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WO1996013372A2 - Materiau constitutif d'un article tridimensionnel - Google Patents

Materiau constitutif d'un article tridimensionnel Download PDF

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Publication number
WO1996013372A2
WO1996013372A2 PCT/US1995/012876 US9512876W WO9613372A2 WO 1996013372 A2 WO1996013372 A2 WO 1996013372A2 US 9512876 W US9512876 W US 9512876W WO 9613372 A2 WO9613372 A2 WO 9613372A2
Authority
WO
WIPO (PCT)
Prior art keywords
resins
resin
build material
dimensional article
sulfonamide
Prior art date
Application number
PCT/US1995/012876
Other languages
English (en)
Other versions
WO1996013372A3 (fr
Inventor
Michael T. Nowak
Manual M. Ferreira
Nadine J. Leonard
Original Assignee
Bpm Technology, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bpm Technology, Inc. filed Critical Bpm Technology, Inc.
Priority to AU41932/96A priority Critical patent/AU4193296A/en
Publication of WO1996013372A2 publication Critical patent/WO1996013372A2/fr
Publication of WO1996013372A3 publication Critical patent/WO1996013372A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/097—Sulfur containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C08K5/435—Sulfonamides

Definitions

  • the present invention relates to a build material and method for forming a three-dimensional article, and, more particularly to a build material and related method for forming a three-dimensional article, such as a model or prototype based upon article defining data.
  • CAD Computer aided design
  • Computer aided milling machines for milling articles in response to computer generated signals are also known.
  • a computer generated data file representative of the article to be produced may be used to control the operation of the machine.
  • Milling tools within the machine shape a solid block of material.
  • Stereolithography has been another approach for producing a prototype of an article.
  • An example of the production of prototypes by stereolithography is disclosed in United States Patent No. 4,575,330 to Hull entitled “Apparatus for Production of Three-Dimensional Objects By Stereolithography.”
  • Hull discloses an apparatus whereby articles are produced by forming successive, adjacent, cross-sectional laminae of the article at the surface of a UV-curable fluid medium.
  • the fluid medium is capable of altering its physical state from a fluid to a solid in response to stimulation, such as by UV radiation, particle bombardment such as electron beams, chemical reaction, or impinging radiation other than UV radiation.
  • the apparatus includes a source of stimulation which may be selectively applied to the surface of the fluid medium to produce cross-sectional laminae of the article.
  • the source of selective stimulation is controlled by a computer in response to computer generated graphics.
  • Stereolithography requires the use of more material than is actually incorporated in the article being produced, and also requires the exact placement of the article being constructed relative to the surface of the fluid medium.
  • the depth of the layer created when the fluid surface is exposed to the stimulation may be difficult to control. As a result, the resolution of surface features may be difficult to control.
  • An apparatus and method for forming three- dimensional articles from a material which is normally solid but flowable when heated is disclosed in United States Patent No. 5,141,680 to Almquist et al.
  • This apparatus includes a nozzle for dispensing a material which has been heated to the point that it flows. Suitable materials are listed as including thermoplastics, hot melt glue, wax, and cerro alloys.
  • the material is dispensed through the nozzle by applying pressure, and the flow of material can be stopped by means of a slidable valve or by lessening, ceasing, or reversing the pressure. Accordingly, precise control of the flow of material may be difficult to obtain. Moreover, unsupported portions of the article may be problematic and may collapse unless support is provided. Accordingly, a second support material is provided. This support material must be removed from the article after fabrication is complete.
  • United States Patent No. 5,121,329 to Crump discloses another apparatus wherein a flow of material through a nozzle is used to create a three-dimensional object.
  • Suitable materials include a variety of thermoplastic resins, waxes, metals and metal alloys.
  • the flow of material is determined by the size of the outlet orifice, a constant pressure, and the vertical height of the tip of the nozzle.
  • a spring-loaded ball check valve may assist in metering the flow of material. Again, precise control of this flow may be difficult to obtain.
  • a major advance in the art of three-dimensional modeling is disclosed in United States Patent No.
  • This patent discloses an apparatus including: an ejection head for emitting small mass particles or droplets of particulate matter; a servo-mechanism for manipulating the ejection head; and a machine controller for controlling the servo-mechanism in response to a data file containing coordinate information representing the design of the article being produced.
  • the mass particles are directed to the coordinates of a three-dimensional article as defined by the computer data file.
  • the mass particles may comprise a ceramic or plastic material, a slurry material having water content, or charged particles which are electrically deflected.
  • the controller causes fabrication particle material to be ejected as droplets forming the three-dimensional object, while a complementary support structure is created by the ejection of support particles. While this scheme allows the fabrication of layers having various angles, the three-dimensional object must later be separated from the support structure. Accordingly, this device requires the use of more material than is ultimately incorporated in the three-dimensional object.
  • United States Patent No. 5,260,009 to Penn entitled “System, Method, and Process for Making Three-Dimensional Objects” discloses another apparatus for forming three-dimensional objects wherein a second material is dispensed with each layer of the three-dimensional article as it is formed. The formation of three-dimensional articles by jetting a photosetting or thermosetting material is disclosed in United States Patent No.
  • Jet head sequentially or intermittently jets the photosetting or thermosetting material in a droplet form along a flight path to an overhead stage. An exposure unit is then used to cure the material. If a photosetting material is used, the exposure unit is a source of light radiation. A mesh sheet may be required in order to form an article having a complicated shape.
  • United States Patent No. 5,140,937 also to Yamane et al. discloses an apparatus for forming a three-dimensional article having plural jet heads for jetting a thermosetting material and a heat supplying unit for curing the thermosetting material.
  • thermosetting resins are listed as including: (1) materials cured through oxidation polymerization reaction by heat (e.g., epoxy resin); (2) materials cured through condensation polymerization reaction by heat (e.g. , amino melamine or urea resins) ; and (3) materials cured through additional reaction by heat (e.g., bisphenol A type epoxy resin).
  • a build material that melts at a temperature of between about 250°C, which cools quickly and adheres to itself, and has a low rate of shrinkage.
  • a build material comprises a solution of a resin having a hydroxyl number of from about 5 to 1000, and molecular weight greater than about 500, dissolved in at least one primary aromatic sulfonamide.
  • the primary aromatic sulfonamide has a melting point greater than about 25°C.
  • the present invention also provides a method for making a three-dimensional article based upon article defining data. The method comprises the step of dispensing a meltable build material comprising a solution of a resin having a hydroxyl number of from about 5 to 1000, and molecular weight greater than about 500, dissolved in at least one primary aromatic sulfonamide in a plurality of droplets toward a platform and which solidify after dispensing to construct the article in successive layers based upon the article defining data.
  • Such a build material comprises a solution of a resin having a hydroxyl number of from about 5 to 1000, and a molecular weight greater than about 500, dissolved in at least one primary aromatic sulfonamide preferably having a melting point greater than about 25°C.
  • the modeling apparatus includes a platform on which the three-dimensional model or prototype is built, and a ballistic droplet jetting head. Ballistic droplets of liquid build material are jetted from the piezoelectric jet on the jetting head to the platform in order to form a model or prototype.
  • the build material is normally solid when at the temperature of the interior of the apparatus.
  • the build material is heated to a temperature of from about 50°C to 250°C and maintained at this temperature within the jetting head in order to maintain the build material in a liquid state. Accordingly, heated liquid droplets of build material are jetted from the jetting head to either the platform or previously jetted build material. On contact with the platform or previously jetted build material, the heated liquid droplets cool quickly, and harden at a low rate of shrinkage.
  • the rheology of the build material is preferably such that a droplet remelts portions of deposited material so as to form a flowable bead.
  • the jet is capable of dispensing at least about 10,000 droplets per second.
  • hydroxyl number As defined by hydroxyl number, through hydrogen bonding, holds together the droplet after jetting through the jetting head.
  • the upper limit of hydroxyl number i.e., 1000 is important in that the higher the hydroxyl number, the higher the heat capacity of the resin, and the resin cools slower. Slower cooling is undesirable in that the build material tends to sag if it cools slowly as the article is being built.
  • Exemplary resins include polyester resins, phenolic resins, polyamides, vinyl ester resins, polyurethanes, amino resins, melamine resins, urea resins, epoxy resins, and naturally-derived polymers such as polystyrene, acrylic polymers, and styrene-acrylic copolymers, coumarin-indene, shellac, protein and celluosics (e.g. ethyl cellulose, ethyl hydroxy ethyl cellulose, nitro cellulose, etc.), and mixtures thereof.
  • Suitable polyester resins include practically any esterification product of a polybasic organic acid and a polyhydric alcohol.
  • Polyester resins can also be derived from the esterification of a polycarboxylic acid or anhydride with a polyhydric alcohol.
  • Suitable phenolic resins include practically any reaction product of an aromatic alcohol with an aldehyde. Particularly preferred, are the phenolic resins prepared by the reaction of phenol with formaldehyde.
  • Suitable vinylester resins include practically any reaction product of an unsaturated polycarboxylic acid or anhydride with anepoxy resin.
  • Exemplary epoxies include virtually any reaction product of a polyfunctional halohydrin, such as epichlorohydrin, with a phenol or polyhydric phenol.
  • the build material includes about 1 to 50 percent of the resin, preferably about 5 to 30 percent, and more preferably about 5 to 15 percent, by weight of the resin.
  • the primary aromatic sulfonamide it is believed that the primary aromatic sulfonamides provide the necessary self adhesion properties to the build material.
  • Suitable aromatic sulfonamides are preferably primary C to C 15 benzenesulfonamides, and most preferably the substitution is alkyl and is at the para position.
  • Exemplary primary aromatic sulfonamides include p-to- luenesulfonamide, p-n-ethylbenzenesulfonamide, p-methoxy-benzenesulfonamide, p-n-nonylbenzene- sulfonamide, p-n-butylbenzenesulfonamide, and mixtures thereof.
  • the build material includes about 1 to 50 percent, preferably about 70 to 90 percent, and more preferably about 75 to 90 percent by weight of one or more of the aromatic sulfonamides. Particularly preferred is a 50/50 mixture of p-toluenesulfonamide and p-n-ethylbenzenesulfonamide.
  • the build material can include antioxidants
  • the build material includes from about 1 to 10 percent by weight of the various additives.
  • Such a build material has a minimum surface tension minimum of 25 dyne cm (measured at 125°C using a DuNoy platinum ring surface tensionmeter) and a Brookfield viscosity at 115°C to 135°C of between about 1 and 20 cps at the jetting temperature of about 120°C.
  • the build material is stable having no significant changes in surface tension, color, or viscosity on aging over 4 weeks.
  • the build material having the above composition is heated to a temperature of 120°C within a reservoir and build material jet, such as described in copending U.S. patent application Serial No. , assigned attorney work docket no. 4855-20.
  • the build material is in its liquid state. Heated liquid droplets are jetted from the jetting head at a rate of O to 12,000 droplets/sec initially to a platform, and then onto previously solidified build material to form a two inch model rocket.
  • the flat velocity over the frequency is essentially about 3 m/sec.
  • the droplets are jetted for 120 minutes.
  • the droplets quickly cool at room temperature in 125 microseconds.
  • the jet such as a piezoelectric jet
  • the jet may be positioned in spaced relation from a target point. Also, the jet may be positioned relatively close to the target position so that the build material may, in a sense, not be considered as traveling ballistically. Accordingly, the terms ejected and jetted may also e used to describe a relatively small gap or no gap between the jet and the target position.
  • the piezoelectric jet is but one embodiment of a dispenser for dispensing build material in metered quantities and to precise target landing positions. It being readily understood by those of skill in the art, that other types of build material dispensers are also contemplated that can meter build material and accurately deliver it to a target position.
  • droplet as used herein is intended to cover individual or discrete volumes of build material that may be ejected, for example, by the piezoelectric jet.
  • droplet is also intended to cover a volumetrically modulated stream of build material, wherein small quantities or volumes of build material may be connected to adjacent volumes without becoming discrete entities, such as because of a relatively small gap or because of the speed of dispensed build material, for example.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)

Abstract

Article tridimensionnel constitué à partir d'un matériau consistant en une résine présentant un indice hydroxyle de 5 à 100 et un poids moléculaire supérieur à environ 500 et dissous dans au moins une sulfamide aromatique primaire. L'invention concerne également un procédé de façonnage d'un article tridimensionnel sur la base de données le définissant consistant: à transformer une solution de résine d'un indice hydroxyle de 5 à 100 et d'un poids moléculaire supérieur à environ 500 en gouttelettes projetées sur une plate-forme où elles se solidifient pour constituer l'article en couches successives conformément à des données de coordonnées tridimensionnelles.
PCT/US1995/012876 1994-10-19 1995-10-18 Materiau constitutif d'un article tridimensionnel WO1996013372A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU41932/96A AU4193296A (en) 1994-10-19 1995-10-18 Build material for forming a three dimensional article

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US32569494A 1994-10-19 1994-10-19
US08/325,694 1994-10-19

Publications (2)

Publication Number Publication Date
WO1996013372A2 true WO1996013372A2 (fr) 1996-05-09
WO1996013372A3 WO1996013372A3 (fr) 1996-06-27

Family

ID=23269016

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/012876 WO1996013372A2 (fr) 1994-10-19 1995-10-18 Materiau constitutif d'un article tridimensionnel

Country Status (2)

Country Link
AU (1) AU4193296A (fr)
WO (1) WO1996013372A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011828A1 (fr) * 1996-08-13 1997-04-03 Yalestown Corporation N.V. Procede de fabrication d'elements polymeres
US6132665A (en) * 1999-02-25 2000-10-17 3D Systems, Inc. Compositions and methods for selective deposition modeling

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4665492A (en) * 1984-07-02 1987-05-12 Masters William E Computer automated manufacturing process and system
DE3671460D1 (de) * 1985-06-25 1990-06-28 Howtek Inc Tinte fuer den tintenstrahldruck.
US5121329A (en) * 1989-10-30 1992-06-09 Stratasys, Inc. Apparatus and method for creating three-dimensional objects
US5230731A (en) * 1990-09-10 1993-07-27 Seiko Epson Corporation Hot-melt ink composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011828A1 (fr) * 1996-08-13 1997-04-03 Yalestown Corporation N.V. Procede de fabrication d'elements polymeres
US6132665A (en) * 1999-02-25 2000-10-17 3D Systems, Inc. Compositions and methods for selective deposition modeling
US6406531B1 (en) 1999-02-25 2002-06-18 3D Systems, Inc. Compositions and methods for selective deposition modeling

Also Published As

Publication number Publication date
AU4193296A (en) 1996-05-23
WO1996013372A3 (fr) 1996-06-27

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