WO1989008021A1 - Stereolithographie utilisant une composition assurant une distortion reduite - Google Patents

Stereolithographie utilisant une composition assurant une distortion reduite Download PDF

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Publication number
WO1989008021A1
WO1989008021A1 PCT/US1989/000774 US8900774W WO8908021A1 WO 1989008021 A1 WO1989008021 A1 WO 1989008021A1 US 8900774 W US8900774 W US 8900774W WO 8908021 A1 WO8908021 A1 WO 8908021A1
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WIPO (PCT)
Prior art keywords
liquid
polyacrylate
polymethacrylate
ultraviolet
reservoir
Prior art date
Application number
PCT/US1989/000774
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English (en)
Inventor
John J. Krajewski
Edward J. Murphy
Robert E. Ansel
Original Assignee
Desoto, 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 Desoto, Inc. filed Critical Desoto, Inc.
Priority to JP1502790A priority Critical patent/JP2931608B2/ja
Publication of WO1989008021A1 publication Critical patent/WO1989008021A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0037—Production of three-dimensional images
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B29C39/006—Monomers or prepolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material

Definitions

  • This invention relates to the production of stereolithographically formed elements which are complexly-shaped usually thin-walled polymeric objects and which are incompletely cured as a result of having been produced by an exposure to actinic light, usually in or near the ultraviolet range, which is inadequate to completely cure the polymer constituting the objects.
  • the thin walled object is incompletely cured and has inadequate strength and durability.
  • these stereolithographic processes are intended to form three dimensional models which conform as accurately as possible with what was intended, this usually being set forth in drawings which are cross-sectioned by computer to guide a laser beam in the production of the superposed layers.
  • drawings which are cross-sectioned by computer to guide a laser beam in the production of the superposed layers.
  • the incompletely cured products tend to be somewhat distorted, so the accuracy of the model is less than desired.
  • the ultraviolet lasers used have limited capacity, so a larger exposure dosage would slow the stereolithographic process. Moreover, a greater exposure would increase the thickness and depth of the exposed line which solidifies, thus reducing the dimensional accuracy of the stereolithographic process.
  • the objects under consideration are formed by the ultraviolet polymerization of liquid ultraviolet-curable ethylenically unsaturated material at the surface of a liquid reservoir of such material using an ultraviolet dosage in the range of 1-15, preferably 1-5, Joules per square centimeter which is sufficient to convert the unsaturated liquid into a lightly cross-linked solvent-swellable three dimensional complexly-shaped polymeric thin-walled element constituted by incompletely polymerized solid polymer.
  • a support is positioned beneath the surface of the reservoir to hold the polymerized layer which is formed. The liquid level is then raised, or the support lowered, and another layer is formed until the photoformed object is completed within the liquid reservoir.
  • the photoformed objects are thus only partially cured and are mechanically weak due to the low degree of cross-linking and the presence of unconverted monomers and oligomers (which are still unsaturated) within the partially polymerized polymeric structure of the solid object which is formed.
  • the problem here is to provide a flowable liquid composition which cures rapidly on exposure to light of appropriate wavelength to speed the stereolithographic process but which, at the same time, exhibits less distortion in its partially cured condition so that the gelatinous and weak solid products produced by ultraviolet exposure will more accurately reflect the shape of the object which it is desired to reproduce.
  • thermoset the photoformed incompletely cured and mechanically weak objects after they have been removed from the liquid ultraviolet-curable ethylenically unsaturated material in which they were formed.
  • the distortion which is encountered is primarily a change in shape, and this is easily measured in various ways, albeit no special measurement technique is advocated herein. Disclosure of Invention
  • the ultraviolet-curable liquid ethylenically unsaturated composition which is used in the stereolithographic process is formulated to include from about 20% to about 80%, preferably from 35% to 70%, of a resinous polyacrylate or polymethacrylate.
  • This resinous polyacrylate or polymethacrylate is dissolved in from about 80% to about 20%, preferably from 65% to 30%, of a liquid polyacrylate or polymethacrylate.
  • polyacrylate and “polymethacrylate” identify a plurality of acrylic acid or methacrylic acid ester groups. The proportions are by weight based on the weight of the unsaturated material present.
  • the ultraviolet-curable liquid composition which is used is formulated to include from 20% to 80%, preferably from 35% to 70%, of a resinous polyacrylate or polymethacrylate.
  • This resinous polyacrylate or polymethacrylate is dissolved in a combination of 10% to 40%, preferably from 15% to 30%, of a liquid polyacrylate or polymethacrylate, and 10% to 40%, preferably from 15% to 30%, of a liquid N-vinyl monomer. It is important that one of the foregoing liquid and resinous polyacrylates or polymethacrylates be a polyacrylate and that the other be a polymethacrylate. If both were polymethacrylates, the composition would cure too slowly. If both were polyacrylates, then severe distortion is seen.
  • the resinous material is selected to contain one of the two specified types of ethylenic unsaturation and the liquid material is selected to provide the other type of ethylenic unsaturation that it is found that good cure speed is accompanied by good distortion resistance.
  • liquid or non-liquid unsaturated materials can be present in the liquid composition so long as they do not change the essential character of the combination of resinous and liquid poly(meth)acrylate.
  • the above-described unsaturated liquid compositions are employed as a liquid reservoir which forms a thin liquid layer above a supporting platform, and the surface of this liquid reservoir is usually exposed to an ultraviolet dosage in the range of 1-15, preferably 1-5, Joules per square centimeter to partially cure the liquid at the surface. This process is repeated many times to superimpose one layer upon another and ultimately produce a three-dimensional object of partially cross-linked polymer within the liquid reservoir.
  • the specified exposure to light is sufficient to convert the unsaturated liquid into a lightly cross-linked solvent-swellable three dimensional complexly-shaped polymeric usually thin-walled element constituted by heat-softenable solid polymer.
  • the photoformed objects are incompletely cured and mechanically weak due to the low degree of cross-linking and the presence of unconverted monomers and oligomers (which are still unsaturated) within the partially polymerized polymeric structure of the solid object which is formed.
  • the liquid compositions specified are found to cure rapidly to a dimensionally stable solid (rigid) condition which exhibits reduced distortion.
  • the resinous polyacrylate or polymethacrylate provides a polymeric matrix which allows the ultimately fully cured rigid object to have the structural strength which is desired, and liquid polyacrylate or polymethacrylate provides the liquidity needed to have the easily flowable liquid which is required by the process.
  • the specified liquid polyacrylates or polymethacrylates which are preferably illustrated by trimethylol propane trimethacrylate and pentaerythritol trimethacrylate, or the corresponding triacrylates, serve to reduce the distortion encountered in going from the drawings which activate the computer-directed laser beam and the three dimensional model which is formed in the liquid reservoir.
  • the resinous component is combined with two other components which provide the liquidity needed to have the easily flowable liquid which is desired by the process.
  • One of these two components, the N-vinyl monomer, is rapid curing to enable the rapid achievement of "green strength"
  • the specified liquid polyacrylates or polymethacrylates which are preferably illustrated by trimethylol propane trimethacrylate and pentaerythritol trimethacrylate, or the corresponding triacrylates, serve to reduce the distortion encountered in going from the drawings which activate the computer-directed laser beam and the three dimensional model which is formed in the liquid reservoir.
  • the resinous polyacrylate or polymethacrylate which provides a polymeric matrix enabling the ultimately fully cured rigid object to have its structural strength is subject to considerable variation so long as it is of resinous nature and contains an average of at least 2.0 acrylate or methacrylate groups per molecule.
  • Resinous character generally denotes relatively viscous and sticky materials, and these generally have a molecular weight of at least about 500.
  • epoxy diacrylates such as Epon 1001 diacrylate or Epon 828 diacrylate, or one can use polyester diacrylates or polyurethane diacrylates.
  • Epon epoxy resins are diglycidyl ethers of bisphenol A, Epon 828 having a number average molecular weight of about 390 and Epon 1001 having a number average molecular weigh tof about 1,000.
  • the corresponding methacrylate resins are also useful, but less preferred. Further useful materials are disclosed in the Examples.
  • blends of polyacrylate resins and polymethacrylate liquids are the preferred blends.
  • the polyacrylate resins which are now preferred are polyurethane diacrylates, and especially those which employ a polyester base. More particularly, one can take an hydroxy-functional polyester, preferably one having an average of from 2.1-5.0 hydroxy groups per molecule, and react it with monoacrylate monoisocyanate to form an acrylate-capped polyurethane polyacrylate.
  • hydroxy-functional polyester preferably one having an average of from 2.1-5.0 hydroxy groups per molecule
  • monoacrylate monoisocyanate to form an acrylate-capped polyurethane polyacrylate.
  • Uvithane 893 from Morton Thiokol, Inc., Chicago, IL
  • the preferred N-vinyl liquid monomer is N-vinyl pyrrolidone, and N-vinyl caprolactam is also useful.
  • liquid polymethacrylate As previously indicated, it is preferred to combine a resinous polyacrylate with a liquid polymethacrylate. While liquid trimethacrylates are preferred, such as trimethylol propane trimethacrylate, dimethacrylates are also useful, such as 1,6-hexane diol dimethacrylate. Liquid polymethacrylates of higher functionality are also useful, such as pentaerythritol tetramethacrylate. When the resinous material is a polymethacrylate, the liquid material must be a polyacrylate, and 1,6-hexane diacrylate and polyacrylates of high functionality, like trimethylol propane triacrylate and pentaerythritol tetraacrylate, can be used in such instance.
  • the liquid materials which are intended are free flowing and generally have a molecular weight of less than about 350.
  • compositions of this invention may include materials other than those which have been identified as essential herein, such as liquid monoacrylates and monomethacrylates, or other liquid or resinous materials of diverse nature. So long as the specified proportions of the two essential components are selected as taught herein, these other materials do not change the reduction in distortion achieved herein.
  • photoinitiators effective on ultraviolet exposure to initiate the polymerization of acrylate unsaturation is included in the reservoir, albeit a liquid composition of this invention can be supplied without the photoinitiator which is added by the user prior to use.
  • photoinitiators are themselves well known and in common use. They are usually ketonic, and frequently aromatic, such as benzophenone. It is presently preferred to use the phenyl ketone photoinitiators shown in the examples. It will be appreciated that photoinitiators for the ultraviolet polymerization of (meth)acrylate functional compounds are well known and in common use.
  • the 3-dimensional model (object) As will be understood, after the 3-dimensional model (object) has been formed within the liquid reservoir, it is withdrawn and excess unsaturated liquid is allowed to drain therefrom, usually back into the reservoir from which it was withdrawn where it can be reused. If desired, one can wash the incompletely cured solid model with an alcoholic liquid before proceeding to complete the cure, but this is usually dispensed with and is not necessary.
  • the draining operation is a simple one which can be carried out at room or slightly elevated temperature to reduce the viscosity of the unconverted liquid adhering to the photoformed object. It is convenient to allow the object to drain for periods of from 5 to 10 minutes, albeit this is not critical.
  • the removal of polymerizable liquid clinging to the photoformed object can be aided by rinsing with an alcoholic solvent having the capacity to dissolve the polymerizable liquid, but which does not dissolve the partially polymerized solid formed from that liquid, albeit present practice does not usually employ such a wash.
  • a typical alcoholic solvent is represented by an alcohol, such as isopropanol. If desired, one can add a minor proportion of an ester solvent, such as butyl acetate. Other useful alcohols are illustrated by ethyl alcohol and butanol. When water-miscible solvents are used, water can be present in the solvent mixture.
  • the time of immersion in the alcoholic wash composition is of secondary significance, albeit it is convenient to immerse the object in the solvent at room temperature for from 5 to 30 seconds to dissolve the adhering polymerizable liquid.
  • the partially cured object is then removed and adhering solvent is allowed to drain therefrom.
  • Completion of the cure can be carried out in various ways. Most simply, the drained (and possibly washed) solid object is placed in an ultraviolet chamber and exposed uniformly to ultraviolet radiation to complete the cure. Other techniques can be used for completing the cure, such as employing other more pentrating radiation or heat, and any of these can be used. It will be understood, however, that the specific technique employed to increase the strength of the incompletely polymerized object withdrawn from the polymerizable liquid reservoir is not itself of importance in this invention.
  • compositions of this invention cure well when exposed to a temperature of about 250°F, and this is unusual.
  • a thermal cure at a temperature up to about 325°F is thus surprisingly effective and is a feature of this invention.
  • the baking temperature will not exceed about 300°F to insure avoidance of distortion during the cure.
  • the thermal cure is advantageous since heat permeates all portions of the three dimensional object whereas exposure of that object to ultraviolet light might not reach all portions of the object.
  • compositions of this invention cure well when exposed to elevated temperature, temperatures in the range of 325°F to
  • thermo cure is advantageous since heat permeates all portions of the three dimensional object whereas exposure of that object to ultraviolet light might not reach all portions of the object.
  • the removal of polymerizable liquid clinging to the photoformed object can be aided by rinsing with an alcoholic solvent having the capacity to dissolve the polymerizable liquid, but which does not dissolve the partially polymerized solid formed from that liquid, albeit present practice does not usually employ such a wash.
  • a typical alcoholic solvent is represented by an alcohol, such as isopropanol. If desired, one may add a minor proportion of an ester solvent, such as butyl acetate. Other useful alcohols are illustrated by ethyl alcohol and butanol. When water-miscible solvents are used, water may be present in the solvent mixture.
  • the time of immersion in the alcoholic wash composition is of secondary significance, albeit it is convenient to immerse the object in the solvent at room temperature for from 5 to 30 seconds to dissolve the adhering polymerizable liquid.
  • the partially cured object is then removed and adhering solvent is allowed to drain therefrom.
  • (meth)acrylate-functional photocurable liquid which is useful to provide the bath of liquid ultraviolet-curable ethylenically unsaturated material the surface of which is exposed to ultraviolet radiation in accordance with this invention was provided by mixing 60 grams of a polyacrylate-functional polyurethane polyester resin (hydroxy-terminated polyester of ethylene glycol and adipic acid (number average molecular weight of 1500) reacted with isophorone diisocyanate and then capped with 2-hydroxyethyl acrylate (Uvithane 893 from Morton Thiokol can be used]), 40 grams of trimethylol propane trimethacrylate, and 4 grams of a benzyl ketal-based photoinitiator (2-hydroxypropyl phenone [Darocur 1173 from EM Chemicals can be used]).
  • a polyacrylate-functional polyurethane polyester resin hydroxy-terminated polyester of ethylene glycol and adipic acid (number average molecular weight of 1500) reacted with isophor
  • Another photoinitiator which is fully useful in this example in the same proportion is 1-hydroxycyclohexyl phenyl ketone available from Ciba-Geigy Corporation, Ardsley, NY, under the trade designation Irgacure 184.
  • the liquid bath of the above photopolymerizable liquid was exposed to ultraviolet light using a Liconix model 4240 N, helium-cadmium light having an output of 15 milliwatts at 325 nanometers focused to 350 micron diameter.
  • the usually used dosage is about 3.0 Joules per square centimeter of surface which results in test specimens of about 20 mil thickness.
  • the drained piece can be washed briefly in an alcoholic solvent mixture of isopropanol and butyl acetate in a weight ratio of 64/33 to facilitate complete removal of polymerizable liquid, but in this example washing was not employed.
  • the drained parts were then exposed to ultraviolet light in a sealed chamber to provide a post-cure, and the exposure was continued until the parts are as fully cured as desired.
  • the drained parts must be rigid enough to avoid distortion when handled and subjected to additional cure. After such additional cure, the cured parts are expected to sustain some significant load without distortion.
  • the above example is also repeated by mixing 60 grams of a polymethacrylate-functional resin (the dimethacrylate of Shell Chemical Company product Epon 1001 which is a diglycidyl ether of bisphenol A having a number average molecular weight of about 1000) 40 grams of trimethylol propane triacrylate, and 4 grams of a benzyl ketal-based photoinitiator (2-hydroxypropyl phenone [Darocur 1173 from EM Chemicals can be used]). Corresponding results are obtained.
  • a polymethacrylate-functional resin the dimethacrylate of Shell Chemical Company product Epon 1001 which is a diglycidyl ether of bisphenol A having a number average molecular weight of about 1000
  • a further illustration of a (meth)acrylate-functional photocurable liquid which is useful to provide the bath of liquid ultraviolet-curable ethylenically unsaturated material is provided by mixing 50 grams of a resinous diacrylate of a bisphenol A-based diepoxide (a diglycidyl ether of bisphenol A having a molecular weight of about 390 reacted with 2 molar proportions of acrylic acid [the Celanese Corporation, Louisville, KY, product Celrad 3700 can be used]), 15 grams of a dimethacrylate of a bisphenol A-based diepoxide (the dimethacrylate of the same diglycidyl ether used in Celrad 3700) [the Celanese product RDX 26936 can be used]), 25 grams of liquid tetraethylene glycol dimethacrylate (the Sartomer Company,
  • (meth)acrylate-functional photocurable liquid which is useful to provide the bath of liquid ultraviolet-curable ethylenically unsaturated material useful in this invention is provided by mixing 50 grams of a resinous diacrylate of a bisphenol A-based diepoxide (the Celanese product Celrad 3700 can be used), 21 grams of liquid tetraethylene glycol dimethacrylate (Sartomer 209), 17 grams of methoxy hexane diol monoacrylate, 8 grams of liquid hexane diol dimethacrylate (Sartomer SR 239), 4 grams of an oligomer amine monoacrylate (Celrad 7100 from Celanese), 4 grams of a benzyl ketal-based photoinitiator (2-hydroxypropyl phenone [Darocur 1173 from EM Chemicals can be used]), and 0.1 grams of methoxy phenol (from Eastman Kodak
  • (meth)acrylate-functional photocurable liquid which is useful to provide the bath of liquid ultraviolet-curable ethylenically unsaturated material useful in this invention is provided by mixing 34 grams of a resinous diacrylate of a diglycidyl ether of bisphenol A having a number average molecular weight of about 390 (the Cargill Incorporated, Carpenterville, IL, product PN 1570 can be used) , 33 grams of a liquid dimethacrylate of a bisphenol A-based ethoxylate (Sartomer SR 348 can be used) , 33 grams of the reaction product of isocyanatoethyl methacrylate from Dow Chemical Company, Midland MI, and 2-ethyl hexanol from Aldrich, 4 grams of a benzyl ketal-based photoinitiator (2-hydroxypropyl phenone [Darocur 1173 from EM Chemicals can be used]), 2 grams of ethyl diethanol amine (from Aldrich),
  • Still another illustration of a (meth)acrylate-functional photocurable liquid which is useful to provide the bath of liquid ultraviolet-curable ethylenically unsaturated material is provided by mixing 34 grams of a resinous diacrylate of a diglycidyl ether of bisphenol A having a number average molecular weight of about 390 (the Cargill Incorporated, Carpenterville, IL, product PN 1570 can be used), 33 grams of a liquid dimethacrylate of a bisphenol A-based ethoxylate (Sartomer SR 348 can be used), 33 grams of liquid tetraethylene glycol dimethacrylate (Sartomer SR 209), 4 grams of a benzyl ketal-based photoinitiator (2-hydroxypropyl phenone [Darocur 1173 from EM
  • a further illustration of a (meth)acrylate-functional photocurable liquid which is useful to provide the bath of liquid ultraviolet-curable ethylenically unsaturated material is provided by mixing 30 grams of a diacrylate-functional urethane polyester resin ( ⁇ vithane 783 from Morton Thiokol can be used), 30 grams of liquid trimethylol propane ethoxylate triacrylate (SR 454 from Sartomer), 40 grams of liquid tetraethylene glycol dimethacrylate, (Photomer 2050 from Henkel Corporation, Morristown, NJ can be used), 4 grams of a benzyl ketal-based photoinitiator (2-hydroxypropyl phenone [Darocur 1173 from EM Chemicals can be used]), and 0.1 grams of methoxy phenol (from Eastman Kodak Company).
  • This composition is fully useful in this invention and exhibits reduced distortion in comparison with the use of a similar all acrylate-functional composition.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Un procédé de stéréolithographie permettant de former un objet tridimensionnel à parois minces consiste à exposer de manière répétée la surface d'un réservoir de matière liquide non saturée par de l'éthylène durcissable aux rayons ultraviolets, à une lumière actinique se situant dans ou près de la plage des rayons ultraviolets, afin de solidifier le liquide proche de la surface pour former une pluralité de couches superposées de matériau polymère tridimensionnel de forme complexe pouvant être gonflé par du solvant et légèrement réticulé, à retirer l'élément du réservoir, tout en drainant le liquide polymérisable excédentaire, et à durcir complétement ledit élément afin de le rigidifier et de le renforcer. La composition se trouvant dans le réservoir se compose d'un photoexcitant et d'environ 20 à 80 % de polyacrylate résineux ou de polymétacrylate dissous dans environ 80 à 20 % de polyacrylate ou de polyméthacrylate liquide, les pourcentages étant basés sur le poids de matière non saturée présente, l'une des matières précitées étant le polyacrylate et le reste un polyméthacrylate. On préconise de remplacer le polyacrylate ou polyméthacrylate liquide par 10 à 45 % de polyacrylate ou polyméthacrylate liquide et 10 à 45 % de monomère de N-vinyle liquide combinés.
PCT/US1989/000774 1988-03-02 1989-03-01 Stereolithographie utilisant une composition assurant une distortion reduite WO1989008021A1 (fr)

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Application Number Priority Date Filing Date Title
JP1502790A JP2931608B2 (ja) 1988-03-02 1989-03-01 変形を軽減させうる組成物を用いる立体造形法

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Application Number Priority Date Filing Date Title
US162,983 1980-06-25
US16298388A 1988-03-02 1988-03-02
US28542888A 1988-12-16 1988-12-16
US285,428 1988-12-16

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Cited By (13)

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WO1992002572A1 (fr) * 1990-07-30 1992-02-20 Dsm N.V. Compositions contenant des melanges reactifs et associatifs
US5437964A (en) * 1991-05-01 1995-08-01 Alliedsignal Inc. Stereolithography using vinyl ether-epoxide polymers
US5498782A (en) * 1993-09-08 1996-03-12 Union Carbide Chemicals & Plastics Technology Corporation Distortion control additives for ultraviolet-curable compositions
US5506087A (en) * 1991-02-27 1996-04-09 Alliedsignal Inc. Stereolithography using vinyl ether based polymers
US5510226A (en) * 1991-05-01 1996-04-23 Alliedsignal Inc. Stereolithography using vinyl ether-epoxide polymers
US5674921A (en) * 1992-07-17 1997-10-07 Ethicon, Inc. Radiation-curable, urethane-acrylate prepolymers and crosslinked polymers
US5705316A (en) * 1993-09-16 1998-01-06 Ciba Specialty Chemicals Corporation Vinyl ether compounds having additional functional groups other than vinyl ether groups and the use thereof in the formulation of curable compositions
US6025114A (en) * 1995-03-11 2000-02-15 Zeneca Limited Liquid photocurable compositions
US6054250A (en) * 1997-02-18 2000-04-25 Alliedsignal Inc. High temperature performance polymers for stereolithography
US6600965B1 (en) 1988-04-18 2003-07-29 3D Systems, Inc. Method and apparatus for production of high resolution three-dimensional objects by stereolithography
US20140129019A1 (en) * 2003-11-14 2014-05-08 Drexel University Methods and apparatus for computer-aided tissue engineering for modeling, design and freeform fabrication of tissue scaffolds, constructs, and devices
US20210001539A1 (en) * 2019-07-02 2021-01-07 Microsoft Technology Licensing, Llc Dynamic balancing of additively manufactured impellers
US11492505B2 (en) 2016-10-28 2022-11-08 Covestro (Netherlands) B.V. Thermosetting compositions and forming three-dimensional objects therefrom

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