EP3687763A1 - Pièces façonnées imprimées en 3d à partir de plus d'un matériau silicone - Google Patents

Pièces façonnées imprimées en 3d à partir de plus d'un matériau silicone

Info

Publication number
EP3687763A1
EP3687763A1 EP17777575.6A EP17777575A EP3687763A1 EP 3687763 A1 EP3687763 A1 EP 3687763A1 EP 17777575 A EP17777575 A EP 17777575A EP 3687763 A1 EP3687763 A1 EP 3687763A1
Authority
EP
European Patent Office
Prior art keywords
printing
materials
segments
crosslinking
forming
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17777575.6A
Other languages
German (de)
English (en)
Inventor
Bernd Pachaly
Christian Georg BAUMANN
Vera SEITZ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP3687763A1 publication Critical patent/EP3687763A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/205—Means for applying layers
    • B29C64/209—Heads; Nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/227—Driving means
    • B29C64/236—Driving means for motion in a direction within the plane of a layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/245—Platforms or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/264—Arrangements for irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/264—Arrangements for irradiation
    • B29C64/291—Arrangements for irradiation for operating globally, e.g. together with selectively applied activators or inhibitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/321—Feeding
    • B29C64/336—Feeding of two or more materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/386—Data acquisition or data processing for additive manufacturing
    • B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
    • B29K2083/005—LSR, i.e. liquid silicone rubbers, or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing

Definitions

  • the invention relates to a method for the additive production of an object using a 3D printing device.
  • the process is characterized in that the printing compositions (A) used are a structure-forming printing material consisting of a first crosslinkable silicone rubber composition and (B) one or more further structure-forming printing materials.
  • the drop-wise application of the printing compounds enables the production of complex models made of different materials with a tailor-made property profile.
  • the invention also relates to objects produced by the aforementioned method.
  • 3D printing three-dimensional objects are built up layer by layer.
  • the structure is computer-controlled from one or more liquid or solid materials according to predetermined geometries from the CAD (Computer Aided Design).
  • CAD Computer Aided Design
  • 3D printing Solidification processes take place.
  • Typical materials for 3D printing are plastics, synthetic resins, ceramics and metals.
  • 3D printers are used in industry, research and also in the consumer sector. 3D printing is a generative manufacturing process and is also referred to as additive manufacturing.
  • An example are objects with internal grid structures.
  • thermoplastic elastomers or thermal loads.
  • US 9,031,680 B2 describes the production of objects from several materials by 3D printing.
  • the printing process is described as multijet printing.
  • materials acrylate used functional organic polymers which are polymerized by UV light. These have a low viscosity and are therefore also referred to as printing inks.
  • Viscosity and low surface tension can not be adapted to the given process window.
  • Silicones are the only real elastomers known for 3D printing.
  • US 2016/0263827 A1 describes a process in which a crosslinking catalyst is added to a bath of liquid silicone via a dispensing needle movable in three-dimensional space and leads to local crosslinking. The cross-linked component is then mechanically removed from the bath and processed. This procedure is on soft
  • Silicone with Shore A smaller than 50 is limited and does not allow the construction of several materials.
  • WO 2017/040874 A1 describes a method in which silicone is extruded from a die that can be moved in three-dimensional space.
  • the silicone can be thermally crosslinked.
  • extrusion which the skilled person also as
  • Disposing refers to a silicone material is pressed through a nozzle needle, forming a strand and is on the Construction platform or already printed surface filed.
  • the force for dosing the silicone material can by
  • Typical nozzle diameters are 0.05 to 1 mm.
  • Typical layer heights are 0.05 to 1 mm.
  • the principle of operation of the valve is that the material flows through a pressure in the valve where it is ejected through a nozzle by a spring, magnetic mechanism or a piezoactuator similar to a piston pump
  • Typical droplet sizes with silicone - Material is 0.05 to 0.5 mm
  • the dispensing is interrupted when the dispenser is moved in a printing phase in which no material is to be printed
  • the droplet frequency is typically 100 to 1000 Hz, up to 10,000 Hz with special valves, but until now this procedure was only for the pressure of a silicone material and
  • the object of the present invention was to provide a method which enables the printing of elastomeric objects made of different materials in one printing operation and by which objects with tailored properties can thus be obtained.
  • crosslinkable silicone rubber compositions homogeneous
  • Figure 1 Printing device for printing on a material
  • Figure 2 Printing device for printing three different materials
  • Figure 3 Printed object with several segments consisting of one material each
  • Figure 4 Printed object with several layers each consisting of a mixture of materials
  • Figure 5 printed test object consisting of silicones of different colors
  • Figure 6 printed test object consisting of silicones of different hardness
  • the invention relates to a method for the additive production of an object using a 3D printing device, the method comprising the following steps:
  • Pressure-mass layer wherein the pressure masses comprise the following materials:
  • A a pattern-forming printing material consisting of a first crosslinkable silicone rubber composition and (B) one or more additional structuring
  • the 3D printing device preferably contains at least one Au wearing device, a source of electromagnetic radiation and a support plate.
  • the discharge device is arranged so that pressure masses in the form of individual isolated drops (voxels) can be delivered.
  • the discharge device for each printing compound may comprise a nozzle which emits drops of liquid from printing compound in the direction of the carrier plate. Such nozzles are also referred to as jetting nozzles.
  • the discharge device preferably comprises jet valves with piezo elements. These allow the discharge of both low-viscosity materials, drop volume for drops of a few picoliters (pL) (2 pL correspond to a droplet diameter of about 0.035 ⁇ ) can be realized, as well as medium and high viscosity materials such as silicone rubber compositions in particular, with piezo printheads with a nozzle diameter between 50 and 500 ⁇ are preferred and drop volume in the nanoliter range (1 to 100 nL) can be generated.
  • pL picoliters
  • medium and high viscosity materials such as silicone rubber compositions in particular
  • these printheads can deliver droplets with a very high dosing frequency (about 1 to 30 kHz), while with relatively high-viscosity masses (above 100 Pa-s), depending on the Theological properties (shear thinning behavior) dosing frequencies up to about 500 Hz can be achieved.
  • Suitable jetting nozzles are known in the art and are described for example in DE 102011108799 AI.
  • the printing compositions are preferably applied by means of drop-on-demand (DOD) processes.
  • DOD drop-on-demand
  • each printed drop is previously created specifically and stored at a location defined for this drop.
  • Figure 1 shows the basic structure of a
  • Printing device for printing a printing material. Via the feed 1 pressure mass is conveyed into the valve 3, which doses by appropriate operation of the printing material in the form of individual droplets from the nozzle 4. The droplets land on the support plate 7 or on before
  • the functions of the valve controls a computer 2.
  • the valve can in the
  • Printing device can be placed by appropriate movement units at each point of the three-dimensional space.
  • Material is still chemically uncrosslinked after the dosage of the individual drops and is crosslinked after the formation of a layer or according to another crosslinking strategy.
  • This can be done with heat-crosslinkable materials by supplying heat, for example by irradiation with infrared light.
  • heat-crosslinkable materials this can be done by
  • the crosslinking can also take place after printing parts of a layer or after printing several layers.
  • Figure 2 shows the basic structure of a
  • the Printing device for printing a plurality of printing materials.
  • the Printing device consists of several valves for one material. In principle, one could also dose several materials through a valve. However, this is impractical due to the need for long flushing times and high material losses.
  • the different materials are dosed by the respective valves, each valve has its own
  • Figure 3 shows three materials 8, 9 and 10 and the associated valves 11, 12 and 13.
  • any number of materials and valves can be used.
  • valves can be arranged.
  • the control of the printing device can be done via a computer 2.
  • the materials will be on the
  • the printing compositions of the present invention comprise at least one pattern-forming printing material consisting of a first crosslinkable silicone rubber composition.
  • a structure-forming printing material is understood to mean a printing material which is used to construct the structure of the object itself.
  • various support materials can be used, which are removed after the construction of the object again.
  • the printing compositions of the present invention comprise, in addition to the first crosslinkable silicone rubber composition, one or more additional pattern-forming printing materials.
  • the printing compositions comprise the following materials: (A) a pattern-forming printing material consisting of a first crosslinkable silicone rubber composition and
  • Silicone rubber composition differs, and
  • Suitable silicone rubber compositions are known in the art. Particularly suitable are in
  • WO 2017/081028 A1 WO 2017/089496 Al and WO 2017/121733 Al described silicone rubber compositions.
  • the crosslinkable silicone rubber composition and / or optionally additional silicone rubber compositions in the uncrosslinked state preferably have a viscosity of 10 Pa.s or more, preferably 40 Pa.s or more, especially
  • the viscosity of the silicone rubber composition can be measured with a rheometer according to DIN EN ISO 3219: 1994 and DIN 53019, whereby a cone and plate system (cone CP50-2) with an opening angle of 2 ° can be used.
  • a suitable rheometer is for example the "MCR 302" of the Fa.
  • the calibration of the device can be done with a standard material, such as 10000 standard oil
  • the silicone rubber compositions can be formulated in one or more components, preferably one-component.
  • Addition-crosslinking silicone rubber compositions are typically prepared by reaction of unsaturated groups, e.g. Alkenyl groups with Si-H groups (Hydro ilyltechnik), crosslinked in the silicone rubber composition.
  • unsaturated groups e.g. Alkenyl groups with Si-H groups (Hydro ilyltechnik)
  • the crosslinking can be either thermally and / or by UV or UV-VIS light
  • the crosslinking is preferably brought about by UV / VIS-induced activation of a photosensitive hydrosilylation catalyst, with platinum complexes being preferred as catalysts.
  • a photosensitive hydrosilylation catalyst with platinum complexes being preferred as catalysts.
  • Numerous photosensitive platinum catalysts are known from the prior art, which are largely inactive with the exclusion of light and can be converted by irradiation with UV / VIS light in active at room temperature platinum catalysts.
  • the printing compositions according to the present invention additionally comprise one or more additional structure-forming printing materials.
  • additional structure-forming printing materials are the following:
  • silicone gels silicone resins, homopolymers or copolymers of monomers selected from the group consisting of acrylates, olefins, epoxides, isocyanates or nitriles, and polymer blends comprising one or more of the aforementioned polymers.
  • acrylates olefins
  • epoxides epoxides
  • isocyanates nitriles
  • polymer blends comprising one or more of the aforementioned polymers.
  • the printing compositions are preferably materials which, at least during processing, are in a flowable form and can be cured or crosslinked after discharge.
  • All printing compounds can be formulated in one or more components, preferably one-component.
  • the structure-forming materials preferably the first and second silicone rubber compositions, optionally other silicone rubber compositions, may be crosslinked, for example, in terms of Shore hardness, electrical conductivity, thermal conductivity, color, transparency, hydrophilicity and / or
  • the structure-forming pressure masses include those above
  • the structure-forming printing compositions consist exclusively of one or more
  • the printing compositions additionally comprise one or more support materials, which after
  • the setting of support material may be required if the object has cavities, undercuts, overhanging, cantilevered or thin-walled parts, since the pressure masses can not be freely suspended in space.
  • the support material fills up during the printing process volume volumes and serves as a base or as a scaffold to put on the pressure masses and harden.
  • the support material is removed after completion of the printing process and releases the cavities, undercuts and overhanging, unsupported or thin-walled areas of the printed object.
  • support material can also be provided at locations where it is not technically necessary. For example, components can be packed in support material in order to increase the quality of the printing result or to influence the surface quality of the printed product.
  • the support material eg. B. non-crosslinking and non-cohesive material.
  • the necessary shape of the support material is calculated.
  • various strategies can be used, for example, to use as little support material as possible or to increase the dimensional stability of the product.
  • the print head can have one or more further discharge devices for the support material or one or more further nozzles. Alternatively or additionally, a further print head with corresponding discharge devices can be provided for the discharge of support material.
  • Suitable support materials are known in the art. Particularly suitable are support materials, as described in WO 2017/020971 AI.
  • the drops of the individual printing compounds are preferably applied so that one or more segments within the Object arise, each consisting of only one structure-forming printing material or support material.
  • Figure 3 shows an example printed object printed from three different materials 14, 15 and 16, where the object consists of three segments, each made of a material whose totality is the volume of the object.
  • the object consists of three segments, each made of a material whose totality is the volume of the object.
  • Printing materials exist and the mixing ratio of the structure-forming printing materials in each segment is constant.
  • Figure 4 shows an exemplarily printed object made up of five different layers 17, 18, 19, 20 and 21. Each layer was made up of two different ones
  • the layers may consist of a layer of individual droplets and 0.05 to 1.0 mm thick or consist of several layers.
  • layer 17 contains 5% material 1 and 95% material 2
  • layer 18 contains 10%
  • Printing materials wherein the mixing ratio of the structure-forming printing materials in each segment one
  • the drops of the individual structure-forming pressure masses can be placed anywhere in the three-dimensional space, whereby they combine homogeneously with each other after placement. Due to the homogeneous connection of the drops
  • crosslinking or crosslinking of the applied printing composition takes place. This is preferably done by electromagnetic radiation.
  • the action of the electromagnetic radiation on the pressure masses is preferably carried out location-selective or areal, pulsed or
  • Intensity It may be expedient to permanently irradiate the entire work area during printing, in order to achieve complete crosslinking, or to expose it to radiation only for a short time, in order to prevent incomplete crosslinking (crosslinking / crosslinking). Green strength), which may be accompanied by better adhesion of the individual layers.
  • the crosslinking or crosslinking of the printing compositions is preferably carried out thermally and / or by UV or UV / VIS radiation, very particularly preferably by UV or UV / VIS radiation.
  • UV radiation has a wavelength in the range of 100 nm to 380 nm, while visible light (VIS radiation) has a wavelength in the range of 380 to 780 nm.
  • UV / VIS-induced crosslinking has advantages.
  • the intensity, exposure time and place of action of the UV / VIS radiation can be precisely dimensioned, while the heating of the discharged structure-forming printing materials (as well as their subsequent cooling) is always delayed due to the relatively low thermal conductivity.
  • the thermal gradients Due to the intrinsically very high thermal expansion coefficients of the silicone rubber compositions, the thermal gradients inevitably present temperature gradients lead to mechanical stresses that can adversely affect the dimensional stability of the object formed, which can lead to unacceptable shape distortions in extreme cases.
  • the speed of the UV / VIS-induced crosslinking depends on numerous factors, in particular the type and concentration of the photosensitive catalyst, the intensity, wavelength and exposure time of the UV / VIS radiation, the transparency, reflectivity, layer thickness and composition of the printing mass and the temperature.
  • a UV / VIS radiation source with a power of between 10 mW / cm 2 and 20,000 mW / cm 2 , preferably between 30 mW / cm 2 and 15,000 mW / cm 2 , and a radiation dose between 150 mJ / cm 2 and 20,000 mJ / cm 2 , preferably between 500 mJ / cm 2 and 10,000 mJ / cm 2 .
  • area-specific irradiation times between a maximum of 2,000 s / cm 2 and a minimum of 8 ms / cm 2 can be achieved.
  • the 3D printing device preferably has a UV / VIS exposure unit.
  • the UV / VIS source is arranged to be movable relative to the support plate and illuminates only selected areas of the object.
  • the UV / VIS source is designed in a variant such that the entire object or an entire material layer of the object is exposed at once.
  • the UV / VIS source is designed such that its light intensity or its energy can be variably adjusted and that the UV / VIS source at the same time exposes only a portion of the object, the UV / VIS source being such can be moved relative to the object that the entire object with the UV / VIS light, possibly in different intensity, can be exposed.
  • the UV / VIS source is designed for this purpose as a UV / VIS LED strip and is moved relative to the object or over the printed object.
  • crosslinking can be effected by IR radiation, for example by means of an (N) IR laser or an infrared lamp.
  • a cure strategy is used to accomplish the cure. Curing of the printing compositions preferably takes place after setting a layer, after setting several layers or directly during printing.
  • Curing the print masses directly during printing is referred to as a direct cure strategy.
  • a direct cure strategy Become, for example, by UV / VIS radiation curable structure-forming
  • the UV / VIS source is active for a very long time, so that it is possible to work with much lower intensity, resulting in slow cross-linking of the object. This limits the heating of the object and leads to dimensionally stable objects, since no expansion of the object due to temperature peaks occurs.
  • the pro-layer curing strategy after the setting of each complete material layer, the radiation-induced crosslinking of the set material layer takes place. During this process, the freshly printed layer combines with the cured underlying printed layer. The curing does not take place immediately after the setting of a pressure mass, so that the pressure masses have time before curing to relax. By this is meant that the pressure masses can flow into one another, resulting in a smoother surface than the direct cure strategy.
  • n-layer curing strategy is similar to the Pro-Layer curing strategy, but curing is done after n layers of material have been set, where n is a natural number. The time available for relaxing the pressure masses is further increased, which further improves the surface quality.
  • the printed object can be post-cured or post-processed after curing.
  • the after-treatment is preferably selected from one or more of the following methods:
  • Heat treatment, surface coating, setting of cuts, parts and separation of segments and assembly of individual components For example, a heat treatment of the component for 4 hours at 200 ° C take place. This corresponds to a tempering treatment typical for silicone elastomers.
  • a particularly suitable tempering treatment is in WO 2010/015547 AI
  • the models can be coated locally or globally after 3D printing, for example, the
  • Optimize surface properties of the model For example, properties that can be optimized by a coating include surface roughness,
  • Post processing is, for example, the setting of cuts, parts or separation of individual segments, or
  • the present invention further relates to an object manufactured by the above-described 3D printing method.
  • the object can also be produced by the combination of such a 3D printing method with at least one other additive or conventional production technology.
  • the printed article according to the invention comprises a
  • Embodiment consists of the invention printed object of a silicone elastomer, one or more others
  • the object printed according to the invention comprises two or more silicone elastomers which are homogeneous with one another
  • the present invention printed ect consists of two or more silicone elastomers, optionally other materials and optionally a foreign component, wherein the silicone elastomers, the other materials and the foreign component is homogeneous
  • the object is preferably 50% by weight or more
  • Silicone elastomers each based on the total weight of
  • the object consists exclusively of one or more
  • the object is manufactured on the basis of a digital 3D model.
  • the creation of the digital model can be done by design using a computer aided design (CAD) software. Also geometries from imaging techniques of
  • Magnetic resonance imaging can serve as a starting point.
  • objects are taken over into the CAD software and further processed there. Scanning also allows digital objects to be created and imported into the CAD software.
  • the file format can be selected in such a way that it becomes a new one through further data processing
  • a standard tessellation language (STL) format is generated from the digital object.
  • Many CAD systems include this interface or separate software is used.
  • a description of the interface between construction and STL file format can be found in Chua Chee Kai, Gan GK Jacob and Tong Mei, Interface between CAD and Rapid Prototyping Systems, The International Journal of Advanced Manufacturing Technology, August 1997, Volume 13, Issue 8, pp 571-576.
  • Texture of the object to be manufactured can take.
  • STL file format is chosen representative of other file formats. This is not intended to be limiting; the method according to the invention can also be executed with other file formats.
  • the object can be segmented into segments
  • each segment has its own STL file, and the mathematical superimposition of the individual segments results in the object in its entire volume.
  • the software of the printing device cuts the object into slices, giving each layer the information on which position to place which material, alternatively the object is present in its entire volume as an STL file, and the
  • the digital 3D model is preferably divided into segments for each printing mass and created by superimposing the individual segments.
  • the digital 3D model preferably represents the entire object, and the pressure of the individual pressure masses via algorithms of software.
  • the software of the printing device typically provides an instruction to control the printing device, after which the printing device prints one layer at a time, placing different materials at the designated positions.
  • the digital 3D model can be reworked digitally before printing the object.
  • Object can be volume, network and / or point-based.
  • For post-processing of digital models can be
  • the network of surface models for further processing is examined for errors, cleaned up and, if necessary, smoothed.
  • WO 2016/071241 AI described.
  • the Printer has been equipped with three different valves. There were three different silicone compositions, which were prepared according to WO 2017/089496 AI, and a support material, which was prepared according to WO 2017/020971 AI used. The printer was set to a layer height of 0.4 mm and printed at a frequency of 200 Hz.
  • Example 1 The test object was a ACEO ® logo consisting of a colorless base plate 50x15x2 mm, onto which a 3.2 mm high lettering "ACEO" was printed with 10 mm large letters.
  • valve 1 From valve 1, first 5 layers of a transparent silicone 1 were printed. After each layer, the silicone 1 was crosslinked with UV light. Subsequently, the printer control switched to valve 2 and printed the lettering "ACEO" in 8 layers of a dark green silicone 2. Here, too, UV light was crosslinked after each layer
  • Test object from example 1 The object thus consisted of two different silicones printed one after the other in a printing process, which were homogeneously interconnected.
  • the test object was an object with integrated function.
  • the external dimensions were 35 x 15 x 25 mm.
  • the object consisted of a housing segment, an inner segment with a grid structure and a non-return flap towards the upper opening.
  • the inner grid structure formed a spring against the check valve.
  • the object acted as a check valve.
  • the outer Shore A hardness silicone housing of 60 was printed from valve 1, valve 2 printed one
  • Test object from Example 2 from two perspectives.
  • the object consisted of simultaneously printed in a printing segments of different silicones, which are homogeneous with each other

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)

Abstract

L'invention concerne un procédé de fabrication additive d'un objet au moyen d'un dispositif d'impression 3D. Ce procédé est caractérisé en ce qu'on utilise comme masses d'impression (A) un matériau d'impression structurant constitué d'une première composition de caoutchouc silicone réticulable et (B) un ou plusieurs matériaux d'impression structurants supplémentaires. L'application goutte à goutte des masses d'impression permet de fabriquer des modèles complexes à partir de différents matériaux avec un profil de propriétés sur mesure. L'invention concerne également des objets fabriqués par ledit procédé.
EP17777575.6A 2017-09-29 2017-09-29 Pièces façonnées imprimées en 3d à partir de plus d'un matériau silicone Withdrawn EP3687763A1 (fr)

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PCT/EP2017/074821 WO2019063094A1 (fr) 2017-09-29 2017-09-29 Pièces façonnées imprimées en 3d à partir de plus d'un matériau silicone

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EP (1) EP3687763A1 (fr)
JP (1) JP2020533202A (fr)
KR (1) KR20200042930A (fr)
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WO (1) WO2019063094A1 (fr)

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DE102019110718A1 (de) * 2019-04-25 2020-10-29 Freudenberg Se Additives Fertigungsverfahren zur Herstellung eines Formkörpers aus Elastomer
TW202134045A (zh) * 2019-10-25 2021-09-16 德商漢高智慧財產控股公司 可三維圖案化之熱介面
CN111070670B (zh) * 2019-12-24 2021-07-13 湖南文理学院 一种三维打印机及打印方法
US20230330927A1 (en) 2020-09-22 2023-10-19 Wacker Chemie Ag Method and 3d printing method for layer-by-layer fabrication of objects using layer transfer printing
JP6949187B1 (ja) * 2020-10-20 2021-10-13 ホッティーポリマー株式会社 ３ｄプリンタによるシリコーンゴム造形物の製造方法
CN112659545B (zh) * 2020-12-18 2022-08-23 河南理工大学 一种熔丝沉积成形—射流电铸组合增材制造方法
US11599084B2 (en) 2021-06-18 2023-03-07 Kyndryl, Inc. Early notification system of degradation of 3D printed parts
CN114161702B (zh) * 2021-10-29 2024-01-05 深圳市纵维立方科技有限公司 一种光固化3d打印装置
US20240051219A1 (en) * 2022-08-15 2024-02-15 Inkbit, LLC Systems and methods of offset surface deposition in additive fabrication
EP4344873A1 (fr) 2022-09-27 2024-04-03 Elkem Silicones France SAS Post-traitement d'un article en silicone élastomère imprimé en 3d

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KR20200042930A (ko) 2020-04-24
JP2020533202A (ja) 2020-11-19
WO2019063094A1 (fr) 2019-04-04
CN111163919A (zh) 2020-05-15
WO2019063094A8 (fr) 2019-07-04
US20200238601A1 (en) 2020-07-30

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