular by way of electrophotography, produced three-dimensional structures that may be present with or without support structure, in particular controlled from the three-dimensional structures produced by electrophotography Again, a portion of the polymer particles, in particular at least a portion of at least one polymer particle type is removable.
  • the invention therefore relates to polymer particles comprising a polymer matrix having a coating of an inorganic metalloid or metal oxide, the polymer matrix having at least one first functional group A and at least one second functional group B, the two functional groups A and B being capable of at least to form a covalent bond with each other, wherein the functional group A is selected from the group consisting of an azide group, CC double bond, CC triple bond, aldehyde group, ketone group, imine group, thioketone group and thiol group and wherein the functional group B is selected from the group consisting from a CC double bond, CC triple bond, CN triple bond, diene group, thiol group and amine group.
  • the functional group A is selected from the group consisting of an azide group, CC double bond, CC triple bond, aldehyde group, ketone group, imine group, thioketone group and thiol group
  • the functional group B is selected from the group consisting from a CC
  • the functional groups A and B capable of undergoing at least one covalent bond with each other are referred to as complementary groups or pairs of complementary groups.
  • a group complementary to the functional group A is therefore the functional group B and a group which is complementary to the functional group B is therefore the functional group A.
  • the functional group A of a polymer particle reacts with the complementary functional group B of another polymer particle so as to achieve fixation of the particles among one another.
  • the present teaching when the present teaching relates to a covalent bond of two functional groups A and B with each other, there is a covalent bond between a first and a further polymer particle or a bond between a polymer particle and a corresponding complementary group having support structure understood.
  • the invention therefore advantageously provides polymer particles which are also referred to as toners or toner particles in the context of the present invention and which, due to their particulate and functionalized structure, are particularly suitable for being applied to support structures in electrophotographic processes.
  • the functional groups A and B applied to the polymer particles according to the invention make it possible to fix the polymer particles on the support structure surface and also to achieve a fixation of the particles among one another.
  • the functional groups containing the functional groups A and B and accordingly functionalized polymer particles preferably react according to FIG. 1 of the present teaching so that a functional group A of a first polymer particle reacts with a functional group B of a second polymer particle to form at least one covalent bond, so that a fixation of the particles takes place with each other.
  • the presence of the functional groups A and B on the polymer particle of the present invention also makes it possible to fix the polymer particle to a support structure to be printed which has a complementary functional group A or B.
  • the reactions between the functional groups A and B therefore lead to an increase in the adhesive force between polymer particles and support structure and between polymer particles and polymer particles.
  • the polymer particles according to the invention enable the construction of high-resolution three-dimensional, in particular in electrophotographic processes Structures, in particular with resolutions below 250 .mu.m, which may advantageously be constructed from different materials due to the inventively provided simultaneous applicability of different polymer particles, which preferably can be selectively transferred to the support structure selectively in one and the same printing cycle, preferably in layers, especially in one and the same applied layer.
  • the polymer particles of the present invention make it possible to provide three-dimensional structures fixed by chemical reactions, wherein the chemical reactions required for the fixation can be selectively initiated in a preferred embodiment.
  • three-dimensional objects can be constructed in this way, the z. B. in medical, biomedical or biological products can be used, for.
  • biocompatible especially biofunctional polymer particles can be produced.
  • the method provided according to the invention which makes it possible to transfer a plurality of different polymer materials, that is to say polymeric material types, with high resolution in the same printing cycle, also makes it possible to construct porous or non-porous structures, for example tube structures which are used, for example, in tissue engineering applications.
  • Process or products as e.g. B. can serve biocompatible support structures for cell cultures, as transport systems or transport vessels or as artificial blood vessels or capillaries.
  • the present invention relates to polymer particles, wherein the polymer matrix forming polymer is selected from the group consisting of polystyrenes, polystyrene derivatives, Polyacrylates, polyacrylic derivatives, polyvinyl acetate, poly (methacrylic acid methyl ester), poly (glycidyl acrylate), polyesters, polyamides, polycarbonates, polyacrylonitriles, polyvinyl chlorides, polyethers, polysulfone, polyether ketones, epoxy resin, melamine-formaldehyde resin or derivatives or combinations or copolymers of said polymers.
  • the polymer matrix forming polymer is selected from the group consisting of polystyrenes, polystyrene derivatives, Polyacrylates, polyacrylic derivatives, polyvinyl acetate, poly (methacrylic acid methyl ester), poly (glycidyl acrylate), polyesters, polyamides, polycarbonates, polyacrylonitriles, polyvinyl chlorides,
  • the polymer is a homopolymer, a copolymer, a terpolymer or a mixture (blend) thereof.
  • the preparation of the polymeric base material, so the polymer matrix can be carried out in a preferred embodiment by free-radical polymerization in which an initiator thermally, radiation-induced, z. B. with a wavelength of 10 -14 m to 10 -4 m, or initiates the polymerization radically due to a redox process.
  • the production is possible by means of ionic polymerization in which either a cationic or an anionic initiator initiates the polymerization.
  • the synthesis of the material by means of polycondensation is possible, in which the polymerization of the monomers takes place under the stoichiometric elimination of by-products.
  • the production by means of polyaddition is possible, in which the polymerization takes place without stoichiometric cleavage of by-products.
  • a further possibility of production in a preferred embodiment is the poly insertion, in which a metal or metal complex initiates the polymerization.
  • both homopolymers, copolymers and terpolymers can be produced, which are suitable for the inventive method.
  • the softening temperature of the material due to a glass transition or a melt transition may be influenced in a preferred embodiment by the choice of the repeating unit of the homopolymer or by the respective mass fractions of the repeat units in the co- or terpolymer or in a mixture (blend) thereof.
  • the softening temperature is in a preferred embodiment of 25 ° C to 250 ° C, in particular low-melting materials whose softening temperature is 35 ° C to 100 ° C, are preferred.
  • the monomers used either contain one or more polymerisable units, so that either linear or crosslinked polymers can form during the polymerization.
  • the polymer can be produced in a preferred embodiment by bulk polymerization, in which the polymerization takes place without the presence of a solvent.
  • the preparation by solution polymerization is possible in which a solvent is used which dissolves both the monomer or the monomers and the resulting polymer.
  • heterogeneous polymerization methods are possible in which the polymer becomes insoluble within a certain molecular weight within the dispersant.
  • the emulsion polymerization wherein the polymerization takes place within micelles, which are produced by surfactant molecules or block copolymers.
  • suspension polymerization wherein the polymerization occurs within dispersed monomer droplets.
  • this group includes dispersion polymerization using a dispersant in which the monomer is soluble under the reaction conditions while the polymer forms an insoluble phase therein beyond a certain molecular weight.
  • the polymer particles of the invention are preferably in spherical or droplet form.
  • the shape of the polymer particles may be altered following the polymerization by thermal or mechanical working of the polymeric material. These processing steps include melting, extruding and grinding the polymer.
  • the polymer particles of the present invention are preferably in powder form.
  • the present invention relates to polymer particles of the present invention, wherein the polymer particles have a size of 0.5 to 50 .mu.m, in particular 1 to 50 .mu.m, preferably 5 to 50 .mu.m, preferably 5 to 45 .mu.m, preferably 5 to 20 .mu.m, preferably 10 to 45 .mu.m, preferably 15 to 40 .mu.m, in particular 20 to 40 microns.
  • the present invention relates to polymer particles of the present invention, wherein the polymer particle has at least one additive, wherein in a preferred embodiment of the present invention, the additive is selected from the group consisting of a dye, for. Carbon black, and a charge control additive.
  • the present invention relates to polymer particles having a coating of semimetal or metal oxide of the present invention, wherein the semimetal or metal oxide is an inorganic metalloid or metal oxide, preferably SiO 2 , TiO 2 or Al 2 O 3 .
  • the metalloid or metal oxide serves to control the adhesive force and charge.
  • the invention preferred, to be used as a coating inorganic semimetal or metal oxide on the surface of the polymer matrix in primary particle sizes of 0.1 nm to 300 nm, in particular 1 to 100 nm before.
  • the coating of the polymer matrix is not a continuous coating, but rather a coating which is only partially, in particular punctually localized.
  • the present invention relates to polymer particles of the present invention, wherein the functional groups A and B are capable of forming a covalent bond with each other by means of a ring-closing or non-ring reaction.
  • the present invention provides polymer particles having complementary functional groups A and B, both preferably being members each one of the following complementary groups i) to vi) are. Accordingly, in a preferred embodiment of the present invention, the polymer particles comprise pairs of complementary functional groups A and B, preferably those which are each variant in one of the complementary groups i) to vi) defined below.
  • the invention also provides a process for the preparation of the polymer particles according to the invention by providing the functional groups A and B comprising particles of the polymer matrix and then provided with a coating of a semimetal or metal oxide and thus obtain polymer particles according to the invention.
  • the invention also provides a process for the preparation of the polymer particles according to the invention, wherein in a first process step Particles from the polymer matrix provided in a second process step, these provided with the functional groups A and B and in a third process step with a coating of a semimetal or metal oxide and polymer particles of the invention are obtained.
  • the polymer particles according to the invention are prepared by carrying out the aforementioned second process step after the third process step or both simultaneously.
  • the invention also provides methods for producing a three-dimensional structure on a support structure, wherein polymer particles are provided according to the present invention and at least one support structure and wherein the polymer particles are applied to the support structure by means of an electrophotographic process, in particular imprinted and obtained a three-dimensional structure with support structure becomes.
  • the electrophotographic process according to the invention is an electrophotographic printing process.
  • the present invention relates to a method of the present invention, wherein the polymer particles are applied by applying in a first step a) in the form of a layer on the support structure and in a second step b) a fixation, preferably a selectively initiated fixation , is carried out.
  • a fixation preferably a selectively initiated fixation
  • the process steps a) and b) in this sequence at least twice, preferably two to five times, in particular two to 14 times, in particular two to 30 times, in particular three to 30 times, in particular four bis 20 times, in particular five to 15 times, in particular five to ten times, in particular 100 to 1000 times, in particular 300 to 800 times, in particular 400 to 600 consecutively carried out, so that forms a corresponding number of layers.
  • the process of the invention is advantageously and in a preferred embodiment feasible without the addition of photoinitiators or UV-polymerizable additives.
  • a support structure is coated, in particular printed, with polymer particles of the present invention, the support structure having a functional group A or B which is complementary to a functional group A or B of the polymer particle to be applied.
  • the inventive method allows controlled in an advantageous manner and in particular layers, three-dimensional polymer structures by means of electrophotographic processes.
  • the functional groups A and B used according to the invention no addition of photoinitiators, in particular UV-labile initiator components, is necessary.
  • the fixation is achieved without stoichiometric formation of by-products.
  • the reaction between the functional groups A and B is selective can be initiated, which makes it possible to specifically react certain polymer particles with each other, in particular to fix.
  • the procedure according to the invention thus enables the combination and fixation of different polymer particles, that is to say different types of polymer particles, in a single or multiple layers, in that different fixing steps can be carried out independently of one another, which advantageously enables the selective fixation of different polymer particles.
  • it is not necessary for the construction of three-dimensional structures due to the specific, coordinated functional groups used to carry out a long or energy-intensive heat treatment, which leads disadvantageously in the prior art in each fixing step to the melting of the structures.
  • a strong deformation of the structures occurs, whereby the spatial resolution is limited.
  • the surface of the object is rapidly wavy and on the hills thus formed in more pressure passes more toner is transmitted as in the valleys, whereby the wave formation further amplified and the height structure is completed after a few layers.
  • a possibly carried out hot rolling or pressing leads to a strong structural deformation and concomitant reduced height structure.
  • the functional groups A and / or B which functionalize the polymer particles of the present invention are freely accessible on the particle surface.
  • the functional groups A and / or B which functionalize the polymer particles of the present invention are below the surface of the polymer particle embedded in the polymer matrix and can be made available in a particularly preferred embodiment by melting or Ansintern a reaction on the particle surface.
  • the method according to the invention can be carried out by applying, heating and fixing the applied polymer particles, preferably in a multiplicity of these method steps, in a repetitive manner.
  • the present invention relates to a method of the present invention, wherein the sequence of method steps a) and b) with an intervening step of melting at least twice, preferably two to 50 times, in particular two to 40 times, in particular two- to 30 times, in particular three to 20 times, in particular four to 20 times, in particular five to 15 times, in particular five to ten times, in particular 100 to 1000 times, in particular 300 to 800 times, in particular 400 to 600 times in succession, so that a corresponding number of layers is generated.
  • each layer is composed of a single polymer particle type.
  • the layers can be constructed from respectively different polymer particle types.
  • at least two different polymer particle types of the present invention are present per applied layer.
  • each of the at least two layers is composed of different types of polymer particles which, in a preferred embodiment, are selective and different from each other due to their different functional group A and B configuration initiate separately and connect accordingly.
  • a three-dimensional structure can be formed, the height differences, ie spatial distances, in the Z plane of 0.5 to 15 mm, in particular 0.5 to 8 mm, in particular 1 to 7 mm, preferably 2 up to 6 mm.
  • the present invention relates to a method of the present invention wherein the fixation is a metal catalyst-mediated, microwave-initiated, thermally-initiated, photoinitiated, or catalyst-free fixation.
  • the present invention provides that the fixing preferably provided according to the invention, in particular selectively initiated fixation, takes place depending on the type of functional groups A and B of the applied polymer particles.
  • a metal catalyst-mediated, in particular copper / zinc-mediated, microwave-initiated or thermally-initiated fixation is used when the functional groups A and B on the polymer particles used are capable of binding to each other by means of ring closure reaction in particular if the functional groups A and B are selected from the complementary groups i), iii) or iv).
  • the fixation is a photo-initiated, in particular UV-initiated fixation, in particular if the polymer particles used have functional groups A and B which are capable of bonding together by means of a ring-closing reaction, in particular that of the complementary group ii).
  • the fixation used takes place catalyst-free, in particular if the functional groups A and B are capable of binding with one another in a ring-free reaction and wherein the functional groups A and B of the polymer particle used are those of the complementary group v) are.
  • the fixation is a photoinitiated fixation, in particular at a wavelength of 365 nm, in particular when the functional groups A and B used are capable of binding with each other by means of a ring-free reaction and in a preferred embodiment the functional groups A and B of the polymer particles used are those of the complementary group vi).
  • the present invention provides a method of the present invention, wherein
  • the fixation ie covalent binding of the functional groups A and B, a metal catalyst-mediated, in particular copper / Zinc-mediated, microwave-initiated or thermally-initiated fixation.
  • a metal-mediated, microwave-initiated or thermally-initiated fixation can be selectively initiated and allows a particularly targeted and controlled construction of three-dimensionally arranged layers also of different composition.
  • the invention provides a method of the present invention, wherein
  • the fixation is a photo-initiated, especially UV-initiated fixation.
  • the inventively preferred photoinitiated fixation allows a particularly targeted and controlled construction of three-dimensionally arranged layers also of different composition.
  • the present invention relates to a method of the present invention, wherein
  • the fixation is a metal catalyst-mediated, in particular copper / zinc-mediated, microwave-initiated or thermally-initiated fixation.
  • a metal-mediated, microwave-initiated or thermally-initiated fixation can be selectively initiated and allows a particularly targeted and controlled construction of three-dimensionally arranged layers also of different composition.
  • the present invention relates to a method of the present invention, wherein
  • the fixation is a thermally-initiated, metal catalyst-mediated, especially copper / zinc catalyst-mediated or microwave-initiated fixation.
  • a metal-mediated, microwave-initiated or thermally-initiated fixation can be selectively initiated and allows a particularly targeted and controlled construction of three-dimensionally arranged layers also of different composition.
  • the present invention relates to a method of the present invention, wherein
  • the present invention relates to a method of the present invention, wherein
  • the fixation is a photoinitiated fixation, especially at a wavelength of 365 nm.
  • a photoinitiated fixation is selectively initiated and allows a particularly targeted and controlled construction of three-dimensionally arranged layers also of different composition.
  • the process according to the invention provides a process in which at least two, preferably two to six, in particular three to five, different polymer particle types of the present invention are applied to the support structure, in particular in a single layer.
  • the present invention relates to a method in which after fixing in step b) controlled from the resulting three-dimensional structure, a part of the polymer particles, in particular at least one part of at least one polymer particle type is removed and thereby, for example, functional three-dimensional hollow structures such as tubular structures and / or porous structures are obtained.
  • the part of the polymer particles to be removed is removed by enzymatic and / or chemical processes, in particular degraded.
  • the part of the polymer particles to be removed in particular at least one part of at least one type of polymer particle, is removed without the support structure being removed.
  • the part of the polymer particles to be removed, in particular at least one part of at least one type of polymer particle, and the support structure are removed.
  • Different types of polymer particles of the present invention may be those particles which, in the presence of the same functional groups A and B, are distinguished solely by a differently constructed polymer matrix as compared to other polymer particles of the present invention.
  • different types of polymer particles of the present invention may also be those polymer particles which, for the same polymer matrix compared to other polymer particles of the present invention, have a different functionalization in the form of at least one dissimilar functional polymer Group A and / or B.
  • Different types of polymer particles of the present invention may also be those which excel in both the polymer material of the matrix and in the functionalizing groups A and / or B.
  • the at least two, preferably several or many different polymer particle types of the present invention are present in a single layer or in at least one, preferably several or many layers of the produced three-dimensional structure.
  • a rigid or flexible support structure is used according to the invention, in particular, the support structure may be made of a plastic material.
  • the support structure may be a plastic film, plastic film, membrane, glass, metal, semi-metal, fleece or paper, preferably of biocompatible, in particular biodegradable material.
  • the present invention provides for separating the three-dimensional structure produced according to the invention from the support structure, for. As by chemical, physical or biological degradation, and so to obtain a three-dimensional structure without support structure.
  • a production according to the invention in particular a printing process according to the invention, will be described with reference to components present in a per se known laser printer arrangement.
  • a conventional laser printer is a to be printed with polymer particles according to the invention support structure, for.
  • glass or paper usually in DIN A4 format, promoted by a conveyor belt to the photo-roll of a printing unit and pressed on rubber or foam rollers, which are arranged under the conveyor belt to the photo-roll.
  • the feed rate of the support structure to be printed is adapted synchronized to the rotational speed of the photo-roll, so that the roller with the structured adhering thereto functionalized polymer particles without slip on the support structure to be printed, for.
  • the functionalized polymer particles adhering to the support structure surface are easily melted to make the functional groups of the polymer particles accessible for bonding.
  • the support structure in this case the piece of paper, is heated homogeneously to a defined temperature for a defined time.
  • the heating of the support structure is preferably carried out in an oven outside the printer, since in this way a uniform heating of the support structure on the one hand very easily possible and on the other hand can be avoided to burden the printer itself thermally.
  • integrated heaters are also conceivable, in which case the support structure is preferably non-contact, for example in the way of applied radiant heat, for. B. by IR emitters to heat.
  • the polymer particles present on the surface of the support structure may be subjected to a chemical aftertreatment in which additives, i. H. For example, any existing charge control additives are removed.
  • the use of a printing device the z. B. from the DE 20 2005 018 237 U1 can be seen, opens up the possibility of a multi-pressure coating of a surface area on a support structure for forming multilayer systems, for example of three-dimensionally structured functional layers or multilayer layers, which consist of a multi-layered structure in which each layer is formed of differently functionalized polymer particles.
  • a multi-pressure coating of a surface area on a support structure for forming multilayer systems, for example of three-dimensionally structured functional layers or multilayer layers, which consist of a multi-layered structure in which each layer is formed of differently functionalized polymer particles.
  • it is advisable to use surface-rigid support structures in order to enable the reproducible positioning accuracy of the support structure in the printer, which is required for several print passes on one and the same support structure.
  • the present invention also provides three-dimensional structures with or without support structure made in accordance with any of the methods of the present invention.
  • the polymer particles used according to the invention and their reaction products formed by fixing the three-dimensional structure can be identified by means of elemental analysis, nuclear magnetic resonance (NMR) spectroscopy, X-rays, photoelectron spectroscopy (XPS) and / or infrared spectroscopy (IR).
  • NMR nuclear magnetic resonance
  • XPS photoelectron spectroscopy
  • IR infrared spectroscopy
  • the three-dimensional structure with or without support structure in particular with targeted removal of at least a portion of the polymer particles, in particular at least one type of polymer particles, is preferably suitable for tissue engineering methods or products.
  • the three-dimensional structure with or without support structure is a test system, implant, support structure or supply structure for tissue engineering procedures and products, for example, an artificial blood vessel, biocompatible porous, non-porous, or tubular branched or unbranched tissue culture matrix or a transport system for liquids or gases.
  • the three-dimensional structures produced are biocompatible, biodegradable and / or biofunctional.
  • the structures produced are non-porous or porous.
  • Inventive structure can, for. B. as test systems for example, biological, chemical or pharmaceutical agents or systems, or as a transplant, in particular as a blood vessel, capillary or tube system.
  • the three-dimensional structure with or without support structure on a biocompatible polymeric material and / or biofunctional toner particles is provided.
  • the particles were filtered off and washed three times with 20 mL n-hexane and dried under reduced pressure for 2 h.
  • the particles were redispersed in 50 mL H 2 O and admixed with 4.45 g EDCHCl. Subsequently, 1.79 g of cysteamine were added and the suspension was stirred for 24 h at RT (room temperature). Subsequently, the particles were filtered off, washed five times with 20 mL H 2 O and dried under reduced pressure for 12 h.
  • the q / m ratio of the polymer particles was adjusted with 25 mg of silica TX-20 to a value of -10 ⁇ C / g to -30 ⁇ C / g in order to then print the particles with an OKI C7000 printing unit.
  • the support structure used was a glass plate (20 ⁇ 20 cm) which had been previously treated with dimethyl allyl silyl chloride at RT for 2 h. Following the printing process, the particles were irradiated with a 9 kW mercury vapor lamp for 15 minutes to fix onto the support structure. Thereafter, another layer of the toner particles was applied to the first toner layer and irradiated again for 15 minutes. In this way, a multilayered polymer structure could be constructed.
  • the particles were dried under reduced pressure for 2 h and then redispersed for 5 min in 200 mL of a 1% copper (I) salicylate solution. Then, the polymer particles were filtered off and dried unwashed under reduced pressure for 6 hours. Subsequently, the q / m ratio was adjusted to a value of -10 ⁇ C / g to -30 ⁇ C / g with 40 mg of silica TX-20 and the particles were printed using an OKI printing unit C7000.
  • the support structure used was a glass plate (20 ⁇ 20 cm) which had been previously treated with (11-azidoundecyl) chlorodimethylsilane at RT for 2 h.
  • the particles were irradiated with microwave radiation (1100 W) for 2 minutes to fix them on the support structure. Thereafter, another layer of the toner particles was applied to the first toner layer and irradiated again for 2 minutes. In this way, a multilayered polymer structure could be constructed.
  • the particles were dried under reduced pressure for 6 hours. Subsequently, the q / m ratio was adjusted with 36 mg of silica TX-20 to a value of -10 ⁇ C / g to -30 ⁇ C / g and the particles were printed with an OKI printing unit C7000.
  • the support structure used was a glass plate (20 ⁇ 20 cm) which had been previously treated with (11-azidoundecyl) chlorodimethylsilane at RT for 2 h. Following the printing process, the particles were irradiated with microwave radiation (1100 W) for 30 minutes to fix them on the support structure. Thereafter, another layer of the toner particles was applied to the first toner layer and irradiated again for 30 minutes. In this way, a multilayered polymer structure could be constructed.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP15176385.1A 2010-09-17 2011-09-07 Particule polymere Not-in-force EP2963500B1 (fr)

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DE102010045679A DE102010045679A1 (de) 2010-09-17 2010-09-17 Verfahren zur chemischen Tonerfixierung
EP11758391.4A EP2616885B1 (fr) 2010-09-17 2011-09-07 Procédé de fabrication d'une structure tridimensionnelle à partir de particules de polymère au moyen d'un procédé électrophotographique

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EP11758391.4A Division EP2616885B1 (fr) 2010-09-17 2011-09-07 Procédé de fabrication d'une structure tridimensionnelle à partir de particules de polymère au moyen d'un procédé électrophotographique

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EP2616885B1 (fr) 2016-04-13
US20150309434A1 (en) 2015-10-29
EP2963500B1 (fr) 2017-12-06
WO2012034666A1 (fr) 2012-03-22
US20130171434A1 (en) 2013-07-04
JP2013543522A (ja) 2013-12-05
US9098000B2 (en) 2015-08-04
EP2616885A1 (fr) 2013-07-24
DE102010045679A1 (de) 2012-03-22

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