Water-soluble polymer composition

Abstract

To provide a water-soluble polymer composition for three-dimensional printing that is soluble in a room temperature water at neutral pH, has affinity for both hydrophilic and hydrophobic polymers, and can be used as a support material for a build chamber temperature of 140°C or higher, which is a desirable temperature when printing high temperature thermoplastic resin, for example.SOLUTION: A miscible water-soluble polymer composition is formed of a water-soluble polymer and saccharide, and the water-soluble polymer composition is dry, and can be used as a support material in additive manufacturing processes.SELECTED DRAWING: Figure 1

Description

Related Applications

[0001]

[0001] This application is a continuation of U.S. Provisional Patent Application No. 62 / 511,585, filed May 26, 2017. Priority is claimed, and the disclosure of that patent application is incorporated herein by reference in its entirety. [Technical field]

[0002] The present invention relates to water soluble polymer compositions and methods of making and using water soluble polymer compositions. [Background technology]

[0003]

[0003] Additive manufacturing processes, commonly referred to as three-dimensional (3D) printing, can be used to fabricate desired objects with potential applications in many industries, such as aerospace, automotive, and medical industries. Typical processes include electron beam melting (EBM), fused deposition modeling (FDM), ink jet printing, layered object manufacturing (LOM), and other additive manufacturing processes. , selective laser sintering (SLS), and stereolithography (SL). Using such a process, a desired object can be modeled in a computer-aided design (CAD) package and then constructed using selected construction materials. Deposition-based methods (e.g. FDM) usually require a The applied build material is extruded through a heated printer in a layered fashion according to computer instructions. Printing with commercially available additive manufacturing devices (e.g., the ARBURG™ Freeformer system) often occurs in a build chamber that can provide the desired heating and temperature control based on the build material selected.

[0004]

[0004] Many additive manufacturing techniques use support layers or structures to build the desired object. However, limited availability of suitable support methods, materials, and structures restricts printing of certain design types. The most basic support method uses the same material for the support as the support for the object being printed (e.g., as described in U.S. Patents 6,228,923, 6,790,403, and 8,404,171). This technique does not allow for the creation of any steep protrusions or areas. The supports are assembled in a similar manner to providing scaffolding for the structure or "props up" that will be 3D printed. This type of support is called "destructible" or "raft" support and, although sometimes effective, is cumbersome, time-consuming, and difficult to remove by mechanical destruction or adjustment. It is common to spend time removing or cutting support material from 3D printed objects using razor blades, scalpels, sandpaper, and even power tools. Methods using different support and print materials are also problematic. For example, certain hydrophobic polymers (e.g., polypropylene) are nearly impossible to print due to incompatibility between the support material and the 3D printing base resin.

[0005]

[0005] The inability to remove internal support materials can further limit the type of design of the object. Depending on the external shape, the internal support materials can be difficult, if not impossible, to remove. For many years, many have tried to solve this problem using support structures that would dissolve in very hot water, in very acidic or very basic conditions, in organic solvents, or in various other chemicals. The resulting products are often messy, even dangerous, and generally not very successful. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 6,228,923 [Patent Document 2] U.S. Patent No. 6,790,403 [Patent Document 3] U.S. Patent No. 8,404,171 Summary of the Invention

[0007]

[0006] Surprisingly, several additive manufacturing problems can be solved using water-soluble polymer compositions that include water-soluble polymers, such as butenediol vinyl alcohol copolymer (BVOH) and sugars, such as trehalose. Such compositions are soluble in room temperature water at neutral pH, have an affinity for both hydrophilic and hydrophobic polymers, and can withstand build chamber temperatures of 140°C or higher, which are desirable for printing high temperature thermoplastics. It can be used as a support material for the

[0008]

[0007] The benefits of water-soluble polymer compositions are perhaps unexpected. Water-soluble polymers are often brittle and therefore not suitable for use in traditional filament-type additive manufacturing techniques. Some have attempted to address this issue by using plasticizers, but this can significantly reduce the heat resistance of the water-soluble polymer, which significantly limits their applicability as support materials and therefore the types of build materials that can be printed. Similarly, sugars are often highly water-soluble, but tend to be brittle at room temperature and have low melt viscosities. Current equipment and methods do not allow sugars to be extruded into useful filaments. Furthermore, most sugars are heat-sensitive and caramelize or decompose above their melting temperature, preventing sustained extrusion.

[0009]

[0008] It is seen from the present invention that the water-soluble polymer and the sugar are substantially compatible. The water-soluble polymer composition comprising the water-soluble polymer and the sugar may exhibit improved rheological properties and improved stiffness at higher temperatures. The addition of the sugar to the water-soluble polymer may provide a tackifying effect, which allows the water-soluble polymer to be attached to various supports (e.g., construction plates). Without wishing to be bound by any particular theory, it is believed that the sugars impart pressure sensitive properties, as described in the Dahlquist Criterion, which facilitate improved adhesion at printing temperatures.

[0010]

[0009] Thus, in one embodiment, the water soluble polymer composition comprises a water soluble polymer and a saccharide. In another embodiment, the water soluble polymer composition comprises a continuous water soluble polymer phase and a saccharide dispersed throughout the continuous water soluble polymer phase. In some embodiments, the water soluble polymer composition may further comprise one or more polymers or additives. In another embodiment, the water soluble polymer composition comprises a water soluble polymer and a saccharide dispersed throughout the continuous water soluble polymer phase. In one embodiment, an article of the present invention comprises a continuous polymer phase comprising a water soluble polymer composition, wherein the water soluble polymer composition further comprises a water soluble polymer, a sugar, and an additive dispersed throughout the continuous polymer phase.

[0011]

[0010] In another embodiment, the method of the present invention includes providing a water-soluble polymer and a sugar, mixing the water-soluble polymer and the sugar, and melt processing the mixture of the water-soluble polymer and the sugar. In another embodiment, the method of using the water-soluble polymer composition includes providing the water-soluble polymer composition, melt processing the water-soluble polymer composition, and printing the water-soluble polymer composition into a desired object. In another embodiment, the method of making a water-soluble polymer composition filament includes melt processing the water-soluble polymer and the sugar to obtain a water-soluble polymer composition, cooling the water-soluble polymer composition, and drawing down the water-soluble polymer composition. In another embodiment, the method of using a water-soluble polymer composition comprising a water-soluble polymer and a sugar as a filament in a fused deposition modeling process includes making a filament containing the water-soluble polymer composition.

[0012] In another embodiment, the water soluble polymeric composition support system is provided with an additive manufacturing apparatus having a build chamber, where the build chamber has a build chamber temperature; a print object having a shape of a high temperature thermoplastic build material; and one or more supports disposed about the print object, wherein the one or more supports comprise the water soluble polymer composition; and a build chamber temperature may reach at least about 140° C.

[0013]

[0012] In another embodiment, the three-dimensional printed article includes a three-dimensional printed object generally disposed on a substantially horizontal build plate; and one or more soluble supports disposed about and supporting one or more portions of the three dimensional printed object, where the soluble supports comprise a water soluble polymeric composition.

[0014]

[0013] The above summary is not intended to describe each disclosed embodiment or every implementation. The following detailed description more particularly exemplifies embodiments. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 shows a butanediol vinyl alcohol copolymer (BVOH) / water-soluble polymer / trehalose composition 3-D printed onto a standard acrylonitrile butadiene styrene (ABS) / nylon build plate. [Diagram 2] FIG. 2 shows a BVOH / trehalose composition that was 3-D printed onto an ultra-high molecular weight polyethylene build plate. [Diagram 3]

[0016] FIG. 3 shows the rheology curves for the BVOH / trehalose blends. [Figure 4]

[0017] Figure 4A shows a 50 / 50 wt % BVOH / trehalose composition filament before drawing, and Figure 4B shows the filament of Figure 4 after drawing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016]

[0019] Unless otherwise stated, the following terms have the following meanings and may apply to both the singular and plural:

[0020] "A, an," "the," "at least one," and and "one or more" are used interchangeably. Thus, for example, a water-soluble polymer composition containing a water-soluble polymer may be This means that the water-soluble polymer composition may contain "one or more" water-soluble polymers.

[0017]

[0021] The terms "additive manufacturing," "three-dimensional printing," or "3D printing" refer to the process by which successive layers of material are fabricated using computer-controlled techniques (e.g., electron beam melting (EBM), thermal Fused Deposition Modeling (FDM), Ink Jetting, Laminated Object Manufacturing (LOM), Selective Laser Sintering (SLS), and The term refers to any process used to create three-dimensional objects, including those formed under the terms of lithography (SL) and stereolithography (STEM).

[0018]

[0022] The term "build chamber" refers to a volume often enclosed in or used by an additive manufacturing device that can print a desired component. An example of a build chamber is, but is not limited to, the ARBURG™ Freeformer (available from Arburg GmbH, Lossburg, Germany).

[0019]

[0023] The term "build chamber temperature" refers to the temperature achieved in the build chamber during additive manufacturing.

[0024] The term "build material" refers to the material that is printed in three dimensions using additive manufacturing processes to obtain a desired object.

[0020]

[0025] The term "build plate" refers to a substrate, often a removable film or sheet, onto which a build material or soluble support can be printed.

[0026] The terms "disaccharide", "double sugar", or "biose" refer to any type of sugar whose molecule contains two monosaccharide residues linked by a glycosidic bond.

[0021]

[0027] The terms "draw," "draw down," "drawn," "drawing," or "stretching" refer to the process of drawing a melt-processed feedstock. It represents the process of elongation at temperatures near (within about 50° C.) the glass transition temperature of the polymer composition.

[0022]

[0028] The term "draw ratio" refers to the ratio of material thickness (eg, filament diameter) before drawing to material thickness after drawing.

[0029] The term "feedstock" refers to the raw materials (e.g., build materials or The term "soluble support" refers to the form of material that can be used. Examples of feedstocks include: These include, but are not limited to, pellets, powders, filaments, billets, liquids, sheets, and shaped materials.

[0023]

[0030] The term "high temperature thermoplastics" refers to those that are generally melt processed at temperatures above about 220°C. It refers to a polymer or polymer composition. Examples of high temperature thermoplastics include, but are not limited to, polycarbonate (PC), polyamide (nylon), polyester (PET), polyetheretherketone (PEEK), and polyetherimide (PEI).

[0024]

[0031] The term "melt processing" refers to techniques for adding thermal and mechanical energy to reform, blend, mix, or improve a polymer or polymer composition (e.g., compounding, extrusion, injection molding, blow molding, rotomolding, or batch mixing method).

[0025]

[0032] The term "mixing" means to combine or combine together to form a single substance, single mass, or single phase, including, but not limited to, any physical blending method, extrusion method, or melting method.

[0026]

[0033] The term "monosaccharide" refers to any single sugar having multiple hydroxyl groups. Based on the number of carbons (e.g., 3, 4, 5, or 6), a monosaccharide can be a triose, tetrose, pentose, or hexose, etc.

[0027]

[0034] The term "oligosaccharide" refers to a small number (eg, 2-6 or 2-4) of covalently linked monosaccharide residues.

[0035] The terms "polymer" and "polymeric" refer to molecules of large relative molecular mass, the structure of which is derived (indeed or not) from molecules of lower relative molecular mass. It essentially contains multiple repeats of a (conceptually) derived structural unit.

[0028]

[0036] The term "polymer composition" refers to a mixture of a water-soluble polymer and a saccharide.

[0037] The term "polysaccharide" refers to carbohydrate polymers containing chains of mono- and disaccharide structural units (eg, starch, cellulose, glycogen, etc.).

[0029]

[0038] The terms "preferred" and "preferably" mean These embodiments represent certain advantages, under certain circumstances, but other embodiments may be preferred, under the same or other circumstances. The recitation of a preferred embodiment does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the claims.

[0030]

[0039] The term "semi-crystalline" refers to a polymer composition having a crystallinity of greater than 5% and less than 90% as measured by Differential Scanning Calorimetry (DSC).

[0040] The terms "soluble support" or "soluble support material" refer to a material that can be printed in three dimensions using an additive manufacturing process to physically support or secure the build material during printing, and that can be removed by chemical salvation or dissolution as needed, either during or after the additive manufacturing process.

[0031]

[0041] The term "substantially dry" means that the material contains no more than about 15% by weight (preferably no more than about 10% by weight) volatile materials at standard conditions, based on the weight of the water-soluble polymer composition.

[0032]

[0042] The term "substantially miscible" or "substantially miscible" refers to the compatibility of the materials in a blend such that the blend behaves as if it were a single phase, often with a single glass transition temperature and / or melting temperature (e.g., as determined by differential scanning calorimetry). When tested using the method, the formulation is

[0033]

[0043] The terms "substantially stable" or "substantially stable" refer to the stability of the material at processing temperatures (e.g., This indicates that the material has high dimensional stability (e.g., little flow and little tendency to melt or deform) at temperatures up to 350° C. (e.g., build chamber temperatures).

[0034]

[0044] The term "water-soluble" means that a material will absorb, swell, dissolve, or change in the presence of water.

[0045] The term "water soluble polymer composition" refers to a composition that includes a water soluble polymer and a saccharide.

[0035]

[0046] The recitation of numerical ranges using endpoints includes all numbers subsumed within that range (eg 1 to 5 includes 1, 1.5, 3, 3.95, 4.2, 5, etc.).

[0047] The present invention relates to water-soluble polymer compositions and methods for making and using the water-soluble polymer compositions. Such water-soluble polymer compositions can solve some of the problems associated with traditional additive manufacturing. As shown in Figures 1 and 2, the water-soluble polymer compositions can be printed onto a standard build plate. Figure 1 shows a typical acrylonitrile butadiene polymer composition. Butenediol vinyl alkenyl styrene (ABS) / nylon build plate 10 FIG. 2 shows a cross-sectional view of a cellulose copolymer (BVOH) / trehalose composition 12. 2 shows a BVOH / trehalose composition 22 printed onto a build plate 20. The BVOH / trehalose composition shown in FIG. 2 adhered well to the build plate upon printing.

[0036]

[0048] FIG. 3 shows the apparent viscosity (Pa) as a function of shear rate (1 / s) at a temperature of 210° C. 3 is a rheology curve plot comparing the viscosity (s) of the trehalose solution (curve 24) for 100 wt% trehalose, curve 26 for 100 wt% BVOH, and curve 27 for 50 / 50 wt% BVOH / trehalose. Curve 28A for 85 / 15 wt% BVOH / trehalose, and curve 28B for 85 / 15 wt% BVOH / trehalose. As can be seen, the BVOH / trehalose blends exhibit improved rheological properties over trehalose alone. In particular, the BVOH can increase the melt viscosity of trehalose, extend the temperature range for processing and printability, and increase the ductility of the mixture.

[0037]

[0049] 4A and 4B show a 50 / 50 wt % BVOH / trehalose composition filament 30, a 50 / 50 wt % BVOH / trehalose composition filament before drawing, and a 50 / 50 wt % BVOH / trehalose composition filament after drawing. FIGs. 4A and 4B, for example, demonstrate the suitability of the water-soluble polymer compositions of the present invention as feedstock (here, filaments) for FDM. FIG. 4A shows that BVOH / trehalose composition 30A is brittle and difficult to blend. It can be seen that stretching can cause collapse. However, as can be seen from FIG. 4B, stretching aligns the BVOH chains, making the material significantly tougher and more flexible while also making it less brittle. For FDM printing, flexibility is important to ensure uniform material delivery during the FDM 3D printing process, ultimately resulting in better prints. Stretching the BVOH / Trehalose composition can also cause crystallization in the BVOH polymer.

[0038]

[0050] A variety of water-soluble polymers can be used in the water-soluble polymer composition. Examples of water-soluble polymers include quaternary polyamines, polydiallyl ammonium chloride (PODA), and polyphenylene sulfide (PDA). coagulants such as poly(DADMAC) and dicyandiamide resins; flocculants such as nonionic, anionic, and cationic materials; amphoteric polymers; polyethyleneimine; polyamide-amine; Polyamine-based polymers; Polyethylene oxide; Sulfonated compounds: Polyvinylpyrrolide Polylactone;Polyacrylate type dispersant;Polyalcohol;Cellulose Examples of commercially available water-soluble polymers include, but are not limited to, BVOH (available from Nippon Goshei under the trademark NICHIGO G-POLYMER), poly-2-ethyloxazoline (available from Polymer Chemistry Innovations under the trademark AQUAZOL), and combinations thereof. and hydroxypropyl methylcellulose (available from The Dow Chemical Company under the trademark AFFINISOL®).

[0039]

[0051] A variety of sugars can be used in the water-soluble polymer composition of the present invention. Such sugars can enhance the solubility and adhesion to the hydrophobic polymer. Examples of sugars include, but are not limited to, monosaccharides, disaccharides, oligosaccharides, polysaccharides, or derivatives thereof. Examples of useful sugars include, but are not limited to, trehalose (TREHA™ available from Cargill). Other representative sugars include sucrose, lactulose, lactose, maltose, cellobiose, chitobiose octaacetate, kojibiose, nigerose octaacetate, isomaltose, isomaltulose, β, β-Trehalose, α,α-Trehalose, Sophorose, Laminaribiose, Gentiobiose Examples of the trehalose include maltulose, β,β-trehalose, α,α-trehalose, sophorose, laminaribiose, gentiobiose, turanose, maltulose, palatinose, gentiobiose, mannobiose, melibiose, melibiose, lactinose, lactimulose, melezitose, and xylobiose. Other representative sugars and their respective melting points are shown in Table 1, but are not limited to these.

[0040] [Table 1]

[0041]

[0052] The water-soluble polymer composition can use a variety of other polymers, which may be miscible or immiscible with the water-soluble polymer composition. Examples of polymers that can be used to make such articles include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), cross-linked polyethylene, and the like. , vulcanized rubber, functional polyolefin copolymers including polyolefin-based ionomers, polypropylene (PP), polyolefin copolymers (e.g., ethylene-butene, ethylene Polystyrene, polystyrene copolymers (e.g., high impact polystyrene, acrylonitrile butadiene styrene copolymer), polyacrylates, polymethacrylates, polyesters, polyvinyl chloride (PVC), fluoro Examples of the resin include, but are not limited to, polymers, polyamides, polyetherimides, polyphenylene sulfides, polysulfones, polyacetals, polycarbonates, polyphenylene oxides, polyurethanes, thermoplastic elastomers (e.g., SIS, SEBS, SBS), epoxy resins, alkyd resins, melamine resins, phenolic resins, urea resins, vinyl ester resins, cyanate ester resins, silicone resins, or combinations thereof.

[0042]

[0053] The water-soluble polymer composition may further employ various additives, which may be miscible or immiscible with the water-soluble polymer composition. Examples of suitable additives include, but are not limited to, antioxidants, light stabilizers, fibers, blowing agents, foaming additives, antiblocking agents, heat reflective materials, heat stabilizers, impact modifiers, biocides, antimicrobial agents, compatibilizers, plasticizers, tackifiers, processing aids, lubricants, coupling agents, thermal conductors, electrical conductors, catalysts, flame retardants, oxygen scavengers, fluorescent tags, inert fillers, minerals, and colorants. The additives may be incorporated into the water-soluble polymer composition as powders, liquids, pellets, granules, or any other extrudable form. The amount and type of conventional additives in the water-soluble polymer composition may vary depending on the polymer matrix and the desired properties of the final composition. One of ordinary skill in the art, having regard to the present disclosure, may select the type and amount of additives to achieve the desired properties in the final material. Typical additive incorporation levels are, for example, about 0.01-5% by weight of the composition. be.

[0043]

[0054] In the water-soluble polymer composition, including any additional polymers and additional additives, A variety of water-soluble polymer / saccharide compositions can be used in the preparation of the water-soluble polymer composition. The water-soluble polymer composition of the present invention may comprise, for example, at least about 10% by weight water-soluble polymer, at least about 20% by weight water-soluble polymer, at least about 40% by weight water-soluble polymer, up to about 50% by weight water-soluble polymer, up to about 85% by weight water-soluble polymer, or up to about 90% by weight water-soluble polymer. In another example, the final composition comprises at least about 0.1% by weight saccharide, at least about 1% by weight sugars, at least about 2% by weight sugars, at least about 5% by weight sugars, at least The sugars may contain up to about 20% by weight sugars, up to about 50% by weight sugars, up to about 75% by weight sugars, up to about 90% by weight sugars, up to about 95% by weight sugars, or up to about 99.9% by weight sugars.

[0044]

[0055] In a preferred embodiment, the water-soluble polymer composition may comprise BVOH and trehalose. BVOH is generally water-soluble and stable above its melting point. Furthermore, trehalose is generally a thermodynamically and kinetically stable, non-reducing, natural disaccharide. Their combination may provide many benefits. As shown in FIG. 3, the BVOH / trehalose mixture may be a suitable blend. Haloside may exhibit better rheological properties than trehalose alone. Trehalose may also increase the water solubility of the composition, and may be used in combination with hydrophobic polymers (e.g., polyolefins). It is possible to improve adhesion to the resin, and increase rigidity at higher temperatures. The adhesive properties of the 3D printed part may be improved, providing improved adhesion to typical build plate materials and increased brittleness at higher loading levels, making separation to or from the 3D printed part easier.

[0045]

[0056] In such preferred embodiments, the water-soluble polymer compositions of the present invention may contain, for example, at least about 10% by weight BVOH, at least about 20% by weight BVOH, at least about 40% by weight BVOH, up to about 50% by weight BVOH, up to about 85% by weight BVOH, or up to about 90% by weight BVOH. In another embodiment, the final composition contains at least about 0.1% by weight trehalose. at least about 1% by weight trehalose, at least about 2% by weight trehalose, at least about 5% by weight trehalose, at least about 20% by weight trehalose, up to about 50% by weight % trehalose by weight, up to about 75% trehalose by weight, up to about 90% trehalose by weight, up to about 95% trehalose by weight, or up to about 99.9% trehalose by weight.

[0046]

[0057] The water-soluble polymer composition, including any polymer and any additives, can be prepared by mixing. Mixing can be carried out using a variety of mixing techniques known to those skilled in the art, depending on the polymer matrix selected. The water-soluble polymer, sugar, and any additives can be mixed using any mixing technique commonly used in the plastics industry, such as a compounding roll. The mixing can be done by any method (using a mixing machine, a Banbury mixer, or a mixing extruder). In another preferred embodiment, a vented twin screw extruder is used. The materials can be used in the form of, for example, powders, pellets, or granules. The mixing operation is best carried out at a temperature above the melting or softening point of the water soluble polymer, the sugar, or both the water soluble polymer and the sugar. The resulting melt processed water soluble polymer composition can be directly extruded into the final product shape, pelletized, or carried on from the melt processing equipment to a second operation for subsequent use. The composition is pelletized (e.g., using a pellet mill or densifier) ​​for pelletization. In another embodiment, a blend of the water soluble polymer composition and any additives can be 3D printed.

[0047]

[0058] Water-soluble polymer compositions offer many advantages. One important advantage is the rapid dissolution. The dissolution rate (e.g., mg / min calculated according to dissolution test method 2) can be significantly increased. In some embodiments, the dissolution rate can be increased by more than 20% when compared to the water-soluble polymer component, in other embodiments, the dissolution rate can be increased by more than 50% when compared to the water-soluble polymer component, and in other embodiments, the water-soluble polymer component can be increased by more than 50% when compared to the water-soluble polymer component. In another embodiment, the dissolution rate of the water-soluble polymer composition is at least 400 mg / min, and in a preferred embodiment, the dissolution rate of the water-soluble polymer composition is at least 75%. In an embodiment, the dissolution rate is at least 600 mg / min, and in a most preferred embodiment, the dissolution rate is The rate is at least 800 mg / min. The water soluble polymer composition is further substantially stable at build chamber temperatures of at least about 140°C, at least about 150°C, at least about 170°C, at least about 190°C, at least about 210°C, and up to about 300°C.

[0048]

[0059] The water soluble polymer compositions of the present invention can be subjected to further processing for the desired end use.

[0060] The water-soluble polymer composition is used as a feedstock in fused deposition modeling (FDM). In some embodiments, the feedstock may be a filament, although other feedstocks (e.g., films, sheets, shaped materials, powders, pellets, etc.) may also be used. Although water-soluble polymer compositions with higher sugar incorporation are well suited for use as water-soluble supports in some additive manufacturing processes, such compositions may be too brittle for use in some FDM processes. In particular, such compositions may be more flexible than others, and may be more flexible than others. Feedstocks containing the sugars may collapse when pulled through a spool and forced into a heated nozzle. To increase toughness, it may be necessary to draw down or stretch the composition while it cools. By drawing down or stretching the composition, the water-soluble polymer chains and sugars align in the direction of pulling, which ultimately toughens the composition and therefore the feedstock does not or is less likely to collapse during the FDM 3D printing process. It is possible to convert it into a fee.

[0049]

[0061] Without wishing to be bound by any particular theory, it is believed that drawing enhances the crystallinity of the extrusion feedstock through a stress ordering phenomenon. In additive manufacturing, it is well known that semi-crystalline and crystalline polymers are difficult to print because they tend to shrink in the build chamber when relaxed. This can result in local warping and curling. Surprisingly, the use of the water-soluble polymer composition results in printed parts that are semi-crystalline but have low warping. This may be due in part to the excellent adhesion of the water-soluble composition to various build materials and to the build plate. The water soluble polymer compositions of the present invention further exhibit excellent adhesion properties to a wide range of build plates and build materials, including polyethylene, polypropylene, ultra high molecular weight polyethylene (UMHWD), polytetrafluoroethylene, polyamides (e.g., nylon 6, nylon 6.6, nylon 12), polyimides (e.g., Kapton), polyether-imides (PEI), polyetheretherketones (PEEK), polyacrylonitrile-butadiene-styrene (ABS), polylactic acid (PLA), polyacrylics (e.g., PMMA), and polycarbonate (PC).

[0050]

[0062] In some embodiments, drawing can be performed at a temperature near the glass transition temperature of the water-soluble polymer. In one embodiment, the feedstock process stretch ratio is at least 1.5 to 10:1, and in a preferred embodiment, the feedstock process stretch ratio is 1.5 to 5:1. In the most preferred embodiment, the stretch ratio is between 1.5 and 3:1. This alignment increases the crystallinity of the extrusion feedstock, improving certain mechanical properties (e.g., tensile strength and elongation). The drawing is significantly more flexible and therefore more functional in the printer. This can be accomplished in a number of ways. In some embodiments, the feedstock can be extruded in a conventional manner, and the extruded feedstock can be processed using a godet operation where the filaments can be heated and drawn at an appropriate temperature. This operation can be carried out either in-line or off-line. Alternatively, the water-soluble polymer composition can be extruded, cooled, and reheated between two or more take-off units operating at different drawing speeds to draw the filaments. Additionally, the extruded composition can be precisely cooled and then reheated between two or more take-off units operating at different drawing speeds to draw the filaments. It may also be possible to dispose of the polymer in a polymer-containing polymer stream and stretch it in-line using a suitable downstream extrusion design. Taking volume into consideration, one of skill in the art will be able to determine the feedstock (e.g., filament) of the water-soluble polymer composition of the present invention. Other methods may be appreciated to achieve the desired draw ratio and chain alignment to obtain the desired stretch rate.

[0051]

[0063] In another embodiment, the feedstock may include a water-soluble polymer that does not contain sugars. In this example, the water-soluble polymer is semi-crystalline and substantially stable at temperatures of 140° C. or greater. and has a water solubility of at least 100 mg / min (by Dissolution Test Method 2). To enhance toughness, the water-soluble polymer feedstock of this composition is optionally stretched. In a preferred embodiment, the stretch ratio is at least 1.5:1 for compositions containing water-soluble polymers. Preferred water-soluble polymers include BVOH, available from Nippon Goshei under the trademark NICHIGO G-POLYMER. Preferred grades include Nichigo G8049 and Nichigo G1028.

[0052]

[0064] In another embodiment, the water soluble polymer compositions of the present invention can be prepared by conventional melt processing methods (e.g. Converting it into various articles using techniques such as compounding, molding, casting, or additive manufacturing For use in additive manufacturing, the water-soluble polymer composition can be used in a variety of additive manufacturing devices, for example as a support material or a build material. Examples of such additive manufacturing devices include the Dremel DigiLab 3D45 printer, LulzBot Mini 3D printer, MakerBot Replicator+, XYZprinting da Vinci Mini, Formlabs Form 2, Ultimaker 3, Flashforge Finder 3D printer, Robo 3D R1+Plus, and Ultimaker The water-soluble polymer composition may be applied manually (e.g., by Selectively remove the build or support material by, for example, dissolving or mechanically, automatically (for example, by computer-controlled dissolution), or a combination of both. It is possible.

[0053]

[0065] Various polymers and additives, such as those previously described, can be added to the water-soluble polymeric compositions of the present invention to make certain articles.

[0066] The compositions and articles of the present invention have broad utility in a variety of industries, including but not limited to additive manufacturing. These compositions and articles can provide great utility to plastics compounders and processors. The compositions and articles of the present invention provide increased solubility and adhesion to hydrophobic polymers, tunable rheological properties, and increased stiffness at higher temperatures.

[0054]

[0067] In the following examples, parts and percentages are by weight unless otherwise stated. EXAMPLES

[0055] [Table 2]

[0056] [Table 3]

[0057] Sample preparation: Formulations 1-17

[0068] Each of Formulations 1-17 was prepared according to the weight ratios listed in Table 3 (Formulations 3-17 were first blended in a plastic bag) and gravimetrically extruded in a 27 mm twin screw extruder. The mixture was fed to an extruder (52:1 L:D, commercially available from ENTEK™ Extruders, Lebanon, Oregon). Compounding was carried out using the following temperature profile in zones 1-13: 100, 350, 400, 400, 400, 400, 400, 400, 400, 400, 400, 400, 400, and 400°F (approximately 38, 177, 204, 204, 204, 204, 204, 204, 204, 204, 204, 204, and 204°C, respectively). The extruder screw speed was approximately 300 rpm, and the throughput was 10 kg / hr. The mixture was then extruded onto an air-cooled belt conveyor and pelletized into approximately 2.5 mm x 2.5 mm cylindrical pellets, which were collected in plastic bags.

[0058] Example 1: Printing of Formulations 1-2, 4, 6-7

[0069] Samples from each of Formulations 1-2, 4, and 6-7 were cut into 8 cm 3Formulations 1-2, 4, and 6-7 were dried at 90°C for 8 hours prior to printing. After drying, each of the formulations was individually loaded into the Freeformer and printed into 2cm cubes using the following parameters: The droplets were printed on a 2 cm x 2 cm x 2 cm cube with the following settings: nozzle size 0.2 mm, layer thickness 0.2 mm, a part density of approximately 35%, a discharge of 80%, and a droplet aspect ratio of 2.2. The nozzle temperatures were 207°C, 200°C, 207°C, 190°C, and 207°C, and the back pressure was 80 bar. and the print speed was 40 mm / sec. A build chamber temperature of 120° C. was used when printing Formulations 1-2, 4, and 7, and a build chamber temperature of 80° C. was used when printing Formulation 6.

[0059] Example 2: Printing of PEI and Formulation 6

[0070] An ARBURG™ Freeformer (available from Arburg GmbH, Lossburg, Germany) was used. The PEI and Formulation 6 were printed on the paper. The PEI was dried at 100°C for 8 hours, and the water-soluble polymer formulation was Mixture 6 was dried at 90° C. for 8 hours. After drying, the material was loaded into the Freeformer and cut into 25 mm pieces. 2 A PEI part with a thickness of 0.4 mm and a 11.50 mm protrusion (0.4 mm thick) attached to a square base by a 1 mm thick arm was printed using the following parameters: The following parameters were used: nozzle size of 0.20 mm, layer thickness of 0.2 mm, a part density of about 90% for both the part material and the support material, an ejection rate of 90%, and a droplet aspect ratio of 1.5. Formulation 6 was printed using a nozzle temperature of 207° C. and a dosing back pressure of 80 bar. For infill, a build chamber temperature of 145° C. and a printing speed of 20 mm / sec were used. The gauging speed was used.

[0060] Example 3: Printing of PEI and Formulation 2

[0071] As in Example 2, PEI and Formulation 2 were printed using an ARBURG™ Freeformer (available from Arburg GmbH, Lossburg, Germany). The PEI was dried at 100° C. for 8 hours. The water-soluble polymer blend 2 was dried at 90° C. for 8 hours. After drying, the materials were loaded into the Freeformer and 2 11.50mm protrusion (0.4mm thick) is attached by a 1mm thick arm. The PEI part attached to the square base was printed using the following parameters: The following parameters were used for the coating: nozzle size 0.20 mm, layer thickness 0.2 mm, part concentration of about 90% for both part and support materials, ejection rate 90%, and droplet aspect ratio 1.5. PEI was coated at a nozzle temperature of 305 °C. Formulation 1 was printed using a nozzle temperature of 207°C and a dosing back pressure of 80 bar. For the infill, a nozzle temperature of 145°C and a dosing back pressure of 50 bar were used. A deposition chamber temperature and a printing speed of 20 mm / sec were used.

[0061] Example 4: Filament preparation of formulations 4 and 6-7

[0072] Filament preparation for formulations 6-7 was carried out according to two methods (Method A and Method B). In Method A, pellets from Formulations 6-7 were dried for 4 hours and then spun at 20 rpm. The mixture was extruded at a clew speed of 180° C. for all extruder zones and at a throughput of 5 kg / h. The resulting filaments were fed onto a heated multi-roll godet downstream unit at 90° C. Godet of Formulation 6 The heated filaments were stretched from an initial stretch ratio to a final stretch ratio of 2:1. The heated filaments were stretched from an initial stretch ratio to a final stretch ratio of 1.5:1.

[0062]

[0073] In Method B, pellets from Formulations 4 and 7 were extruded in a 1.50" single screw extruder. Machine (available from Automated Manufacturing Systems, Inc., West Palm Beach, Florida) The filaments were extruded using a 20 rpm screw speed and a throughput of 5 kg / hr. All temperature zones after the feed throat were heated to 200°C. The extruded filaments were cooled with air to about 90-120°C and then drawn using downstream take-up and winding equipment to obtain a final draw ratio of about 2:1. The resulting filament had a thickness of about 1.75 mm.

[0063] Example 5: Makerbot Filament of Formulation 4

[0074] A 1.75 mm thick filament of Formulation 4 made according to Method B was printed on a MAKERBOT REPLICATOR™ 2X (commercially available from MakerBot Industries, LLC) using the following conditions: The filament was fed directly into the Makerbot extruder. The extruder temperature was 190°C. I printed the stock files that came with the Makerbot software (shark). The conditions used were:

[0064] Dissolution test method 1: Formulations 1 and 3-5

[0075] For each of the formulations 1 and 3-5, a 2.5 g pellet sample was heated at approximately 70° C. The samples were placed in approximately 50 ml of deionized water at 100° C. The dissolution time was recorded when the samples were completely dissolved, with no visible pellets. The results are shown in Table 4.

[0065] [Table 4]

[0066] Dissolution test method 2: Formulations 1-2, 4, 6-7

[0076] Printed cube samples (described in Example 1) for each of Formulations 1-2, 4, and 6-7 were subjected to Dissolution Test Method 2 as described below. 3 A cube with volume The sample was placed in a 250 ml beaker containing 100 ml of deionized water at 70°C. The recoats were sampled, dried for 24 hours and the amount of dissolved material was determined gravimetrically. The dissolution rate was calculated using the following formula:

[0067]

number

[0068] Calculation based on experimental model (Weibull)

[0069]

number

[0070] In the above formula, M t is the mass dissolved at time T; M i is the initial mass of the cube; a is the scale parameter of the process; b determines the shape of the melting curve; T i Dissolution is (Usually this value is zero.) From this experimental model, we can see that the cube The time interval required to dissolve 63.2% (T d) can be calculated using the following relationship:

[0071]

number

[0072] Although this is an experimental model, the initial mass of the cube (M i ) and an approximate dissolution rate based on the time interval it takes to dissolve approximately 63.2% of the sample is obtained.

[0073]

number

[0074]

[0077] The results obtained are shown in Table 5.

[0075] [Table 5]

[0076] Mandrel knot testing of formulations 4 and 6

[0078] Filaments made using formulations 4 and 6 were subjected to mandrel knot testing. Twelve-inch long pieces of filament were knotted into single knots on several HDPE cylindrical mandrels of various diameters (3 inches, 2 inches, and 1 inch) and hand knotted. The filament was pulled at 100 rpm. Filaments that did not break during this test were considered to have passed the test. The results are shown in Table 6. As shown in.

[0077] [Table 6]

[0078] Analysis by DSC

[0079] The differentials for the filaments of formulation 6 with and without drawing were A differential scanning calorimetry (DSC) experiment was carried out. From Table 7, it can be seen that the filaments were stretched at a stretch ratio of about 3:1. This means that the melting enthalpy for compound 6 increases from 1.7 J / g to 8.7 J / g. However, removing the thermal history (which is the process of lowering the drawn filament below its melting temperature) The melting enthalpy was measured by heating the sample to a temperature above the melting temperature, cooling to room temperature, and then reheating above the melting temperature. Such stress-induced crystallization behavior was evident by DSC, which indicates that Those skilled in the art will appreciate that the material is semi-crystalline in nature.

[0079] [Table 7]

[0080]

[0080] Furthermore, as shown in Table 8, DSC was performed on Sugar 1 and Formulations 1-2 and 6-7. The results in Table 8 show that formulations 6 and 7 are miscible formulations. Specifically, Only one glass transition temperature and melting temperature are observed.

[0081] [Table 8]

[0082]

[0081] Although specific embodiments have been described, it will be readily apparent to one skilled in the art that the disclosure set forth in this specification is also applicable to still other embodiments within the scope of the appended claims. [1] A water-soluble polymer composition comprising a water-soluble polymer and a saccharide, wherein the water-soluble polymer and the saccharide form a substantially miscible water-soluble polymer composition, and the water-soluble polymer composition is substantially dry. [2] The water-soluble polymer composition of [1], wherein the water-soluble polymer composition is substantially stable at a build chamber temperature of at least about 140°C. [3] The water-soluble polymer composition of [1], wherein the water-soluble polymer composition is substantially stable at a build chamber temperature of at least about 150°C. [4] The water-soluble polymer composition of [1], wherein the water-soluble polymer composition is substantially stable at a build chamber temperature of at least about 170°C. [5] The water-soluble polymer composition of [1], wherein the water-soluble polymer composition is substantially stable at a build chamber temperature of at least about 190°C. [6] The water-soluble polymer composition of [1], wherein the water-soluble polymer composition is substantially stable at a build chamber temperature of at least about 210°C. [7] The water-soluble polymer composition of [1], wherein the water-soluble polymer comprises a butenediol-vinyl alcohol copolymer. [8] The water-soluble polymer composition according to [1], wherein the saccharide comprises trehalose. [9] The water-soluble polymer composition according to [1], further comprising one or more additives or polymers.

[10] The water-soluble polymer composition according to [1], wherein the water-soluble polymer composition is semi-crystalline.

[11] The water-soluble polymer composition according to [1], wherein the water-soluble polymer composition has a dissolution rate of 400 mg / min according to Dissolution Test Method 2.

[12] The water-soluble polymer composition according to [1], wherein the water-soluble polymer composition has a dissolution rate of at least about 400 mg / min as measured by Dissolution Test Method 2.

[13] A method comprising: treating a mixture of a water soluble polymer and a sugar to form a water soluble polymer composition, such that the resulting water soluble polymer composition is substantially miscible and substantially dry; forming a feedstock from the water soluble polymer composition; and stretching the feedstock, such that the feedstock has a stretch ratio.

[14] The method of

[13] , wherein the stretch ratio is at least about 5:1.

[15] The method of

[13] , wherein the stretch ratio is at least about 3:1.

[16] The method of

[13] , wherein the stretch ratio is at least about 1.5:1.

[17] A water-soluble support composition comprising: a semi-crystalline, water-soluble polymer having a dissolution rate of at least 100 mg / min according to Dissolution Test Method 2 and being substantially stable at a build chamber temperature of at least 140°C.

[18] The water-soluble support material composition according to

[17] , which draws down during processing.

[19] A three-dimensional printed article comprising: a three-dimensionally printed object generally disposed on a substantially horizontal build plate; and one or more soluble supports disposed about the three-dimensionally printed object and supporting one or more portions of the three-dimensionally printed object, the soluble supports comprising a water-soluble polymer composition.

[20] The three-dimensional printed article of

[19] , wherein the water-soluble polymer comprises butenediol-vinyl alcohol copolymer. [Explanation of symbols]

[0083] 10 Acrylonitrile Butadiene Styrene (ABS) / Nylon Build Plate 12 Butenediol vinyl alcohol copolymer (BVOH) / trehalose composition 22 BVOH / Trehalose Composition 20 Ultra High Molecular Weight Polyethylene Build Plates 24 Curve for 100% trehalose by weight 26 Curve for 100% BVOH by weight 28A Rheological curve for 50 / 50 wt% BVOH / Trehalose 28B Rheological curve for 85 / 15 wt% BVOH / Trehalose 30 Filaments of 50 / 50 wt% BVOH / Trehalose composition 30A Filament of 50 / 50 wt% BVOH / Trehalose composition before drawing 30B Filaments of 50 / 50 wt% BVOH / Trehalose composition after drawing

Claims

1. A water-soluble polymer composition for three-dimensional printing comprising a water-soluble polymer and a sugar, The water-soluble polymer composition, wherein the water-soluble polymer and the sugar form a miscible water-soluble polymer composition, the water-soluble polymer composition is dry, and the water-soluble polymer content in the water-soluble polymer composition is 40% by weight or more, and the sugar content in the water-soluble polymer composition is 50% by weight or less.

2. 10. The water soluble polymer composition of claim 1, wherein the water soluble polymer composition is stable at a build chamber temperature of at least 140°C.

3. 10. The water soluble polymer composition of claim 1, wherein the water soluble polymer composition is stable at a build chamber temperature of at least 150°C.

4. 10. The water soluble polymer composition of claim 1, wherein the water soluble polymer composition is stable at a build chamber temperature of at least 170°C.

5. 10. The water soluble polymer composition of claim 1, wherein the water soluble polymer composition is stable at a build chamber temperature of at least 190°C.

6. 10. The water soluble polymer composition of claim 1, wherein the water soluble polymer composition is stable at a build chamber temperature of at least 210°C.

7. The water soluble polymer composition of claim 1 , wherein the water soluble polymer comprises a butenediol vinyl alcohol copolymer.

8. The water soluble polymer composition of claim 1 , wherein the sugar comprises trehalose.

9. The water soluble polymer composition of claim 1 further comprising one or more additives or polymers.

10. The water-soluble polymer composition of claim 1 , wherein the water-soluble polymer composition is semi-crystalline.

11. 10. The water soluble polymer composition of claim 1, wherein the water soluble polymer composition has a dissolution rate of 400 mg / min according to Dissolution Test Method 2.

12. 10. The water soluble polymer composition of claim 1, wherein the water soluble polymer composition has a dissolution rate of at least 400 mg / min as measured by Dissolution Test Method 2.

13. a 3D printed object roughly positioned on a horizontal build plate; one or more soluble supports disposed about the three-dimensional printed object and supporting one or more portions of the three-dimensional printed object; 13. A three-dimensional printed article comprising: a soluble support comprising the water-soluble polymer composition according to any one of claims 1 to 12.

14. The three dimensional printed article of claim 13 , wherein the water soluble polymer comprises a butenediol vinyl alcohol copolymer.

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