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WO1998036323A9 - Polymeres performants a hautes temperatures et destines a la stereolithographie - Google Patents

Polymeres performants a hautes temperatures et destines a la stereolithographie

Info

Publication number
WO1998036323A9
WO1998036323A9 PCT/US1998/002679 US9802679W WO9836323A9 WO 1998036323 A9 WO1998036323 A9 WO 1998036323A9 US 9802679 W US9802679 W US 9802679W WO 9836323 A9 WO9836323 A9 WO 9836323A9
Authority
WO
WIPO (PCT)
Prior art keywords
polymer precursor
vinyl ether
liquid polymer
photoinitiator
precursor
Prior art date
Application number
PCT/US1998/002679
Other languages
English (en)
Other versions
WO1998036323A1 (fr
Filing date
Publication date
Priority claimed from US09/013,159 external-priority patent/US6054250A/en
Application filed filed Critical
Priority to AU62766/98A priority Critical patent/AU6276698A/en
Priority to EP98905054A priority patent/EP0960354A1/fr
Priority to JP53588498A priority patent/JP2001527590A/ja
Publication of WO1998036323A1 publication Critical patent/WO1998036323A1/fr
Publication of WO1998036323A9 publication Critical patent/WO1998036323A9/fr

Links

Definitions

  • This invention concerns the art of stereohthography, which is a technique for forming solid shapes from a liquid polymer precursor. More particularly, the invention relates to improvements in such polymer precursors.
  • the liquid polymer precursors of this invention produce green products having good strength at high glass transition temperatures. More particularly, this invention concerns a composition of matter useful in stereohthography that includes at least one vinyl ether, at least one epoxy, at least one acrylate and at least one photoinitiator.
  • this invention is a stereohthography polymer precursor solution that includes a pyrene sensitizer.
  • Stereohthography is described in U.S. Pat. No. 4,575,330 to Hull.
  • the method involves building up a predetermined three-dimensional shape by forming a series of layers of polymerized solids. A cross-section of the solid is traced out on the surface of a bath of polymer precursors under the direction of a computer controlled system which causes the liquid to be exposed to a form of radiation such as an ultraviolet laser. After each polymerized layer is formed, it is lowered in the bath so that a new layer can be formed on top.
  • Stereohthography solutions are disclosed in WO 89/08021 and U.S. Pat. No. 4,942,001.
  • the references disclose the use of a formulation which combines both acrylates and methacrylates.
  • the polymer precursor solution is comprised of resinous polyacrylates and polymethacrylates dissolved in liquid polyacrylates and polymethacrylates.
  • U.S. Pat. No. 4,844,144 discloses dispersing a thermoplastic material in a stereohthography liquid polymer precursor so that the solid formed by stereohthography contains a thermoplastic material.
  • a solid polymer is said to be useful in the investment casting process since the thermoplastic material prevents the acrylate polymer from expanding when the solid is burned out of a mold.
  • the acrylates and methacrylates used as polymer precursors are closely related to those disclosed in WO 89/08021 discussed above.
  • coatings intended for use in optical glass fibers were said to have application to stereohthography as well.
  • Such coatings included vinyl ether terminated polyurethane produced from certain diisocyanates reacting with polyols and then capping with monohydroxyl vinyl ethers.
  • WO 90/03989 addressed the use of vinyl ethers in stereohthography using a transvinylation reaction product to react with a diisocyanate to form urethane oligomers.
  • the transvinylation reaction converted a polyhydric alcohol into products having one or more of the hydroxyl groups in the alcohol converted to a vinyl ether group.
  • the mixture was then reacted with a diisocyanate via the residual hydroxyl groups to produce a vinyl ether urethane.
  • Vinyl ethers have been combined with epoxy compounds for use as coatings.
  • Crivello reported (Journal of Radiation Curing, Jan. 1983, p. 6-13) UV cure of vinyl ether-epoxy mixtures using cationic photoinitiators.
  • the faster curing of vinyl ethers was advantageous, while the epoxy compounds provided their inherent properties to the film.
  • stereohthography fabricated plastic parts An important and still frequently encountered problem in using stereohthography fabricated plastic parts is their capacity to soften and subsequently distort at moderately elevated temperatures. This phenomenon to distort when heated can usually be traced to a moderate or low glass transition temperature (Tg) (most stereohthography parts exhibit a Tg in the range of 50°C to 85°C) which, ultimately is a function of the polymer precursors used to fabricate the parts.
  • Tg glass transition temperature
  • Another problem with current high accuracy stereohthography resins including resins based on epoxy-polyol acrylate polymers is their water/humidity sensitivity. Water exposure leads to lower effective modulus of elasticity and lower dimensional accuracy rendering the stereohthography parts unsuitable for high temperature applications.
  • compositions useful in stereohthography have been sought, particularly with regard to improving the accuracy of the finished parts.
  • the present invention relates to improved stereohthography polymer precursor compositions which provide advantages over those previously disclosed.
  • One object of this invention is a liquid polymer precursor composition that is useful in a sterolithography process to manufacture solid articles that are not tacky to the touch.
  • Another object of this invention is a liquid polymer precursor composition that is useful in a stereohthography process to manufacture a solid article that has a glass transition temperature (Tg) greater than the boiling point of water.
  • Tg glass transition temperature
  • Yet another object of this invention is a liquid polymer precursor composition including vinyl ethers do not terminate polymerization by chain transfer.
  • Still another object of this invention is a liquid polymer precursor composition that produces a stereohthography product that is harder and less tacky than conventional stereohthography products.
  • a further object of this invention is a stereohthography polymer precursor that includes a pyrene sensitizer.
  • the liquid polymer precursor includes at least one vinyl ether functionalized compound, at least one epoxy functionalized compound, at least one acrylate functionalized compound, and an effective amount of at least one photoinitiator.
  • this invention is a liquid polymer precursor comprising from about 5 to about 15 weight percent of difunctional, and poly functional vinyl ether terminated monomers, oligomers and mixtures thereof, at least one cycloaliphatic diepoxy in an amount of from 4 to 7 times the amount of the vinyl ether present in the polymer precursor, at least one non-volatile diacrylate in an amount of from 3 to 5 times the amount of vinyl ether present in the polymer precursor, at least one cationic photoinitiator, at least one free radical photoinitiator, and at least one compound selected from an alcohol, a diol, a polyol, and mixtures thereof.
  • this invention is a process for forming a three- dimensional object from a liquid polymer precursor of this invention comprising repeatedly exposing the surface of a bath of said precursor to a beam of actinic light to solidify successive layers of said precursor to make a green structure. The green is then cured.
  • this invention is a cured stereohthography product manufactured using the liquid polymer precursors of this invention.
  • the present invention includes novel polymer precursor compositions useful in stereohthography.
  • the present invention is a method of manufacturing articles using the polymer precursor compositions of this invention in a stereohthography process.
  • This invention includes stereohthography parts having a glass transition temperatures greater than the boiling point of water that are manufactured using the compositions of this invention.
  • the polymer precursor compositions of this invention are useful in the manufacture of stereohthography parts with improved Glass Transition temperatures (Tg) as well as low water sensitivity and long shelf-life.
  • the polymer precursor compositions of this invention have a specific blend of vinyl ether, acrylate, and epoxy pre-polymers.
  • the terms "vinyl ether” "epoxy”, and acrylate” as used herein each refer to a single individual compound and mixtures of like compounds.
  • the compositions of this invention incorporate a novel photoinitiator package that improves the useful wavelength over which the polymer precursor compositions can be polymerized.
  • the polymer precursor compositions of this invention can be formed into a high melting point solid product using a stereohthography process.
  • the vinyl ether functionalized compounds useful in compositions of this invention include any vinyl ether composition including, but not limited to those described in U.S. Patent No. 5,510,226 which is incorporated herein by reference.
  • Vinyl ether functionalized compounds useful in the compositions of this invention include all vinyl ether terminated monomers and oligomers known to one of skill in the art to be useful in a stereohthography polymer precursor solutions and mixtures thereof.
  • Useful vinyl ethers have as many as possible of the following properties: fast cure under UV laser exposure, a relatively high modulus of elasticity as first formed by the laser beam; and have minimal absorption of light from the laser beam.
  • the vinyl ethers may be monofunctional, difunctional or polyfunctional vinyl ethers with difunctional and polyfunctional vinyl ether terminated monomers and oligomers being preferred. Most preferred are difunctional vinyl ethers capable of promoting a high modulus such as bis-(4-vinyloxy butyl) isophthalate.
  • Epoxy functionalized compounds useful in the compositions of this invention include any epoxy pre-polymers recognized by one having skill in the art as being useful in stereohthography polymer precursor solutions and mixtures thereof.
  • the epoxides which are most useful in the compositions of this invention should have as many of the following properties as possible: a functionality of at least two; a high cure rate relative to the vinyl ethers used in the formulation; contribute a low viscosity to the formulation; miscibility with the selected vinyl ethers; and minimal absorption of light from the selected laser beam.
  • Preferred epoxy functional groups include those derived from phenols, such as bisphenol A, novolacs, linear and cycloaliphatic diols, and of particular glycidyl ethers of phenols.
  • glycidyl ethers are bisphenol A diglycidyl ethers (e.g. DER 331, 332, Dow Chemical and Epon 828, Shell Chemical).
  • Other examples are epoxy novolacs (e.g. Quatrex 240, DEN 431, Dow Chemical) and epoxy cresols (e.g. Quatrex 3310, Dow Chemical).
  • Most preferred epoxy functionalized compounds are cycloaliphatic epoxy compounds and especially cycloaliphatic diepoxies.
  • Cycloaliphatic diepoxies are preferred because they effectively compete with vinyl ether functional groups for photo-generated acids.
  • the epoxy functionalized compounds scavenge the photo generated acids, in the preference to the vinyl ethers the vinyl ethers can effectively be incorporated into a growing radical initiated acrylate copolymer.
  • Tg's By permitting the vinyl ether to react to selectively form a vinyl ether acrylate copolymer higher product Tg's are attained.
  • useful cycloaliphatic epoxides include ERL-4221, ERL-4299, ERL-4234, manufactured by Union Carbide and:
  • acrylate functional groups include one or more acrylates and mixtures of acrylates and methacrylates.
  • Preferred acrylates functional compounds are moderate to low viscosity non-volatile acrylates with aromatic groups.
  • useful acrylates include EDBA, Ebecryl.
  • the acrylate used may be mono-, di-, tri- or polyfunctional acrylates or mixtures thereof. It is preferred that the acrylate is difunctional and a polyether ether or polyether acrylate. A most preferred acrylate is ethoxylated bisphenol diacrylate. It is also preferred that the chosen acrylate has a molecular weight of from about 300 to about 1000.
  • the relative amounts of vinyl ether, epoxy, and acrylate compounds in the polymer precursor compositions of this invention is important.
  • the vinyl ether undergoes a radical polymerization, a opposed to its generally more efficient cationic route (which is followed by the epoxies), which, in turn, gives high Tg thermoset stereohthography products with good flexibility and tack free surfaces in cured stereohthography parts.
  • An important aspect to this invention is the manner in which the VE is selectively and preferentially incorporated into the acrylate polymer. This is accomplished using a specific epoxy and adjusting the amount of acrylate and vinyl ether as well as the relative amounts of cationic photoinitiator to radical photoinitiators to achieve the desired polymerization route and rates.
  • the polymer precursor composition of this invention undergoes photopolymerization to form an interpenetrating network (LPN) consisting of a predominately acrylate-vinyl ether copolymer with an epoxy polymer.
  • LPN interpenetrating network
  • the highly cross- linked thermoset exhibit a high Tg and HDT.
  • the composition also shows flexibility/ductility, water insensitivity during photofabrication and after, low color, and fast photoresponse.
  • the preferred weights of the polymer precursor ingredients in the compositions of this invention are based upon the amount of vinyl ether in the composition.
  • the amount of vinyl ether functionalized compound in the composition should range from about 5 to about 25 weight percent and preferably from about 5 to about 15 weight percent vinyl ether in the final composition.
  • At least one epoxy functionalized compound is present in the composition in an amount ranging from about 2 to about 10 times the weight of vinyl ether, and preferably from about 4 to about 7 times the weight of vinyl ether functionalized compound in the composition.
  • the acrylate functionalized compound is present in the composition in an amount ranging from about 2 to about 8 times the weight of vinyl ether functionalized compound in the composition and preferably from about 3 to about 5 times the weight of the vinyl ether functionalized compound in the composition.
  • compositions of this invention include a photoinitiator.
  • the photoinitiator may be one or more compositions that are useful in initiating polymerzation of the composition of this invention upon excitation by a wavelength of radiation from about 300 to about 380 nm.
  • the photoinitiator is preferably a combination of at least one cationic photoinitiator and ate least one free radical photoinitiator.
  • a cationic photoinitiator is used to cause the epoxies to react and produce the desired polymer.
  • the recognized classes of cationic photoinitiators include various compounds which respond to irradiation by producing acid species capable of catalyzing cationic polymerization. See Crivello, Advances in Polymer Science, 62, p. 1-48 (1984).
  • Onium salts of Group V, VI, and VII elements are stated to be the most efficient and versatile of the cationic photoinitiators. They generate strong Lewis acids which can promote cationic polymerization. Curing the compositions of the invention is not limited to a particular class of such photoinitiators, although certain types are preferred, including onium salts based on halogens and sulfur.
  • Preferred photoinitiators are triarylsulfonium salts, and diaryliodonium salts.
  • Preferred anions are hexafluorophosphate and hexafluoroantimony.
  • the composition of this invention will include from about 0.1 to about 2.0 pph of a cationic photoinitiator and preferably from about 0.5 to about 1.5 phh of a cationic photoinitiator.
  • cationic photoinitiator depends on the excitation wavelength. For example at a wavelength of 324 nm triaryl sulfonium hexafluoroantimonate salts are useful and above 355 nm orN 2 Y0 4 is useful. Most preferred cationic photoinitiators include Ar 3 S + SbF 6 ' A I " coupled with phosphate or antiminate counterions, and mixtures thereof either alone or in combination with other photoinitiators such as phosphate salts, sulfonium salts and iodonium salts.
  • the photoinitiator package used to form multi-layered SL parts from the vinyl/acrylate/ epoxy polymer precursor compositions will preferably include a free radical photoinitiator (for example, a substituted acetophenone) in addition to or in lieu of a cationic photoinitiator.
  • a free radical photoinitiator is useful for promoting free radical polymerization and typically absorbs light in the mid UV range of from 300-360 nm and undergoes Norrish Type I photocleavage.
  • useful radical photoinitiators include the free radical photoinitiator will preferably be present in the compositions of this invention in amount ranging from about 0.5 to about 4.0 wt% and preferably from about 1.0 to about 2.0 wt %.
  • Quinones such as 2-ethyl anthraquimone, 2-t-butyl anthraquinone, octamethyl althraquinone, and 1,2-benzanthraquinone; ⁇ -ketaldonyl alcohols or others such as benzoin,
  • ketones such as -phenyl benzoin, ⁇ - ⁇ '-diethoxy acc(ophenone, benzophenone, 4,4'-bisdialkylamino benzopherione; thioxamthoric derivates; 2,4,5-triaryl imidazolyl dimers and the like.
  • ketones such as -phenyl benzoin, ⁇ - ⁇ '-diethoxy acc(ophenone, benzophenone, 4,4'-bisdialkylamino benzopherione; thioxamthoric derivates; 2,4,5-triaryl imidazolyl dimers and the like.
  • compositions of this invention preferably include at least one alcohol, diol, or polyol.
  • Alcohols, diols, and polyols facilitate the speed of epoxy crosslinking reaction which lowers the Tg of the resulting stereohthography matrix thereby improving the flexibility of resulting product.
  • Any alcohol, polyether diol or polyol may be used in the compositions of this invention.
  • Diols are preferred, however to keep the hydroxy functionally low. It is also preferred that diols and polyols with a molecular weight of at least 200 are and most preferably greater than 500 are used in the composition.
  • Alcohols, diols, polyols and mixtures thereof will preferably be included in composition of this invention in amounts ranging from about 5.0 to about 15.0 weight percent.
  • the polymer precursor composition of this invention may include a stabilizer to maintain good vat-life stability.
  • a useful stabilizer should be a weak Lewis base.
  • an aromatic sensitizer and, in particular, pyrene, significantly enhances the cationic cure rate of all types of stereohthography polymer precursor solutions.
  • the aromatic sensitizer provides a more efficacious solution gel point using less light.
  • Pyrene has heretofore never been appreciated as a useful stereohthography polymer precursor sensitizer.
  • the preferred pyrene sensitizer should be present in a polymer precursor solution in an amount ranging from about 0.05 to about 0.5 pph, and preferably from about 0.1 to about 0.3 pph.
  • compositions of this invention should have a viscosity in the range of 200 to about 10,000 centipoise and preferably from 200-800 centipoise.
  • the viscosity of the formulation are low to facilitate the movement of the liquid prepolymers over the solid piece being formed by the stereohthography apparatus.
  • the formulations may also contain dyes, stabilizers, fillers, pigments, and antioxidants such as hindered phenols, wetting agents such as fluorosurfactants e.g. FC-430 from 3-M, photosensitizers such as benzophenone, thioxanthone, perylene and other components familiar to those skilled in the art.
  • the vinyl ether acrylate/epoxy formulations of this invention may be polymerized by exposure to known sources of energy such as electron beams, ultraviolet light, high temperatures, and the like.
  • the polymer formulation forms a liquid bath in which the precursors are polymerized in successive layers, typically by repeated exposure to actinic light, particularly a UV or visible laser beam, such as ultraviolet light from helium/cadmium laser or an argon ion laser or visible light from an argon ion laser.
  • actinic light particularly a UV or visible laser beam
  • ultraviolet light from helium/cadmium laser or an argon ion laser or visible light from an argon ion laser After the three-dimensional shape has been formed, it is removed from the bath, washed as necessary with isopropanol or other suitable solvent, and cured further by thermal means, which could be supplemented by ultraviolet or visible light means if desired.
  • compositions of this invention having the formulas reported in Table I below were prepared by combining the ingredients in a container. The order of incorporation of the
  • compositions were coated on a glass plate and cured by UV irradiation at 500
  • This Example evaluates the effect of adding a pyrene stabilizer to a stereohthography precursor composition.
  • Two polymer precursor compositions of this invention, one with pyrene stabilizer, and one without were coated onto a glass plate, exposed to actinic light, and cured according to the method described in Example 1.
  • the compositions and test results are reported in Table 3, below.
  • test results indicate that polymer precursor solutions stabilized with pyrene maintain their viscosities, i.e, are protected against cross-linking and polymerization in comparison to the same polymer precursor solution that contains no pyrene.

Abstract

La présente invention concerne des précurseurs de polymères utilisés dans la stéréolithographie, et elle concerne notamment une nouvelle résine possédant une température de transition vitreuse (Tg) sensiblement supérieure à celle des résines existantes. Ces précurseurs de polymères comprennent un ajout d'un mélange d'au moins un composé éther vinylique fonctionnalisé et d'au moins un composé époxy fonctionnalisé, au moins un composé acrylate fonctionnalisé ainsi qu'un photoamorceur. L'invention est caractérisée en ce que la composition du précurseur de polymère durcit selon un double processus de durcissement mettant en oeuvre un système de radicaux libres ainsi qu'un système cationique, ce qui permet d'obtenir une résistance en vert améliorée.
PCT/US1998/002679 1997-02-14 1998-02-13 Polymeres performants a hautes temperatures et destines a la stereolithographie WO1998036323A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU62766/98A AU6276698A (en) 1997-02-14 1998-02-13 High temperature performance polymers for stereolithography
EP98905054A EP0960354A1 (fr) 1997-02-14 1998-02-13 Polymeres performants a hautes temperatures et destines a la stereolithographie
JP53588498A JP2001527590A (ja) 1997-02-18 1998-02-13 ステレオリソグラフィのための耐熱性ポリマー

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US3841897P 1997-02-18 1997-02-18
US1370098A 1998-01-26 1998-01-26
US09/013,700 1998-01-26
US09/013,159 1998-01-26
US09/013,159 US6054250A (en) 1997-02-18 1998-01-26 High temperature performance polymers for stereolithography
US60/038,418 1998-01-26

Publications (2)

Publication Number Publication Date
WO1998036323A1 WO1998036323A1 (fr) 1998-08-20
WO1998036323A9 true WO1998036323A9 (fr) 1999-02-04

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EP (1) EP0960354A1 (fr)
JP (1) JP2001527590A (fr)
WO (1) WO1998036323A1 (fr)

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US6100007A (en) * 1998-04-06 2000-08-08 Ciba Specialty Chemicals Corp. Liquid radiation-curable composition especially for producing cured articles by stereolithography having high heat deflection temperatures
US6379866B2 (en) * 2000-03-31 2002-04-30 Dsm Desotech Inc Solid imaging compositions for preparing polypropylene-like articles
US6762002B2 (en) 1998-07-10 2004-07-13 Dsm Desotech, Inc. Solid imaging compositions for preparing polypropylene-like articles
US6287748B1 (en) * 1998-07-10 2001-09-11 Dsm N.V. Solid imaging compositions for preparing polyethylene-like articles
CA2398160A1 (fr) * 2000-02-08 2001-08-16 Vantico Ag Composition liquide durcissable par rayonnement, destinee notamment a la stereolithographie
JP4743736B2 (ja) * 2001-08-31 2011-08-10 株式会社Adeka 光学的立体造形用樹脂組成物およびこれを用いた光学的立体造形方法
US6777027B2 (en) 2002-10-08 2004-08-17 Rohm And Haas Company Coating powders for smooth, low gloss finishes, and powder coatings formed therefrom
US6890997B2 (en) 2002-10-08 2005-05-10 Rohm And Haas Company Powder coating of free radical curable epoxy resin and another free radical curable resin
US7696260B2 (en) * 2006-03-30 2010-04-13 Dsm Ip Assets B.V. Cationic compositions and methods of making and using the same
KR101486692B1 (ko) * 2009-06-08 2015-01-29 산요가세이고교 가부시키가이샤 감광성 조성물
CA2950215A1 (fr) 2014-06-23 2015-12-30 Carbon, Inc. Resines de polyurethane presentant de multiples mecanismes de durcissement destinees a etre utilisees dans la production d'objets tridimensionnels
CN107428092B (zh) 2015-03-19 2021-06-08 陶氏环球技术有限责任公司 使用光调节自由基聚合的增材制造方法
US10975193B2 (en) * 2015-09-09 2021-04-13 Carbon, Inc. Epoxy dual cure resins for additive manufacturing
US10316213B1 (en) 2017-05-01 2019-06-11 Formlabs, Inc. Dual-cure resins and related methods

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JP2898761B2 (ja) * 1990-12-27 1999-06-02 旭電化工業株式会社 光学的造形用樹脂組成物
JP2667934B2 (ja) * 1991-05-01 1997-10-27 アライド−シグナル・インコーポレーテッド ビニルエーテル−エポキシドポリマー類を用いた立体リソグラフィー
TW269017B (fr) * 1992-12-21 1996-01-21 Ciba Geigy Ag
US5639413A (en) * 1995-03-30 1997-06-17 Crivello; James Vincent Methods and compositions related to stereolithography
JP3724893B2 (ja) * 1996-09-25 2005-12-07 ナブテスコ株式会社 光学的立体造形用樹脂組成物

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