EP2963500A1 - Polymer particles - Google Patents

Abstract

The present invention relates to polymer particles comprising a polymer matrix having a coating of an inorganic metalloid or metal oxide, wherein the polymer matrix has at least one first functional group A and at least one second functional group B, wherein the two functional groups A and B are capable of at least one 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 of a CC double bond, CC triple bond, CN triple bond, diene group, thiol group and amine group.

Description

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 production of three-dimensional objects with the help of computer-generated models is becoming increasingly important. The layered structure, which is carried out regularly, enables individual adaptation of the desired structure. The demand for multi-component parts and their increasingly complex geometry increases the requirements for the spatial resolution of the manufacturing process. Especially in medical technology, the specific production of transplants is associated with great effort, since the objects must be individually adapted to each patient.

Various methods are known which enable the construction of three-dimensional plastic objects. They are grouped under the name "rapid prototyping" (or "solid freeform fabrication") ( Wang, Trends in Biotechnology, 25 (11), pages 505-513 ). However, these methods are either limited to the application of a single polymer component or have resolutions above> 250 microns.

The melting of toner or polymer particles by means of electromagnetic radiation is known by the term "non-contact fusing". In this method, 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 μm). 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. In principle, in electrophotography, 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.

Also known are electrophotographic processes, with which multilayer objects can be printed from metal powder ( van der Eijk et al., Metal Printing Process: A Rapid Manufacturing Process Based on Xerography using Metal Powders Materials, Science & Technology, 2005 ). In addition, electrophotographic generated surfaces were structured three-dimensionally by means of foaming agents ( JP 002005004142 AA ). However, 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 application of such processes for biologically and medically usable three-dimensional plastic parts, however, represents a hitherto unsolved problem, above all because of the necessary spatial fixation of the individual particles ( US 6,066,285 A ).

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. In particular, 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.

In particular, 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.

In the context of the present invention, 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.

In a preferred embodiment, it is provided that 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. In the context of the present invention, 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. In a particularly advantageous manner, 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. According to the invention, 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. In a particularly advantageous manner, 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. Advantageously, three-dimensional objects can be constructed in this way, the z. B. in medical, biomedical or biological products can be used, for. As in transplants or as transplants, and advantageously from 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.

In a preferred embodiment, 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.

In a preferred embodiment, 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. Moreover, in a preferred embodiment, the production is possible by means of ionic polymerization in which either a cationic or an anionic initiator initiates the polymerization. Furthermore, in a preferred embodiment, 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. In addition, in a preferred embodiment, 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. In particular, in this way, 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. Also, in a preferred embodiment, 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. Furthermore, in a preferred embodiment, heterogeneous polymerization methods are possible in which the polymer becomes insoluble within a certain molecular weight within the dispersant. These include in a preferred embodiment, the emulsion polymerization, wherein the polymerization takes place within micelles, which are produced by surfactant molecules or block copolymers. Also included in this group is suspension polymerization wherein the polymerization occurs within dispersed monomer droplets. In addition, 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.

In addition, in a preferred embodiment of the present invention, 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.

According to the invention, the polymer particles of the present invention are preferably in powder form.

In a preferred embodiment, 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.

In a preferred embodiment, 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.

In a preferred embodiment, 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.

In an advantageous embodiment of the present invention, 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.

In a particularly preferred embodiment of the present invention, the coating of the polymer matrix is not a continuous coating, but rather a coating which is only partially, in particular punctually localized. In a particularly preferred embodiment of the present invention, 5 to 50%, preferably 20 to 50%, preferably 20 to 40%, preferably 30 to 40%, preferably 5 to 20%, preferably 7 to 18%, in particular 8 to 16% of the surface of the polymer particle coated by the coating.

In a preferred embodiment, 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.

In a particularly preferred embodiment, 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.

1. i) wenn die funktionelle Gruppe A eine Azidgruppe ist, ist die funktionelle Gruppe B eine C-C-Doppelbindung, C-C-Dreifachbindung oder C-N-Dreifachbindung,
2. ii) wenn die funktionelle Gruppe A eine C-C-Doppelbindung oder C-C-Dreifachbindung ist, ist die funktionelle Gruppe B eine C-C-Doppelbindung oder C-C-Dreifachbindung,
3. iii) wenn die funktionelle Gruppe A eine C-C-Doppelbindung oder C-C-Dreifachbindung ist, ist die funktionelle Gruppe B eine Diengruppe oder
4. iv) wenn die funktionelle Gruppe A ausgewählt ist aus der Gruppe bestehend aus einer Aldehydgruppe, Ketongruppe, Imingruppe oder Thioketongruppe, ist die funktionelle Gruppe B eine Diengruppe.

In a preferred embodiment, the present invention relates to polymer particles of the present invention wherein the functional group A is selected from the group consisting of azide group, CC double bond, CC triple bond, aldehyde group, ketone group, imine group and thioketone group and the functional group B is selected from A group consisting of a CC double bond, a CC triple bond, a CN triple bond and a diene group and wherein both are capable of forming a covalent bond with each other by means of a ring closure reaction and wherein:

1. i) when the functional group A is an azide group, the functional group B is a CC double bond, CC triple bond or CN triple bond,
2. ii) when the functional group A is a CC double bond or CC triple bond, the functional group B is a CC double bond or CC triple bond,
3. iii) when the functional group A is a CC double bond or CC triple bond, the functional group B is a diene group or
4. iv) when the functional group A is selected from the group consisting of an aldehyde group, ketone group, imine group or thioketone group, the functional group B is a diene group.

• v) wenn die funktionelle Gruppe A eine C-C-Doppelbindung oder C-C-Dreifachbindung ist, ist die funktionelle Gruppe B eine Thiol- oder Amingruppe oder
• vi) wenn die funktionelle Gruppe A eine Thiolgruppe ist, ist die funktionelle Gruppe B eine C-C-Doppelbindung oder C-C-Dreifachbindung.

In a preferred embodiment, the present invention relates to polymer particles of the present invention wherein the functional group A is selected from the group consisting of CC double bond, CC triple bond and thiol group and the functional group B is selected from the group consisting of thiol group, amine group, CC Double bond and CC triple bond and both being able to form a covalent bond with each other by means of a ring-free reaction and where:

• v) when the functional group A is a CC double bond or CC triple bond, the functional group B is a thiol or amine group or
• vi) when the functional group A is a thiol group, the functional group B is a CC double bond or CC triple bond.

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. In a preferred embodiment, 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.

In a preferred embodiment, the electrophotographic process according to the invention is an electrophotographic printing process.

In a preferred embodiment, 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. The inventively provided fixation, in particular the selectively provided selectively initiated fixation, on the one hand fixes the functional groups A and B having polymer particles on the support structure and on the other hand, the polymer particles with each other.

In a particularly preferred embodiment, 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.

In a particularly preferred embodiment, according to the invention, 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. Advantageously, due to the functional groups A and B used according to the invention, no addition of photoinitiators, in particular UV-labile initiator components, is necessary. In a particularly preferred manner, the fixation is achieved without stoichiometric formation of by-products. Moreover, it is advantageous that, in a preferred embodiment of the present invention, 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. According to the invention, 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. According to the methods known hitherto, a strong deformation of the structures occurs, whereby the spatial resolution is limited. Furthermore, 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.

In a particularly preferred embodiment, the functional groups A and / or B which functionalize the polymer particles of the present invention are freely accessible on the particle surface. In a further preferred embodiment, 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.

In a particularly preferred embodiment of the present invention, the, preferably in layer form, applied to the support structure polymer particles of the present invention at low temperatures of 30 to 150 ° C, preferably 60 to 150 ° C, especially 60 to 120 ° C, more preferably 70th fused or sintered to 90 ° C, so that possibly on the particle surface not yet directly accessible functional groups for a fixation on the support structure or other applied polymer particle layers causing reaction are accessible.

In a particularly preferred embodiment of the present invention, 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.

In a preferred embodiment, 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.

In a particularly preferred embodiment of the present invention, at least two, preferably more layers of polymer particles are applied, in particular printed, by means of the electrophotographic process. In a particularly preferred embodiment, it is provided that each layer is composed of a single polymer particle type. In a preferred embodiment, it is provided that, if more than one layer is present, the layers can be constructed from respectively different polymer particle types. In a further particularly preferred embodiment, it is provided that at least two different polymer particle types of the present invention are present per applied layer. In a particularly preferred embodiment of the present invention, it is provided that at least two layers of polymer particles are applied, wherein 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.

In a particularly preferred embodiment of the present invention, 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.

In a preferred embodiment, 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.

By selecting the particular functional groups A and B having polymer particles of the present invention and the corresponding selection of the fixing method can be targeted control the fixation and thus the structure of the three-dimensional structure of the present invention.

In a particularly preferred embodiment, 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.

In a particularly preferred embodiment, it is provided that 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).

In a further preferred embodiment it is provided that 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).

In a particularly preferred embodiment, it is provided that 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.

In a further preferred embodiment, it is provided that 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).

In a particularly preferred embodiment, the present invention provides a method of the present invention, wherein

i) when the functional group A is an azide group and the functional group B is a CC double bond, a CC triple bond or CN triple bond, 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. Such 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.

In a further preferred embodiment, the invention provides a method of the present invention, wherein

ii) when the functional group A is a C-C double bond or C-C triple bond and the functional group B is a C-C double bond or a C-C triple bond, 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.

In a particularly preferred embodiment, the present invention relates to a method of the present invention, wherein

iii) when the functional group A is a C-C double bond or C-C triple bond and the functional group B is a diene, the fixation is a metal catalyst-mediated, in particular copper / zinc-mediated, microwave-initiated or thermally-initiated fixation. Such 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.

In a particularly preferred embodiment, the present invention relates to a method of the present invention, wherein

iv) when the functional group A is selected from the group consisting of an aldehyde group, ketone group, imine group or thioketone group and the functional group B is a diene group, the fixation is a thermally-initiated, metal catalyst-mediated, especially copper / zinc catalyst-mediated or microwave-initiated fixation. Such 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.

In a further preferred embodiment, the present invention relates to a method of the present invention, wherein

v) when the functional group A is a C-C double bond or C-C triple bond and the functional group B is a thiol or an amine, the fixation, a catalyst-free, d. H. non-selectively initiated fixation.

In a further preferred embodiment, the present invention relates to a method of the present invention, wherein

vi) when the functional group A is a thiol group and the functional group B is a C-C double or C-C triple bond, the fixation is a photoinitiated fixation, especially at a wavelength of 365 nm. Such a photoinitiated fixation is selectively initiated and allows a particularly targeted and controlled construction of three-dimensionally arranged layers also of different composition.

In a preferred embodiment, 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.

In a preferred embodiment, 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.

In a preferred embodiment, 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 by enzymatic and / or chemical processes, in particular degraded.

In a preferred embodiment of the invention, 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. In a preferred embodiment of the invention, 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. However, 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.

In a particularly preferred embodiment it can be provided that 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.

In a particularly preferred embodiment, a rigid or flexible support structure is used according to the invention, in particular, the support structure may be made of a plastic material. In a particularly preferred embodiment, 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.

In a preferred embodiment, 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.

In the following, 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. When using a conventional laser printer is a to be printed with polymer particles according to the invention support structure, for. As 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. As paper, unrolls and the functionalized polymer particles are transferred to the paper surface. If it is necessary to deposit a plurality of different polymer particles on one and the same support structure, correspondingly many printing units with corresponding photo-rollers are arranged one behind the other along the conveyor belt.

In the subsequent step, 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. For this purpose, 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. Of course, 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.

If necessary, in a subsequent treatment step, 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.

In particular, 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. For this purpose, 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).

In a particularly preferred embodiment, 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.

In a preferred embodiment, 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.

In a preferred embodiment, the three-dimensional structures produced are biocompatible, biodegradable and / or biofunctional. In a particularly preferred embodiment, 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.

In a particularly preferred embodiment, the three-dimensional structure with or without support structure on a biocompatible polymeric material and / or biofunctional toner particles.

Further advantageous embodiments of the invention will become apparent from the dependent claims.

• Aspekt 1: Polymerpartikel, umfassend eine Polymermatrix mit einer Beschichtung eines anorganischen Halbmetall- oder Metalloxids, wobei die Polymermatrix mindestens eine erste funktionelle Gruppe A und mindestens eine zweite funktionelle Gruppe B aufweist, wobei die beiden funktionellen Gruppen A und B fähig sind, mindestens eine kovalente Bindung miteinander einzugehen, wobei die funktionelle Gruppe A ausgewählt ist aus der Gruppe bestehend aus einer Azidgruppe, C-C-Doppelbindung, C-C-Dreifachbindung, Aldehydgruppe, Ketongruppe, Imingruppe, Thioketongruppe und Thiolgruppe und wobei die funktionelle Gruppe B ausgewählt ist aus der Gruppe bestehend aus einer C-C-Doppelbindung, C-C-Dreifachbindung, C-N-Dreifachbindung, Diengruppe, Thiolgruppe und Amingruppe.
• Aspekt 2: Polymerpartikel nach Aspekt 1, wobei das die Polymermatrix ausbildende Polymer ausgewählt ist aus der Gruppe bestehend aus Polystyrol, Polyvinylacetat, Poly(methacrylsäuremethylester), Poly(acrylsäureglycidylester), Polyester, Polyether, Polysulfon, Polyetherketon, Epoxidharz oder Copolymere davon.
• Aspekt 3: Polymerpartikel nach einem der vorhergehenden Aspekte, wobei das Halbmetall- oder Metalloxid SiO₂, TiO₂ oder Al₂O₃ ist.
• Aspekt 4: Polymerpartikel nach einem der vorhergehenden Aspekte, wobei die funktionellen Gruppen A und B fähig sind, miteinander mittels einer Ringschlussreaktion oder ringfreien Reaktion mindestens eine kovalente Bindung einzugehen.
• Aspekt 5: Polymerpartikel nach einem der vorhergehenden Aspekte, wobei die funktionellen Gruppen A und B fähig sind, miteinander eine Ringschlussreaktion durchzuführen und wobei gilt:
  1. i) wenn die funktionelle Gruppe A eine Azidgruppe ist, ist die funktionelle Gruppe B eine C-C-Doppelbindung, C-C-Dreifachbindung oder C-N-Dreifachbindung,
  2. ii) wenn die funktionelle Gruppe A eine C-C-Doppelbindung oder C-C-Dreifachbindung ist, ist die funktionelle Gruppe B eine C-C-Doppelbindung oder C-C-Dreifachbindung,
  3. iii) wenn die funktionelle Gruppe A eine C-C-Doppelbindung oder C-C-Dreifachbindung ist, ist die funktionelle Gruppe B eine Diengruppe oder
  4. iv) wenn die funktionelle Gruppe A ausgewählt ist aus der Gruppe bestehend aus einer Aldehydgruppe, Ketongruppe, Imingruppe und Thioketongruppe, ist die funktionelle Gruppe B eine Diengruppe.
• Aspekt 6: Polymerpartikel nach einem der vorhergehenden Aspekte 1 bis 4, wobei die funktionellen Gruppen A und B fähig sind, miteinander eine ringfreie Reaktion durchzuführen und wobei gilt:
  • v) wenn die funktionelle Gruppe A eine Thiolgruppe ist, ist die funktionelle Gruppe B eine C-C-Doppelbindung oder C-C-Dreifachbindung oder
  • vi) wenn die funktionelle Gruppe A eine C-C-Doppelbindung oder C-C-Dreifachbindung ist, ist die funktionelle Gruppe B eine Thiol- oder Amingruppe.
• Aspekt 7: Polymerpartikel nach einem der vorhergehenden Aspekte, wobei der Polymerpartikel eine Größe von 0,5 bis 50 µm aufweist.
• Aspekt 8: Polymerpartikel nach einem der vorhergehenden Aspekte, wobei der Polymerpartikel ein weiteres Additiv aufweist, ausgewählt aus der Gruppe bestehend aus einem Farbstoff und einem Ladungssteuerungszusatz.
• Aspekt 9: Verfahren zur Herstellung der Polymerpartikel nach einem der Aspekte 1 bis 8, wobei die mindestens eine funktionelle Gruppe A und mindestens eine funktionelle Gruppe B aufweisende Polymerpartikel mit einer Beschichtung eines anorganischen Metall- oder Halbmetalloxids versehen werden.
• Aspekt 10: Verfahren zum Herstellen einer dreidimensionalen Struktur auf einer Stützstruktur, wobei Polymerpartikel gemäß der Aspekte 1 bis 8 mittels eines elektrofotografischen Verfahrens auf die Stützstruktur aufgebracht werden und eine dreidimensionale Struktur mit Stützstruktur erhalten wird.
• Aspekt 11: Verfahren nach Aspekt 10, wobei die Polymerpartikel aufgebracht werden, in dem sie in einem ersten Verfahrensschritt a) in Form einer ersten Schicht auf die Stützstruktur aufgebracht und in einem zweiten Verfahrensschritt b) eine Fixierung durchgeführt wird. Aspekt 12: Verfahren nach einem der Aspekte 10 oder 11, wobei die Verfahrensschritte a) und b) mindestens zweimal hintereinander durchgeführt werden.
• Aspekt 13: Verfahren nach einem der Aspekte 10 bis 12, wobei die Fixierung eine Metallkatalysator-vermittelte, eine Mikrowellen-initiierte, eine thermisch initiierte, eine fotoinitiierte oder katalysatorfreie Fixierung ist.
• Aspekt 14: Verfahren nach einem der vorhergehenden Aspekte 10 bis 13, wobei mindestens zwei unterschiedliche Polymerpartikeltypen gemäß der Ansprüche 1 bis 8 auf die Stützstruktur aufgebracht werden.
• Aspekt 15: Dreidimensionale Struktur mit oder ohne Stützstruktur, hergestellt gemäß einem der Verfahren der Aspekte 10 bis 14.
• Aspekt 16: Dreidimensionale Struktur mit oder ohne Stützstruktur nach Aspekt 15, wobei die dreidimensionale Struktur ein biokompatibles Polymermaterial und biofunktionale Tonerpartikel aufweist.
• Aspekt 17: Dreidimensionale Struktur mit oder ohne Stützstruktur nach den Aspekten 15 oder 16, wobei die Struktur mit oder ohne Stützstruktur ein Testsystem, Implantat, eine Trägerstruktur oder eine Versorgungsstruktur für Tissue-Engineering-Verfahren und - Produkte, eine biokompatible Matrix für Gewebekultur oder ein Transportsystem für Flüssigkeiten oder Gase ist.

The present invention also relates to the following aspects:

• Aspect 1: A polymer particle comprising a polymeric 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 one covalent one Bonding to 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 of a CC double bond, CC triple bond, CN triple bond, diene group, thiol group and amine group.
• Aspect 2: Polymer particles according to aspect 1, wherein the polymer matrix-forming polymer is selected from the group consisting of polystyrene, polyvinyl acetate, poly (methacrylic acid methyl ester), poly (glycidyl acrylate), polyester, polyether, polysulfone, polyether ketone, epoxy resin or copolymers thereof.
• Aspect 3: Polymer Particles according to one of the preceding aspects, wherein the semimetal or metal oxide is SiO ₂ , TiO ₂ or Al ₂ O ₃ .
• Aspect 4: Polymer particles according to any one of the preceding aspects, wherein the functional groups A and B are capable of bonding together to undergo at least one covalent bond by means of a ring-closing reaction or ring-free reaction.
• Aspect 5: Polymer particles according to one of the preceding aspects, wherein the functional groups A and B are capable of carrying out a ring-closing reaction with one another and in which:
  1. i) when the functional group A is an azide group, the functional group B is a CC double bond, CC triple bond or CN triple bond,
  2. ii) when the functional group A is a CC double bond or CC triple bond, the functional group B is a CC double bond or CC triple bond,
  3. iii) when the functional group A is a CC double bond or CC triple bond, the functional group B is a diene group or
  4. iv) when the functional group A is selected from the group consisting of an aldehyde group, ketone group, imine group and thioketone group, the functional group B is a diene group.
• Aspect 6: Polymer Particles according to one of the preceding aspects 1 to 4, wherein the functional groups A and B are capable of carrying out a ring-free reaction with one another and wherein:
  • v) when the functional group A is a thiol group, the functional group B is a CC double bond or CC triple bond or
  • vi) when the functional group A is a CC double bond or CC triple bond, the functional group B is a thiol or amine group.
• Aspect 7: Polymer particles according to one of the preceding aspects, wherein the polymer particle has a size of 0.5 to 50 μm.
• Aspect 8: Polymer particles according to any one of the preceding aspects, wherein the polymer particle comprises a further additive selected from the group consisting of a dye and a charge control additive.
• Aspect 9: A process for the preparation of the polymer particles according to any of aspects 1 to 8, wherein the at least one functional group A and at least one functional group B-containing polymer particles are provided with a coating of an inorganic metal or semimetal oxide.
• Aspect 10: A method for producing a three-dimensional structure on a support structure, wherein polymer particles according to aspects 1 to 8 are applied to the support structure by means of an electrophotographic process and a three-dimensional structure with support structure is obtained.
• Aspect 11: Process according to aspect 10, wherein the polymer particles are applied, in which they are applied in a first process step a) in the form of a first layer on the support structure and in a second process step b) a fixation is performed. Aspect 12: Method according to one of the aspects 10 or 11, wherein the method steps a) and b) are carried out at least twice in succession.
• Aspect 13: The method of any one of aspects 10 to 12, wherein the fixation is a metal catalyst mediated, microwave initiated, thermally initiated, photoinitiated or catalyst free fixation.
• Aspect 14: Method according to one of the preceding aspects 10 to 13, wherein at least two different polymer particle types according to claims 1 to 8 are applied to the support structure.
• Aspect 15: Three-dimensional structure with or without support structure made according to any of the methods of Aspects 10 to 14.
• Aspect 16: A three-dimensional structure with or without a support structure according to aspect 15, wherein the three-dimensional structure comprises a biocompatible polymeric material and biofunctional toner particles.
• Aspect 17: Three-dimensional structure with or without support structure according to aspects 15 or 16, wherein the structure with or without support structure, a test system, implant, a support structure or supply structure for tissue engineering procedures and - products, a biocompatible matrix for tissue culture or a Transport system for liquids or gases.

The invention will be explained in more detail with reference to the following examples and the associated figures.

• Figur 1 zeigt eine schematische Darstellung der chemischen Fixierung gemäß vorliegender Erfindung durch Reaktion der funktionellen Gruppe A eines ersten Partikels mit der funktionellen Gruppe B eines anderen Partikels und der funktionellen Gruppe B des ersten Partikels mit der funktionellen Gruppe A der Stützstruktur.
• Figur 2 zeigt die Größenverteilung der erfindungsgemäß aufgebrachten Polymerpartikel.
• Figur 3 zeigt eine mikroskopische Aufnahme der aufgebrachten Polymerpartikel nach Bestrahlung.
• Figur 4 zeigt eine mikroskopische Aufnahme der funktionalisierten Polymerpartikel.

The figures show:

• FIG. 1 shows a schematic representation of the chemical fixation according to the present invention by reaction of the functional group A of a first particle with the functional group B of another particle and the functional group B of the first particle with the functional group A of the support structure.
• FIG. 2 shows the size distribution of the invention applied polymer particles.
• FIG. 3 shows a micrograph of the applied polymer particles after irradiation.
• FIG. 4 shows a micrograph of the functionalized polymer particles.

Abbreviations: Poly (MMA-co-VAc) Copolymer of poly (methacrylic acid methyl ester) and poly (vinyl acetate) EDCHCI N- (3-dimethylaminopropyl) -N-ethylcarbodiimide hydrochloride q / m Charge / mass Poly (MMA-co-GMA) Copolymer of poly (methacrylic acid methyl ester) and poly (acrylic acid glycidyl ester)

example 1

2.0 g of poly (MMA-co-VAc) particles were dispersed in 50 mL H ₂ O and then 5 mL glacial acetic acid added. The suspension was stirred for one hour to hydrolyze the surface of the polymer particles. The particles were then filtered off and washed in triplicate with 20 ml of phosphate buffer (pH 7) and with 20 ml of H ₂ O. Thereafter, the particles were dried under reduced pressure for 4 hours. The surface-activated particles were dispersed in 90 ml of n-hexane and treated dropwise with a solution of 3.39 ml (3.13 g) of dimethylallylsilyl chloride in 10 ml of n-hexane.

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 μC / g to -30 μC / 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.

Example 2

a) 3.0 g of poly (MMA-co-GMA) particles were dispersed in 75 ml of toluene and the suspension was cooled to 0 ° C. Subsequently, a solution of 1.68 g of propargylamine in 5 mL of toluene was added dropwise over 20 minutes. After the suspension had been stirred for 1 h, a solution of 8.87 g (11-azidoundecyl) chlorodimethylsilane in 25 mL n-hexane was added and the reaction mixture was warmed to RT. After 4 h, the particles were filtered off and washed in each case five times with 50 ml of n-hexane. Thereafter, 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 μC / g to -30 μC / 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. Following the printing process, 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.

b) 3.0 g of poly (MMA-co-GMA) particles were dispersed in 75 mL of toluene and the suspension was cooled to 0 ° C. Subsequently, a solution of 1.68 g of propargylamine in 5 mL of toluene was added dropwise over 20 minutes. After the suspension Was stirred for 1 h, a solution of 8.87 g of (11-azidoundecyl) chlorodimethylsilane in 25 mL of n-hexane was added and the reaction mixture was warmed to RT. After 4 h, the particles were filtered off and washed in each case five times with 50 ml of n-hexane. Thereafter, 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 μC / g to -30 μC / 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.

Claims (6)

A polymer particle 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 forming at least one covalent bond with one another 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 and thioketone group and wherein the functional group B is selected from the group consisting of a CC double bond, CC Triple bond, CN triple bond and diene group, wherein the functional groups A and B are capable of performing a ring closure reaction with each other and where: i) when the functional group A is an azide group, the functional group B is a CC double bond, CC triple bond or CN triple bond, ii) when the functional group A is a CC double bond or CC triple bond, the functional group B is a CC triple bond, iii) when the functional group A is a CC double bond or CC triple bond, the functional group B is a diene group or iv) when the functional group A is selected from the group consisting of an aldehyde group, ketone group, imine group and thioketone group, the functional group B is a diene group. The polymer particle of claim 1, wherein the polymer matrix forming polymer is selected from the group consisting of polystyrene, polyvinyl acetate, poly (methacrylic acid methyl ester), polyester, polyether, polysulfone, polyether ketone, epoxy resin or copolymers thereof. Polymer particles according to one of the preceding claims, wherein the semimetal or metal oxide is SiO ₂ , TiO ₂ or Al ₂ O ₃ . Polymer particles according to one of the preceding claims, wherein the polymer particle has a size of 0.5 to 50 microns. The polymer particle of any preceding claim, wherein the polymer particle comprises a further additive selected from the group consisting of a dye and a charge control additive. A process for the preparation of the polymer particles according to any one of claims 1 to 5, wherein the at least one functional group A and at least one functional group B having polymer particles are provided with a coating of an inorganic metal or semimetal oxide.

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