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    • 专利摘要:
    coalescing agent for three-dimensional (3d) printing. a coalescing agent for three-dimensional printing (3d) including a co-solvent, a surfactant having a hydrophilic lipophilic balance (hlb) value that is less than 10, a carbon black pigment, a polymeric dispersant and a water balance. the co-solvent is present in an amount ranging from about 15% by weight to about 30% by weight of a % by total weight of the coalescing agent. the surfactant is present in an amount ranging from about 0.5% by weight to about 1.4% by weight of the total weight of the coalescing agent. the carbon black pigment is present in an amount ranging from about 3.0% by weight to about 6.0% by weight of the total weight percentage of the coalescing agent. the polymeric dispersant has a weight average molecular weight ranging from about 12,000 to about 20,000.
    公开号:BR112017005750B1
    申请号:R112017005750-6
    申请日:2014-09-29
    公开日:2021-09-08
    发明作者:Keshava A. Prasad；Ali Emamjomeh；Glenn Thomas Haddick
    申请人:Hewlett-Packard Development Company, L.P；
    IPC主号:
    专利说明:

    FUNDAMENTALS OF THE INVENTION
    [001] Three-dimensional (3D) printing is an additive printing process used to produce three-dimensional solid objects from a digital model. 3D printing is often used in rapid product prototyping, mold generation and master mold generation. 3D printing techniques are considered additive processes because they involve the combined application of successive layers of material. This is different from traditional machining processes, which often rely on material removal to create the final object. Materials used in 3D printing often require curing or fusing, which for some materials can be achieved using extrusion or heat assisted sintering, and for other materials it can be achieved using digital light projection technology. BRIEF DESCRIPTION OF THE FIGURES
    [002] The features and advantages of the examples of the present disclosure will become apparent with reference to the following detailed description and figures, in which like reference numerals correspond to like, though perhaps not identical, components. For the sake of brevity, reference numbers or features which have a function described above may or may not be described in connection with other figures in which they appear.
    [003] Figure 1 is a flow diagram illustrating an example of a 3D printing method disclosed herein; Figures 2A to 2D are sectional views of the steps involved in forming a layer of a 3D object using an example of the 3D printing method disclosed herein; Figure 2E is a sectional view of an example of the 3D object that can be formed after carrying out the steps of Figures 2A to 2D several times; Figure 3 is a perspective view of the object of Figure 2E; and Figure 4 is a simplified isometric view of an example of a 3D printing system that can be used in an example of the 3D printing method as described herein. DETAILED DESCRIPTION OF THE INVENTION
    [004] Examples of the coalescing agent disclosed herein are used in a three-dimensional (3D) printing system. This printing system is based on a manufacturing process that involves the use of electromagnetic radiation to fuse a building material using the coalescing agent(s) applied by inkjet to selectively define the object / part in question (layer by layer ). Under this manufacturing process, an entire layer of a building material (eg a polyamide material or other suitable polymer) is exposed to electromagnetic radiation, but only a selected region of the building material is fused and hardened to become a 3D object layer. The coalescing agent is selectively applied by an inkjet applicator so that the coalescing agent is in contact with the building material in the selected region. The coalescing agent includes a polymerically dispersed carbon black pigment, which improves radiation absorption efficiency in the selected region. The polymerically dispersed carbon black pigment is capable of converting the absorbed radiation into thermal energy, which in turn melts and/or sinters the building material that is in contact with the polymerically dispersed carbon black pigment. This causes the construction material to fuse together to form the 3D object layer.
    [005] In addition, the coalescing agent includes a co-solvent and a surfactant that allows the coalescing agent to spread relatively evenly over the building material, due, at least in part, to the surfactant penetrating the building material layer. The co-solvent has a boiling point of less than 300°C and the surfactant has a hydrophilic lipophilic balance (HLB) of less than 10. The coalescing agent, with these particular components, has a lower dynamic surface tension (ie, the coalescing agent reaches an equilibrium surface tension of 26 dynes/cm (0.026 n/m) within 10 milliseconds after being applied). The lower the dynamic surface tension, the better the dispersion of the coalescing agent and the better the optical density of the resulting object. This results in a 3D object with improved and more uniform cosmetic properties.
    [006] Using the coalescing agent disclosed here, the resulting object has improved mechanical properties (eg tensile strength, Young's modulus, % tensile strength), for example, when compared to 3D objects formed with different coalescing agents including different co-solvents and a designated HLB-free amphoteric surfactant. In some examples, it is believed that improved mechanical properties can be obtained even when using less of the coalescing agent described herein.
    [007] The coalescing agent disclosed herein is water-based and includes a particular co-solvent and surfactant. As mentioned above, the aqueous nature and particular components of the coalescing agent enhance the moisture properties of the coalescing agent, even in the building material, which may be hydrophobic. This allows the polymerically dispersed carbon black pigment within the coalescing agent to be spread more evenly over the surface of the building material.
    [008] In one example, the coalescing agent includes water (e.g., deionized water), the co-solvent having a boiling point of less than 300°C, the surfactant having an HLB of less than 10, and a polymeric carbon black pigment scattered. The amount of water in the coalescing agent can vary depending on the amounts of the other components, but water constitutes a balance of the coalescing agent (ie, so that a total weight % of the coalescing agent is 100).
    [009] As mentioned above, the co-solvent has a boiling point of less than 300°C. In some examples, the co-solvent has a boiling point of less than 250°C. Some examples of the co-solvent include 2-pyrrolidinone, 1,5-pentanediol, triethylene glycol, tetraethylene glycol, 2-methyl-1,3-propanediol, 1,6-hexanodol and tripropylene glycol methyl ether. In the examples described herein, the coalescing agent is to be understood to include one of the co-solvents listed alone, or two or more of the co-solvents listed in combination, and exclude other co-solvents. As such, if the co-solvent is 2-pyrrolidinone, the 2-pyrrolidinone co-solvent alone is included. In another example, if the co-solvent is a combination of 2-pyrrolidinone and 1,5-pentanediol, these isolated solvents are included. The co-solvent may be present in the coalescing agent in an amount ranging from about 15% by weight to about 30% by weight based on the total weight % of the coalescing agent. In one example, the co-solvent may be present in the coalescing agent in an amount of about 25% by weight based on the total weight % of the coalescing agent.
    [0010] Also as mentioned above, the surfactant has an HLB of less than 10. This component contributes, at least in part, to the coalescing agent with low dynamic surface tension (as defined above). Any surfactant with an HLB less than 10 can be used. In one example, the surfactant is a self-emulsifiable surfactant based on acetylenic diol chemistry (eg, SURFYNOL® SE-F from Air Products and Chemical Inc.). In other examples, the surfactant is an ethoxylated low foam wetting agent (eg SURFYNOL® 440 or SURFYNOL® CT-111 from Air Products and Chemical Inc.) or an ethoxylated wetting agent and a molecular defoamer (eg SURFYNOL® 420 from Air Products and Chemical Inc.). Still other suitable surfactants with an HLB of less than 10 include nonionic wetting agents and molecular defoamers (eg SURFYNOL® 104E from Air Products and Chemical Inc.) or water-soluble nonionic surfactants (eg TERGITOL TM TMN-6 from The Dow Chemical Company). A fluorinated surfactant can also be added to the surfactant having the HLB less than 10 to improve the wetting of the building material. As such, in another example, the coalescing agent includes a combination of the surfactant with an HLB of less than 10 (eg, the self-emulsifying surfactant based on acetylenic diol chemistry) and a nonionic fluorinated surfactant (eg, CAPSTONE® FS-35 from DuPont).
    [0011] Whether a single surfactant or a combination of surfactants is used, the total amount of surfactant(s) in the coalescing agent can range from about 0.5% by weight to about 1.4% by weight based on % in total weight of the coalescing agent. In one example, the surfactant having the HLB less than 10 is included in an amount ranging from about 0.5% by weight to about 1.25% by weight, and the fluorinated surfactant is included in an amount ranging from about 0.03% by weight to about 0.10% by weight.
    [0012] An anticoagulation agent may be included in the coalescing agent. Coking refers to the deposit of dry ink (eg, coalescing agent) on a heating element of an inkjet thermal printhead. The anticoagulation agent(s) is (are) included to assist in preventing the buildup of clotting. Examples of suitable anticoagulation agents include ole-3-phosphate (eg commercially available as CRODAFOS™ 03A or CRODAFOS™ N-3 acid from Croda), or a combination of ole-3-phosphate and a polyacrylic acid polymer from low molecular weight (eg <5,000) (eg commercially available as CARBOSPERSETM K-7028 Polyacrylate from Lubrizol). Whether a single anti-clotting agent or a combination of anti-clotting agents is used, the total amount of anti-clotting agent(s) in the coalescing agent can range from more than 0.20% by weight to about 0.62% by weight based on % in total weight of the coalescing agent. In one example, the ole-3-phosphate is included in an amount ranging from about 0.20% by weight to about 0.60% by weight, and the low molecular weight polyacrylic acid polymer is included in an amount ranging from about 0.005% by weight to about 0.015% by weight.
    [0013] In the coalescing agent disclosed herein, the carbon black pigment acts as a radiation absorbing agent or active material. Examples of carbon black pigments include those manufactured by Mitsubishi Chemical Corporation, Japan (such as, for example, carbon black 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, and No. 22008); various RAVEN® series carbon black pigments manufactured by Columbian Chemicals Company, Marietta, Georgia (such as, for example, RAVEN® 5750, RAVEN® 5250, RAVEN® 5000, RAVEN® 3500, RAVEN® 1255 and RAVEN® 700) ; various carbon black pigments from the REGAL® series, the MOGUL® series or the MONARCH® series manufactured by Cabot Corporation, Boston, Massachusetts (such as, for example, REGAL® 400R, REGAL® 330R and REGAL® 660R); and various black pigments manufactured by Evonik Degussa Corporation, Parsippany, New Jersey, (such as, for example, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black 8150, Color Black 8160, Color Black 8170, PRINTEX® 35, PRINTEX® U, PRINTEX® V, PRINTEX® 140U, Special Black 5, Special Black 4A and Special Black 4).
    [0014] The carbon black pigment is polymerically dispersed in the coalescing agent by a polymeric dispersant having a weight average molecular weight ranging from about 12,000 to about 20,000. In some of the examples disclosed herein, the carbon black pigment is initially in the form of a water-based pigment dispersion. The water-based pigment dispersion includes carbon black pigment (which is not surface treated), polymeric dispersant and water (with or without a co-solvent). When included, an example of the co-solvent might be 2-pyrrolidinone. The polymeric dispersant can be any styrene acrylate or any polyurethane having its weight average molecular weight ranging from about 12,000 to about 20,000. Some commercially available examples of the styrene acrylate polymeric dispersant are JONCRYL® 671 and JONCRYL® 683 (both available from BASF Corp.). Within the water-based pigment dispersion, a ratio of carbon black pigment to polymeric dispersant ranges from about 3.0 to about 4.0. In one example, the ratio of carbon black pigment to polymeric dispersant is about 3.6. The polymeric dispersant is believed to contribute to the carbon black pigment by exhibiting improved electromagnetic radiation absorption.
    [0015] The amount of carbon black pigment that is present in the coalescing agent is between about 3.0% by weight and about 6.0% by weight based on the total % by weight of the coalescing agent. In other examples, the amount of carbon black pigment present in the coalescing agent ranges from greater than 4.0% by weight to about 6.0% by weight. These pigment loadings are considered to provide a balance between coalescing agent 26 with jet reliability and electromagnetic radiation absorption efficiency. When the carbon black pigment is present in the water-based pigment dispersion, the amount of the water-based pigment dispersion that is added to the coalescing agent can be selected so that the amount of the carbon black pigment in the agent coalescent is within the given ranges.
    [0016] The coalescing agent may also include a chelator, a biocide/antimicrobial and/or combinations thereof. The chelator can be added in any amount ranging from about 0.03% by weight to about 0.10% by weight based on the total weight % of the coalescing agent. An example of a suitable chelator includes TRILON® (an aminopolycarboxylate, available from BASF Corp.). The biocide or antimicrobial can be added in any amount ranging from about 0.30% by weight to about 0.40% by weight relative to the total weight of the coalescing agent. Examples of suitable biocides/antimicrobials include PROXELTM GXL (an aqueous solution of 1,2-benzisothiazolin-3-one, available from Arch Chemicals, Inc.) and KOROEK™ MLK (a formaldehyde-free microbicide from The Dow Chemical Co.).
    [0017] Examples of the coalescing agent disclosed herein can be used in any suitable printing method and system. An example of 3D printing method 100 is shown in Figure 1 and an example of printing system 10 used in various steps of method 100 is shown in Figures 2A to 2E. It should be understood that each of the steps of method 100 illustrated in Figure 1 will be discussed in detail here, and in some cases, Figures 2A through 2E will be discussed in conjunction with Figure 1.
    [0018] As illustrated in reference numeral 102 in Figure 1 and Figure 2A, an example of method 100 includes applying a building material 12 using the 3D printing system 10 . In the example shown in Figure 2A, a layer 14 of building material 12 was applied, as will be discussed in more detail below.
    [0019] The material of construction 12 can be a powder, a liquid, a paste or a gel. Examples of material of construction 12 include polymeric semi-crystalline plastic materials with a wide processing window greater than 5°C (i.e., the temperature range between the melting point and the recrystallization temperature). In one example, the processing window ranges from 15°C to about 30°C.
    [0020] Examples of suitable materials of construction 12 include polyamides, polyethylene, polyethylene terephthalate (PET) and amorphous variations of these materials. Still other examples of suitable materials of construction 12 include polystyrene, polyacetals, polypropylene, polycarbonate, polyester, polyurethanes, other engineering plastics, and blends of any two or more of the polymers listed herein. Polymeric core shell particles of these materials can also be used.
    The material of construction 12 may have a melting point ranging from about 55°C to about 450°C. Some specific examples of building material 12 with its melting point within this range include nylon 11, nylon 12, nylon 6, nylon 8, nylon 9, nylon 66, nylon 612, nylon 812, nylon 912, etc. As examples, polyamide 12 (i.e., nylon 12) has a melting point of about 180°C, polyamide 6 (i.e., nylon 6) has a melting point of about 220°C, and polyamide 11 (i.e., nylon 11) has a melting point of about 200°C.
    [0022] The material of construction 12 can also be a modified polyamide. In one example, the modified polyamide material is an elastomeric modified polyamide that melts at a lower temperature than nylon 12.
    [0023] When the building material 12 is in powder form, the polyamide structure 12 can be made up of particles of similar size (as shown in Figure 2A) or particles of different sizes. In one example, material of construction 12 includes particles of three different sizes. In this example, the average size of the first particle is greater than the average size of the second particle and the average size of the second polymer particle can be larger than the average size of the third polymer particle. The term "size" as used herein refers to the diameter of a spherical particle or the average diameter of a non-spherical particle (i.e., the average of multiple diameters across the non-spherical particle). In general, the average particle size of the material of construction 12 ranges from about 10 µm to about 100 µm. In some examples, the average particle size of the material of construction 12 ranges from about 40 µm to about 50 µm. As an example of the different sizes for each of the particles, the average size of the first particle can be greater than 50 µm, the average size of the second particle can be between 10 µm and 30 µm, and the average size of the third particle can be the same or less than 10 µm. In one example, the first polyamide particle is present in an amount ranging from about 70% by weight to about 95% by weight, the second polyamide particle is present in an amount ranging from about 0.5% by weight to about 21% by weight and the third polyamide particle is present in an amount ranging from greater than 0% by weight to about 21% by weight.
    [0024] It should be understood that the building material 12 may include, in addition to building material particles, a filler, a flow aid, or combinations thereof. The charge agent(s) can be added to suppress the tribe charge. Examples of suitable loading agent(s) include aliphatic amines (which may be ethoxylated), aliphatic amides, quaternary ammonium salts (for example behentrimonium chloride or cocamidopropyl betaine), phosphoric acid esters, polyethylene glycol esters or polyols. Some suitable commercially available fillers include HOSTASTAT® FA 38 (natural ethoxylated alkylamine), HOSTASTAT® FE2 (fatty acid ester) and HOSTASTAT® HS 1 (alkane sulfonate), each of which is available from Clariant Int. Ltd.). In one example, the filler is added in an amount ranging from more than 0% by weight to less than 5% by weight based on the total weight % of the building material particles.
    [0025] Flow aids may be added to improve the fluidity of the coating of building material 12. The flow aid(s) may be particularly desirable when the particles are less than 25 µm in size. The flow aid improves the fluidity of the material of construction 12 by reducing friction, side drag, and tribe charge build-up (increasing particle conductivity). Examples of suitable flow aids include tricalcium phosphate (E341), cellulose powder (E460 (ii)), magnesium stearate (E470b), sodium bicarbonate (E500), sodium ferrocyanide (E535), potassium ferrocyanide (E536 ), sodium phosphate (E542), sodium silicate (E550), silicon dioxide (E551), calcium silicate (E552), magnesium trisilicate (E553a), powdered talc (E553b), sodium aluminum silicate (E554) , calcium aluminum silicate (E556), bentonite (E558), aluminum silicate (E559), stearic acid (E570) or polydimethylsiloxane (E900). In one example, the flow aid is added in an amount ranging from more than 0% by weight to less than 5% by weight based on the total weight % of the building material particles.
    [0026] Returning to Figure 2A, the printing system 10 for forming the 3D object includes a feed bed 16 (including a supply of building material 12), a distribution plunger 18, a roller 20, a fabrication bed 22 (with a contact surface 23) and each of these physical elements may be operatively connected to a central processing unit (not shown) of the printing system 10. The central processing unit (for example, executing computer readable instructions stored in a non-transient, tangible, computer-readable storage medium) manipulates and transforms data represented as physical (electronic) quantities within the printer's registers and memories in order to control the physical elements to create the 3D object. Data for selective distribution of building material 12, coalescing agent, etc. can be derived from a model of the 3D object to be formed.
    [0027] The dispensing piston 18 and the manufacturing piston 24 may be of the piston type, but are programmed to move in opposite directions. In one example, when a first layer of the 3D object is to be formed, the dispensing plunger 18 can be programmed to push a predetermined amount of the building material 12 out of the opening in the feed bed 16 and the fabrication plunger 24 can be programmed to move in the opposite direction of the distribution piston 18 to increase the depth of the fabrication bed 22. The distribution plunger 18 will advance sufficiently so that when the roller 20 pushes the building material 12 into the fabrication bed 22 and to the contact surface 23, the depth of the fabrication bed 22 is sufficient that a layer 14 of the building material 12 can be formed on the bed 22. The roller 20 is capable of spreading the building material 12 on the fabrication bed 22 to form layer 14, which is relatively uniform in thickness. In one example, the thickness of layer 14 ranges from about 90 µm to about 11 µm, although thinner or thicker layers can also be used.
    [0028] It should be understood that roller 20 can be replaced by other tools such as a blade which may be desirable for spreading different types of powders, or a combination of a roller and a blade.
    [0029] After layer 14 of building material 12 is introduced into fabrication bed 22, layer 14 is exposed to heating (as shown in reference 104 in Figure 1 and Figure 2B). Heating is carried out to preheat the building material 12 and thus it is desirable that the heating temperature be lower than the melting point of the building material 12. As such, the selected heating temperature will depend on the building material 12 which is used. As examples, the heating temperature can be from about 5°C to about 20°C below the melting point of building material 12. In one example, building material 12 is heated to a temperature ranging from about 50°C to about 430°C. In an example where material of construction 12 is polyamide 12, the preheat temperature ranges from about 160°C to about 170°C.
    [0030] Pre-heating of layer 14 of building material 12 can be carried out using any suitable heat source that exposes all of building material 12 in fabrication bed 22 to heat. Examples of the heat source include an electromagnetic radiation source, such as an infrared light source or a near infrared light source.
    [0031] After preheating layer 14, coalescing agent 26 previously described is selectively applied to a portion of building material 12 in layer 14, as shown in reference numeral 106 in Figure 1 and Figure 2C. As illustrated in Figure 2C, coalescing agent 26 can be dispensed from an inkjet applicator 28 (e.g., a thermal inkjet printhead or a piezoelectric inkjet printhead). Although a single inkjet applicator 28 is shown in Figure 2C, it is to be understood that multiple inkjet applicators can be used that span the width of the manufacturing bed 22. The inkjet applicator(s) Ink 28 can be connected to an XY moving stage or to a translation carriage (none of which is shown) which moves the inkjet applicator(s) (28) adjacent to the manufacturing bed (22) to deposit the coalescing agent (26) in desirable areas.
    [0032] The inkjet applicator(s) 28 can be programmed to receive orders from the central processing unit and to deposit the coalescing agent 26 according to a pattern of a cross section for the 3D object layer to be formed. As used herein, the cross section of the layer of the object to be formed refers to the cross section that is parallel to the contact surface 23. The ink jet applicator(s) 28 selectively apply the coalescing agent 26 to the portions of layer 14 that will be merged to become an object layer. As an example, if the first layer is to be in the form of a cube or cylinder, the coalescing agent 26 will be deposited in a square pattern or a circular pattern (from a top view), respectively, on at least a portion of the layer 14 of building material 12. In the example illustrated in Figure 2C, coalescing agent 26 is deposited in a square pattern on area or portion 30 of layer 14 and not on areas or portions 32.
    [0033] In the example of method 100 described here, a single coalescing agent 26 can be selectively applied to form the 3D object layer. It should be understood that the amount of coalescing agent 26 that is applied can be digitally adjusted to change properties in the final product.
    [0034] After the coalescing agent(s) 26 are/are selectively applied to the desired area(s) or portions 30, the entire layer 14 of the building material 12 and the(s) Coalescing agent(s) applied to at least a part of it are exposed to electromagnetic radiation. This is shown in step 108 in Figure 1 and Figure 2D.
    [0035] In an example, electromagnetic radiation can be infrared or near-infrared radiation. Electromagnetic radiation is emitted from a radiation source 34, such as an IR or quasi-IR curing lamp, IR or quasi-IR light emitting diodes (LED), or lasers of desirable electromagnetic wavelengths. In one example, the electromagnetic wavelengths of the light source range from about 100 nm (UV) to about 10 µm. In another example, the light source is a near-infrared light source with wavelengths of about 800 nm. In yet another example, the light source is an infrared light source with wavelengths of about 2 µm. The radiation source 34 may be connected, for example, to a carriage which also holds the ink jet applicator(s) 28. The conveyor may move the radiation source 34 to a position which is adjacent to the bed of fabrication 22. Radiation source 34 can be programmed to receive commands from the central processing unit and expose layer 14 and coalescing agent 26 applied to electromagnetic energy (e.g., IR or quasi-IR energy).
    [0036] The period of time during which the radiation is applied, or the time of exposure to energy, may depend, for example, on one or more of the following characteristics of the radiation source 34; building material characteristics 12; and/or characteristics of the coalescing agent 26.
    [0037] It should be understood that variations in the level of fusion can be achieved by changing (increasing or decreasing) the time of exposure to energy along the X, Y and/or Z axes. fusion decreases along the Z axis, the radiation exposure time may be highest in the first layer and decreased in subsequently formed layers. In yet another example, variations in the level of fusion can be achieved by altering (increasing or decreasing) the amount of coalescing agent 26 that is applied along the X, Y and/or Z axes.
    [0038] The coalescing agent 26 increases the absorption of electromagnetic energy, converts the absorbed electromagnetic energy into thermal energy and promotes the transfer of thermal heat to the building material 12 in contact with the coalescing agent 26 (i.e., in the area(s ) / portion(s) 32). In one example, the coalescing agent 26 sufficiently raises the temperature of the building material 12 in the area(s) 32 near or above its melting point, allowing for melting (which may include melting, sintering, bonding, etc.). ) of the building material 12. In a specific example, the temperature is raised to about 50°C above the melting temperature of the building material 12. The coalescing agent 26 can also cause, for example, heating of the building material 12 below its melting point, but at a temperature suitable for softening and sticking. It should be understood that the area(s) 32 without the coalescing agent 26 applied thereto absorb less energy and thus the building material 12 within these areas 32 generally does not exceed the melting point and does not melt. This forms a layer 40 of the 3D object 50 (Figures 2E and 3) to be formed.
    [0039] As mentioned above, exposure to electromagnetic radiation fuses building material 12 in area(s) 32 to form layer 40 of 3D object 50. Steps 102 to 108 of Figure 1 can be repeated as often as desirable to create subsequent layers 42, 44, 46 (Figure 2E) and to finally form the 3D object 50. It should be understood that heat absorbed (during energy application) by a portion of the building material 12 in which the coalescing agent 26 has been applied or penetrated can propagate to a previously solidified layer, such as layer 40, causing at least part of that layer 40 to heat above its melting point. This effect helps to create a strong bond between adjacent layers (eg 40 and 42) of the 3D object 50.
    [0040] Figure 2E illustrates an example of the 3D object 50 formed in the fabrication bed 22. It should be understood that the subsequently formed layers 42, 44, 46 may have any desirable shape and/or thickness and may be the same or different of any other layer 40, 42, 44,46, depending on size, shape, etc. of the 3D object you want to form.
    [0041] As illustrated in Figure 2E, as the subsequent layers 42, 44, 46 have been formed, the distribution plunger 18 is pushed closer to the opening of the distribution bed 16 and the supply of building material 12 in the bed. of distribution 16 is decreased (comparatively, for example, to Figure 2A, at the beginning of method 100). The fabrication plunger 24 is pushed further away from the fabrication bed opening 22 so as to accommodate the subsequent layer(s) of building material 12 and the selectively applied coalescing agent 26. Since at least part of the building material 12 remains unfused after each layer 40, 42, 44, 46 is formed, the 3D object 50 is at least partially surrounded by the unfused building material 12 in the fabrication bed 22.
    [0042] When the 3D object is completed, it can be removed from the fabrication bed 22, and the unfused building material 12 that remains in the fabrication bed 22 can be reused depending, in part, on the process conditions.
    [0043] Figure 3 illustrates a perspective view of the 3D object 50. Each of the layers 40, 42, 44, 46 includes cast material of construction (cast, sintered, bonded, etc.) and at least some components of the coalescing agent 26 (that is, those that did not evaporate).
    [0044] Referring now to Figure 4, another example of the printing system 10' is shown. System 10' includes a central processing unit (CPU) 56 that controls the general operation of additive printing system 10'. As an example, the central processing unit (CPU) 56 may be a microprocessor-based controller that is coupled to a memory 52, for example via a communications bus (not shown). Memory 52 stores computer readable instructions 54. Central processing unit 56 can execute instructions 54, and thus can control the operation of system 10' in accordance with instructions 54.
    [0045] In this example, the printing system 10' includes the inkjet applicator 28 for selectively delivering/applying the coalescing agent 26 to a layer 14 (not shown in this figure) of building material 12 placed on a support element 60. In one example, support element 60 has dimensions ranging from about 10 cm by 10 cm to about 100 cm by 100 cm, although support element 60 may have larger or smaller dimensions depending on the 3D object 50 a be formed.
    [0046] The central processing unit 56 controls the selective distribution of the coalescing agent 26 to the layer 14 of the building material 12 according to delivery control data 58.
    [0047] In the example illustrated in Figure 4, it is to be understood that the inkjet applicator 28 is a printhead, such as a thermal printhead or a piezoelectric inkjet printhead. The inkjet applicator 28 can be an on-demand print head or a continuous print head.
    [0048] The inkjet applicator 28 can be used to selectively distribute the coalescing agent 26 when in the form of a suitable fluid. As described above, coalescing agent 26 includes an aqueous vehicle, such as water, co-solvent, surfactant, etc., to allow it to be delivered through inkjet applicator 28.
    [0049] In one example, the inkjet applicator 28 can be selected to deliver drops of coalescing agent 26 with a resolution of between about 300 dots per inch (1 inch = 2.54 cm) (DPI) and about 1200 DPI. In other examples, the inkjet applicator 28 may be selected to be able to deliver drops of coalescing agent 26 at a greater or lesser resolution.
    [0050] The inkjet applicator 28 may include an array of nozzles through which the inkjet applicator 28 is capable of selectively ejecting drops of fluid. In one example, each droplet may be on the order of about 10 pico liters (pl) per droplet, although it is contemplated that a larger or smaller droplet size may be used. In some examples, the inkjet applicator 28 is capable of delivering variable size drops.
    [0051] The inkjet applicator 28 can be an integral part of the printing system 10', or it can be user replaceable. When the inkjet applicator 28 is user replaceable, it can be removably inserted into a suitable dispensing receiver or interface module (not shown).
    [0052] In another example of the 10' print system, a single inkjet printhead can be used to selectively deliver different coalescing agents 26. For example, a first set of printhead printhead nozzles can be configured to deliver one of the coalescing agents 26 and a second set of printhead printhead nozzles can be configured to release the other of the coalescing agents 26.
    [0053] As illustrated in Figure 4, the inkjet applicator 28 has a length that allows it to cover the entire width of the support element 60 in a page set configuration. In another example, the matrix configuration of the entire page is achieved by a single inkjet applicator 28 with a set of nozzles having a length to allow it to cover the width of the support element 60. printing 10', the inkjet applicator 28 may have a shorter length that does not allow them to travel the entire width of the support member 60.
    [0054] Although not illustrated in Figure 4, it is to be understood that the inkjet applicator 28 can be mounted on a mobile cart to allow it to move bi-directionally along the length of the support element 60 along the Y axis. illustrated. This allows selective distribution of coalescing agent 26 across the entire width and length of support element 60 in a single pass. In other examples, the ink jet applicator 28 can be fixed while the support member 60 is configured to move relative thereto.
    [0055] As used herein, the term "width" generally denotes the shortest dimension in the plane parallel to the X and Y axes illustrated in Figure 4 and the term 'length' denotes the longest dimension in this plane. However, it should be understood that in other examples the term "width" may be interchangeable with the term "length". As an example, the ink jet applicator 28 can have a length that allows it to travel the entire length of the support element 60 while the movable carriage can move bidirectionally across the width of the support element 60.
    [0056] In examples where the inkjet applicator 28 has a shorter length that does not allow it to travel the entire width of the support element 60, the inkjet applicator 28 can also be moved bidirectionally across the width of the element. bracket 60 on the illustrated X-axis. This configuration allows selective distribution of coalescing agent 26 across the entire width and length of support element 60 using multiple passes.
    The inkjet applicator 28 may include a supply of coalescing agent 26 therein, or it may be operatively connected to a separate supply of coalescing agent 26.
    [0058] As illustrated in Figure 4, the printing system 10' also includes a building material dispenser 64. This dispenser 64 is used to provide the layer (e.g., layer 14) of the building material 12 on the support element 60. Suitable building material dispensers 64 may include, for example, a windshield wiper blade, a roller, or combinations thereof.
    [0059] Building material 12 may be supplied to building material distributor 64 from a hopper or other suitable distribution system. In the illustrated example, the building material dispenser 64 moves along the length (Y axis) of the support member 60 to deposit a layer of building material 12. As previously described, a first layer of building material 12 will be deposited on the support element (60), while subsequent layers of building material (12) will be deposited on a previously deposited (and solidified) layer.
    [0060] It should additionally be understood that the support element 60 may also be movable along the Z axis. In one example, the support element 60 is moved in the Z direction such that as new layers of material of construction 12, a predetermined gap is maintained between the surface of the most recently formed layer and the lower surface of the inkjet applicator 28. In other examples, however, the support member 60 may be secured along the axis. Z, and the inkjet applicator 28 can be movable along the Z axis.
    [0061] Similar to system 10, system 10' also includes the radiation source 34 to apply energy to the deposited layer of building material 12 and the coalescing agent 26 selectively applied to cause solidification of the part(s) 32 of building material 12. Any of the radiation sources 34 described above may be used. In one example, the radiation source 34 is a single energy source that is capable of uniformly applying energy to the applied materials, and in another example, the radiation source 34 includes an array of energy sources to uniformly apply energy to the materials. deposited.
    [0062] In the examples disclosed herein, the radiation source 34 is configured to apply energy substantially uniformly to the entire surface of the deposited building material 12. This type of radiation source 34 may be referred to as a non-energy source. focused. Exposing the entire layer to energy simultaneously can help increase the speed at which a three-dimensional object 50 can be generated.
    [0063] Although not illustrated, it should be understood that the radiation source 34 can be mounted on the mobile cart or can be in a fixed position.
    [0064] The central processing unit 56 can control the radiation source 34. The amount of energy applied can be in accordance with delivery control data 58.
    [0065] The system 10' may also include a preheater 62 which is used to preheat the deposited building material 12 (as shown and described with reference to Figure 2B). The use of preheater 62 can help to reduce the amount of energy that has to be applied by the radiation source 34.
    [0066] To further illustrate the present description, examples are given here. It is understood that these examples are provided for illustrative purposes and are not to be construed as limiting the scope of the present disclosure. EXAMPLE 1
    [0067] A coalescing agent was prepared according to the examples disclosed herein. The example coalescing agent formulation is shown in Table 1. A comparative coalescing agent was also prepared. The comparative coalescing agent formulation is also shown in Table 1. Amounts are given as percentages by weight. The carbon black pigments were added to the formulation as an aqueous dispersion (including water and a polymeric dispersant), but the amount given in Table 1 represents the actual amount of the carbon black pigment. Table 1: Example and Comparative Example Coalescent Agents (CAs)
    aaa Amphoteric Surfactant Coco-Betaine from Solvay Novacare, HLB value not assigned; aa Fluorinated Surfactant from Chemguard Inc. and DuPont, respectively; aaa Self-emulsifying surfactant based on acetylenic diol chemistry from Air Products and Chemical Inc.; b Ole-3-phosphate from Croda;bb From Lubrizol;bbb Styrene acrylate polymeric dispersant from BASF Corp. (100% active); c Aminopolycarboxylate from BASF Corp.; d Aqueous solution of 1,2-benzisothiazolin-3-one, available from Arch Chemicals, Inc.; dd Formaldehyde-free microbicide from The Dow Chemical Co.; and CB1 was a carbon black ink dispersion from Cabot, including a surface treated (non-polymerically dispersed) carbon black pigment; and CB2 was a carbon black ink dispersion from Hewlett-Packard, including a carbon black pigment. smoke from untreated surface, dispersed with JONCRYL® 671
    [0068] Example CA1 and comparative example CA1 were used to form 3D objects with two different types of polyamide-12, namely PA2200 (available from Electra Optical Systems) and VESTOSINT X1556 (available from Evonik). A layer of each of the polyamide-12 (PA-12) materials was applied to a fabrication bed. To form a part of example PA2200, example CA1 was thermal inkjet printed with a 9 ng print head in a pattern on a portion of the PA2200 layer and was exposed to IR radiation. To form an example of the VESTOSINT X1556 part, example CA1 was thermal inkjet printed with a 9 ng print head in a pattern on a portion of the VESTOSINT X1556 layer and was exposed to IR radiation. To form a part of Comparative Example PA2200, Comparative Example CA1 was thermal inkjet printed with a 9 ng print head in a pattern on a portion of the PA2200 layer and was exposed to IR radiation. To form a comparative example of the VESTOSINT X1556 part, the comparative example CA1 was thermal inkjet printed with a 9 ng printhead in a pattern on a portion of the VESTOSINT X1556 layer and was exposed to IR radiation. Each of example CA1 and comparative example CA1 was applied the same amount in the XY direction and the Z direction. Radiation exposure was about 5 inches per second (127 mm/sec).
    [0069] The parts of example PA2200, example VESTOSINT X1556, comparative example PA2200 and comparative example VESTOSINT X1556 were tested to determine various mechanical properties, including tensile strength, Young's modulus, % strain to yield, % deformation of break, and % deformation (yield - break). Each of the example parts and the comparative example parts were tested in uniaxial tension using the method described in ASTM 0638 ("Standard Test Method for Tensile Properties of Plastics"). The results are shown in Table 2.Table 2: Mechanical Properties of the Example and Comparative Example parts


    [0070] As shown in Table 2, in the XY and Z directions, all the mechanical properties of the example part PA2200 (made with example CA1) were better than the mechanical properties of the comparative example part PA2200 (made with the comparative example CA1). As such, both the XY axis and the Z axis intensity have been improved in the example part PA2200.
    [0071] Also as shown in Table 2, in the XY direction, all the mechanical properties of the example part VESTOSINT X1556 were better than the mechanical properties of the comparative example part VESTOSINT X1556.
    [0072] Furthermore, it is believed that the mechanical properties can be further improved by adjusting the amount of example coalescing agent that is used. EXAMPLE 2
    [0073] To test the effect of the type of pigment used in the coalescing agent on the mechanical properties of the 3D object formed, three different carbon black pigment dispersions were used to make three different coalescing agents. The vehicle of the different coalescing agents was otherwise the same. It is noted that the vehicle does not include the surfactant with HLB less than 10. An example coalescing agent was prepared (Example CA2) and two comparative coalescing agents were prepared (Comparative Example CA2 and 3). The carbon black pigment in Comparative Example CA2 was CB1 from Example 1 (i.e., a surface treated carbon black pigment that was not polymerically dispersed). The carbon black pigment in Comparative Example CA3 was a polymerically dispersed carbon black pigment with a styrene acrylate having an average molecular weight of less than 12,000. The carbon black pigment in Example CA2 was CB2 from Example 1 (i.e. a carbon black pigment dispersed with JONCRYL® 671 - a styrene acrylate with an average molecular weight of about 17,000). The formulations are shown in Table 3. Table 3: Example and Comparative Example of Coalescing Agents

    a Fluorinated surfactants from Chemguard Inc. aa Anionic surfactant from Air Products and Chemical Inc. b Styrene malic anhydride polymer from Satomer Co.c CB1 was a carbon black ink dispersion from Cabot, including a carbon black pigment with surface treated (not polymerically dispersed).cc CB3 was a DIC Corp. carbon black ink dispersion including polymerically dispersed carbon black pigment with a styrene acrylate having an average molecular weight of less than 12,000.ccc CB2 was a dispersion of Hewlett-Packard carbon black ink, including carbon black pigment with untreated surface dispersed with JONCRYL® 671.
    [0074] Example CA2 and comparative examples CA2 and CA3 were used to form 3D objects with polyamide-12. A layer of each of the polyamide-12 materials (PA-12) was applied to a fabrication bed. To form an example part, example CA2 was thermal inkjet printed with a 9 ng print head in a pattern on a portion of the PA-12 layer and was exposed to IR radiation. To form parts of comparative example PA-12, comparative examples CA 2 and CA 3 were respectively thermal inkjet printed with a 9 ng printhead in a pattern on a portion of layer PA-12, and were exposed to IR radiation. Each of the CA 2 examples and the comparative examples CA 2 and CA 3 was applied the same amount in the XY direction and the Z direction. Radiation exposure was about 5 inches per second (127 mm/sec).
    [0075] The example part and comparative example parts were tested to determine various mechanical properties including tensile strength, Young's modulus and % strain to yield. Each of the example parts and the comparative example parts were tested in uniaxial stress using the method described in ASTM 0638 ("Standard Test Method for Tensile Properties of Plastics"). The results are shown in Table 4. Mechanical properties along the Z axis were not tested. Table 4: Mechanical Properties of the Example and Comparative Example Parts
    *Numbers are lower than in Example 1 because doctors were taken without a strain gauge.
    [0076] The mechanical properties of the example part formed with CB2 were better than any of the parts formed with the other carbon black ink dispersions (CB1 and CB3). It is believed that the mechanical properties of the parts formed with Example CA2 can be further improved by incorporating the surfactant with an HLB value that is less than 10. EXAMPLE 3
    [0077] To test the effect of the level of anticoagulation agent used in the coalescing agent on the mechanical properties of the formed object, two different levels of anticoagulation agent were used to make two different coalescing agents. An example coalescing agent (Example CA3) was prepared and a comparative coalescing agent was prepared (Comparative Example CA4). The formulations are shown in Table 5. Table 5: Example and Comparative Example of Coalescent Agents
    a Fluorinated surfactant from Chemguard Inc. aa Self-emulsifiable surfactant based on acetylenic diol chemistry from Air Products and Chemical Inc. b Ole-3-phosphate from Croda. bb From Lubrizol.c Aminopolycarboxylate from BASF Corp.d an aqueous solution of 1,2-benzisothiazolin-3-one, available from Arch Chemicals, Inc.dd a formaldehyde-free microbicide from The Dow Chemical Co.e CB2 was a dispersion of Hewlett-Packard carbon black ink, including carbon black pigment with untreated surface dispersed with JONCRYL® 671.
    [0078] Example CA3 and comparative example CA4 were used to form 3D objects with polyamide-12. A layer of each of the polyamide-12 (PA-12) materials was applied to a fabrication bed. To form an example part, example CA3 was thermal inkjet printed with a 9 ng print head in a pattern on a portion of the PA-12 layer, and was exposed to IR radiation. To form comparative example PA-12, comparative example CA4 was thermal inkjet printed with a 9 ng printhead in a pattern on a portion of layer PA-12 and was exposed to IR radiation. Each of example CA3 and comparative example CA4 was applied the same amount in the XY direction and the Z direction. Radiation exposure was about 5 inches per second (127 mm/sec).
    [0079] The example part and the comparative example part were tested to determine various mechanical properties, including tensile strength, Young's modulus, % yield strain, % break strain and % strain (yield - break). Each of the example parts and the comparative example parts were tested in uniaxial tension using the method described in ASTM 0638 ("Standard Test Method for Tensile Properties of Plastics"). The results are shown in Table 6. Mechanical properties along the Z axis were not tested. Table 6: Mechanical Properties of the Example and Parts of the Comparative Example

    [0080] As shown in Table 6, all mechanical properties, with the exception of % deformation (yield - breakage) of example part PA-12 (made with example CA3) were better than or equal to the mechanical properties of the part of the comparative example PA-12 (made with comparative example CA4). As such, the level of anticoagulation agent can be included in a suitable amount in the coalescing agent disclosed herein to improve the mechanical properties of the 3D object.
    [0081] Reference throughout the report to "an example", "another example", "an example" and so on means that a particular element (eg characteristic, structure and/or characteristic) described in linkage with the example is included in at least one example described herein and may or may not be present in other examples. Furthermore, it should be understood that the elements described for any one example may be combined in any suitable way in the various examples unless the context clearly indicates otherwise.
    [0082] It is to be understood that the ranges provided herein include the indicated range and any value or sub-range within the indicated range. For example, a range from about 55°C to about 450°C should be interpreted to include not only the explicitly recited range of about 55°C to about 450°C, but also to include individual values such as such as 57°C, 95°C, 125°C, 250°C, etc. , and sub-ranges, such as from about 70°C to about 325°C, from about 60°C to about 170°C, etc. Also, when "about" is used to describe a value, it means covering small variations (up to +/- 10%) from the indicated value.
    [0083] In describing and claiming the examples disclosed herein, the singular forms "a", "an" and "o" include plural referents unless the context clearly indicates otherwise.
    [0084] Although several examples have been described in detail, it will be evident that the examples described can be modified. Therefore, the above description is to be considered non-limiting.
    权利要求:
    Claims (15)
    [0001]
    1. Coalescing agent for three-dimensional (3D) printing, the coalescing agent CHARACTERIZED in that it comprises: a co-solvent present in an amount ranging from 15% by weight to 30% by weight of a total % by weight of the coalescing agent; a surfactant present in an amount ranging from 0.5% by weight to 1.4% by weight of the total % by weight of the coalescing agent, the surfactant having a hydrophilic lipophilic equilibrium (HLB) value that is less than 10; smoke present in an amount ranging from 3.0% by weight to 6.0% by weight of the total % by weight of the coalescing agent; a polymeric dispersant having an average molecular weight ranging from 12,000 to 20,000; and a water balance.
    [0002]
    2. Coalescing agent according to claim 1, characterized in that it further comprises a chelator present in an amount ranging between 0.03% by weight and 0.10% by weight of the % by weight of the total coalescing agent.
    [0003]
    3. Coalescing agent according to claim 1, CHARACTERIZED by the fact that the polymeric dispersant is selected from the group consisting of a styrene acrylate and a polyurethane.
    [0004]
    4. Coalescing agent, according to claim 1, CHARACTERIZED by the fact that the co-solvent has a boiling point lower than 300°C.
    [0005]
    5. Coalescing agent, according to claim 4, CHARACTERIZED by the fact that the co-solvent is selected from the group consisting of 2-Pyrrolidinone, 1,5-Pentanediol, Triethylene glycol, Tetraethylene glycol, 2-methyl-1,3-propanediol, 1 ,6-Hexanediol, tripropylene glycol methyl ether, and combinations thereof, and wherein the coalescing agent excludes other co-solvents.
    [0006]
    6. Coalescing agent according to claim 1, CHARACTERIZED in that the surfactant is a self-emulsifiable surfactant based on acetylenic diol chemistry or is a combination of a fluorinated surfactant and a self-emulsifiable surfactant based on diol chemistry acetylenic.
    [0007]
    7. Coalescing agent according to claim 1, characterized in that it further comprises an anticoagulation agent consisting of a combination of a polymer of polyacrylic acid and ole-3-phosphate, and wherein the combination is present in an amount ranging from more than 0.20% by weight to 0.62% by weight of the total % by weight of the coalescing agent.
    [0008]
    8. Three-dimensional (3D) printing coalescing agent, according to claim 1, further comprising: an anticoagulation agent present in an amount ranging from more than 0.20% by weight to 0.62% by weight of the % by total weight of the coalescing agent; a chelator present in an amount ranging from 0.03% by weight to 0.10% by weight of the total % by weight of the coalescing agent; and optionally a biocide.
    [0009]
    9. Coalescing agent according to claim 8, characterized in that the biocide is present in an amount ranging from 0.30% by weight to 0.40% by weight of the total % by weight of the coalescing agent.
    [0010]
    10. Layer of a 3D printed object, CHARACTERIZED by comprising: a construction material; and the coalescing agent as defined in claim 1, applied to a surface of at least part of the building material.
    [0011]
    11. The layer according to claim 10, CHARACTERIZED by the construction material being a polymer selected from the group consisting of polyamide, polyethylene, polyethylene terephthalate (PET), polystyrene, polyacetal, polypropylene, polycarbonate, polyester, polyurethanes and their mixtures .
    [0012]
    The layer of claim 10, CHARACTERIZED by the coalescing agent further comprising: an anticoagulation agent present in an amount ranging from more than 0.20% by weight to 0.62% by weight of the total % by weight of the agent coalescent; a chelator present in an amount ranging from 0.03% by weight to 0.10% by weight of the total % by weight of the coalescing agent; and a biocide present in an amount ranging from 0.30% by weight to 0.40% by weight of the total % by weight of the coalescing agent.
    [0013]
    The layer of claim 10, characterized in that the co-solvent has a boiling point of less than 300°C, and wherein the co-solvent is selected from the group consisting of 2-pyrrolidinone, 1,5-pentanediol, triethylene glycol, tetramethylene glycol, 2-methyl-1,3-propanediol, 1,6-hexanediol and tripropylene glycol methyl ether.
    [0014]
    The layer of claim 10, characterized in that the surfactant is a self-emulsifiable surfactant based on acetylenic diol chemistry or includes a combination of a fluorinated surfactant and a self-emulsifiable surfactant based on acetylenic diol chemistry.
    [0015]
    15. Layer according to claim 10, CHARACTERIZED by the polymeric dispersant being selected from the group consisting of styrene acrylate and polyurethane.
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    同族专利:
    公开号 | 公开日
    KR20170063601A|2017-06-08|
    US11173659B2|2021-11-16|
    EP3201258A4|2017-09-13|
    BR112017005750A2|2018-06-26|
    CN106795291A|2017-05-31|
    CN106795291B|2020-02-07|
    US20200199383A1|2020-06-25|
    WO2016053248A1|2016-04-07|
    KR102221213B1|2021-02-26|
    EP3201258A1|2017-08-09|
    US10640661B2|2020-05-05|
    JP2017531572A|2017-10-26|
    EP3201258B1|2018-08-29|
    JP6420902B2|2018-11-07|
    US20170247552A1|2017-08-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5925692A|1997-03-12|1999-07-20|Lexmark International, Inc.|High performance ink compositions|
    GB9725929D0|1997-12-05|1998-02-04|Xaar Plc|Radiation curable ink jet ink compositions|
    WO2000022056A1|1998-10-15|2000-04-20|Seiko Epson Corporation|Ink composition for ink-jet recording and method of ink-jet recording|
    US6436180B1|2000-03-31|2002-08-20|Hewlett-Packard Company|Color ink composition for graphic art ink jet image printers|
    GB0103754D0|2001-02-15|2001-04-04|Vantico Ltd|Three-dimensional structured printing|
    AU2003900180A0|2003-01-16|2003-01-30|Silverbrook Research Pty Ltd|Method and apparatus |
    JP4403384B2|2003-03-07|2010-01-27|リコープリンティングシステムズ株式会社|Three-dimensional additive manufacturing method|
    WO2005023524A2|2003-08-29|2005-03-17|Z Corporation|Absorbent fillers for three-dimensional printing|
    DE102004020452A1|2004-04-27|2005-12-01|Degussa Ag|Method for producing three-dimensional objects by means of electromagnetic radiation and applying an absorber by inkjet method|
    US7351278B2|2004-06-09|2008-04-01|E.I. Du Pont De Nemours And Company|Additive for high optical density inkjet ink|
    US7192474B2|2004-06-22|2007-03-20|Pitney Bowes Inc.|IR absorbing photosensitive optically variable ink compositions and process|
    US7401552B2|2004-09-16|2008-07-22|Agfa Graphics N.V.|Method for manufacturing a flexographic printing master|
    DE102004062761A1|2004-12-21|2006-06-22|Degussa Ag|Use of polyarylene ether ketone powder in a three-dimensional powder-based tool-less production process, and moldings produced therefrom|
    US20070139476A1|2005-12-15|2007-06-21|Schwartz Nathaniel R|Curable inkjet ink|
    KR100980746B1|2005-12-22|2010-09-07|가부시키가이샤 리코|Pigment dispersion, recording ink, ink cartridge, ink-jet recording method and ink-jet recording apparatus|
    JP4866079B2|2005-12-22|2012-02-01|株式会社リコー|Pigment dispersion, recording ink, ink cartridge, ink jet recording method, and ink jet recording apparatus|
    AU2007308150B2|2006-10-11|2011-09-01|Kao Kabushiki Kaisha|Radiation curable inks|
    US8142860B2|2006-12-21|2012-03-27|Agfa Graphics Nv|3D-inkjet printing methods|
    JP5170508B2|2007-03-16|2013-03-27|株式会社リコー|Ink media set, ink jet recording method, recorded matter, and recording apparatus|
    US9187664B2|2009-12-21|2015-11-17|Hewlett-Packard Development Company, L.P.|Inkjet ink composition containing anti-kogation agents|
    JP5725396B2|2010-04-30|2015-05-27|株式会社リコー|Inkjet recording ink, recording apparatus using the same, and recorded matter|
    US20120172490A1|2010-12-31|2012-07-05|Xiaorong Cai|Carbon black pigmented inkjet ink to reduce kogation and improve text quality|
    US8784549B2|2011-09-16|2014-07-22|Eastman Kodak Company|Ink set for continuous inkjet printing|
    US8455570B2|2011-09-16|2013-06-04|Eastman Kodak Company|Ink composition for continuous inkjet printing|
    CN103827233A|2011-09-16|2014-05-28|伊斯曼柯达公司|Ink composition for continuous inkjet printer|
    JP2013203850A|2012-03-28|2013-10-07|Konica Minolta Inc|Inkjet ink|
    US8980406B2|2012-08-28|2015-03-17|3D Systems, Inc.|Color stable inks and applications thereof|
    CN104837609B|2012-12-13|2016-10-26|佳能株式会社|For manufacturing the method for structure and for manufacturing the equipment of structure|EP3200977B1|2014-09-29|2021-06-02|Hewlett-Packard Development Company, L.P.|Three-dimensionalprinting system|
    CN108603062A|2016-04-28|2018-09-28|惠普发展公司有限责任合伙企业|Embedded photoluminescent material group|
    JP6845864B2|2016-04-28|2021-03-24|ヒューレット−パッカード デベロップメント カンパニー エル．ピー．Ｈｅｗｌｅｔｔ‐Ｐａｃｋａｒｄ Ｄｅｖｅｌｏｐｍｅｎｔ Ｃｏｍｐａｎｙ， Ｌ．Ｐ．|3D printing|
    WO2017196321A1|2016-05-12|2017-11-16|Hewlett-Packard Development Company, L.P.|Material sets|
    WO2017196358A1|2016-05-13|2017-11-16|Hewlett-Packard Development Company, L.P.|Material sets|
    JP6630853B2|2016-07-20|2020-01-15|ヒューレット−パッカード デベロップメント カンパニー エル．ピー．Ｈｅｗｌｅｔｔ‐Ｐａｃｋａｒｄ Ｄｅｖｅｌｏｐｍｅｎｔ Ｃｏｍｐａｎｙ， Ｌ．Ｐ．|Formation of microstructure in 3D printing|
    EP3551427A4|2016-12-08|2020-07-22|Hewlett-Packard Development Company, L.P.|Material sets|
    JP6832438B2|2017-04-21|2021-02-24|ヒューレット−パッカード デベロップメント カンパニー エル．ピー．Ｈｅｗｌｅｔｔ‐Ｐａｃｋａｒｄ Ｄｅｖｅｌｏｐｍｅｎｔ Ｃｏｍｐａｎｙ， Ｌ．Ｐ．|3D forming object using high melting temperature polymer|
    US20210291441A1|2018-01-26|2021-09-23|Hewlett-Packard Development Company, L.P.|Three-dimensional printing|
    US11014293B2|2018-03-08|2021-05-25|Ricoh Co., Ltd.|Additive manufacturing using photothermal dyes for high efficiency sintering|
    US10926460B2|2018-09-28|2021-02-23|The Boeing Company|Methods and apparatus for additively manufacturing a structure with in-situ reinforcement|
    US10926461B2|2018-09-28|2021-02-23|The Boeing Company|Methods and apparatus for additively manufacturing a structure with in-situ reinforcement|
    US10926325B2|2018-09-28|2021-02-23|The Boeing Company|Methods and apparatus for additively manufacturing a structure with in-situ reinforcement|
    WO2021221624A1|2020-04-29|2021-11-04|Hewlett-Packard Development Company, L.P.|Three-dimensional printing|
    法律状态:
    2018-07-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-03-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-08-04| B25G| Requested change of headquarter approved|Owner name: HEWLETT - PACKARD DEVELOPMENT COMPANY, L.P. (US) |
    2021-08-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-24| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2021-09-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/09/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/US2014/058091|WO2016053248A1|2014-09-29|2014-09-29|Coalescing agent for three-dimensionalprinting|
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