High temperature three-dimensional printing compositions

{
  "publication_number": "US9873761B1",
  "country": "US",
  "kind": "B1",
  "title": "High temperature three-dimensional printing compositions",
  "abstract": "A thermosetting resin composition has particular applications in three dimensional (3-D) printing. The thermosetting resin composition exhibits high performance and is characterized by a high temperature two stage cure resin composition. The thermosetting resin composition comprises cyanate esters and other high temperature resins, photo curable monomers, photo initiator, metal catalyst or ionic liquid catalyst. The thermosetting resin composition cures at room temperature to form 3-D objects and upon further post cure these objects exhibit high temperature properties enabling use at temperatures exceeding 150 C.",
  "claims": [
    "1. A high performance and high temperature resin composition for three dimensional printing formed from a two stage cure comprising a first stage curable group (Component A), a second stage curable group cured by thermal/heat cure (Component B); wherein Component A is selected from a photo-curable group, a peroxide curable group, an electron beam (EB) curable group, a cationic curable group, an IR curable group, an addition cure group, a condensation reactive group, and/or a chemical additive curable group; wherein Component A further comprises a second reactive group pre-reacted with Component B to generate a homogenous resin at room temperature having viscosity as low as about 100 mPA*s and suitable for three-dimensional printers; wherein Component B is selected from a cyanate ester, bismaleimide (BMI), benzoxazine, polyimide, phthalonitrile resin (PN), bismaleimide triazine (BT), silicone resin, epoxy, cyanate epoxy and mixtures thereof.",
    "2. The resin composition of claim 1, wherein said viscosity ranges from about 100 mPa*s to 100000 mPa*s at room temperature.",
    "3. The resin composition of claim 1, wherein said viscosity ranges from about 34 mPa*s to 712 mPa*s at 40° C.",
    "4. The resin composition of claim 1, wherein said viscosity ranges from about 172 mPa*s to 9050 at 90° C.",
    "5. The resin composition of claim 1, wherein the first stage cure comprises ultraviolet radiation (UV) or cationic cure, electron beam (EB), Infrared (IR), addition cure, condensation reaction, peroxide cure or chemical additives.",
    "6. The resin composition of claim 5, wherein a gel material is formed after said first stage cure and wherein after said second stage cure said high performance and high temperature resin composition is formed.",
    "7. The resin composition of claim 1, wherein the second stage cure is a thermal post cure to finish curing the resin.",
    "8. The resin compositions of claim 1, wherein the second stage cure is affected in a microwave oven to finish the cure in a few seconds.",
    "9. The resin composition of claim 1 comprising a photo-initiator and, optionally, a thermal catalyst.",
    "10. The resin composition of claim 1, wherein Component A is selected from a group consisting of vinyl, acrylate, methacrylate, and acrylonitrile.",
    "11. The resin composition of claim 1, wherein Component A is selected from a group consisting of monomers, oligomers, and polymers.",
    "12. The resin composition of claim 1, wherein the second reactive group is selected from a group consisting of OH, NH, SH, COOH, epoxy, amine and anhydride.",
    "13. The resin composition of claim 1, wherein the cyanate ester may contain a photo curable group.",
    "14. The resin composition of claim 1, wherein following pre-reaction a polymerization initiator is added.",
    "15. The resin composition of claim 14, wherein an optional thermal catalyst is added.",
    "16. The resin composition of claim 1, wherein Component A comprises an elastomeric material that reacts with special aromatic amines to initiate reaction at room temperature or react with cyanate ester to cure at room temperature.",
    "17. The resin composition of claim 1, wherein first stage curing of the material provides a non-melting gummy to solid material that can be thermally post-cured in an oven to give solid materials with high glass transition temperatures.",
    "18. The resin composition of claim 1, wherein Component A makes up between 10-90%; Component B makes up between 10-90%.",
    "19. The resin composition of claim 1, wherein photo-initiator and catalyst are used in the range of 0.1-10%.",
    "20. The resin composition of claim 1, wherein component B comprises cyanate esters with low dielectric properties suitable for use in flexible and rigid circuit (PCB) boards applications.",
    "21. The resin composition of claim 1, wherein an ionic liquid catalyst is used in the range of 0.3-5%.",
    "22. The resin composition of claim 1 having a Tg >200° C. and high modulus after post cure.",
    "23. The resin composition of claim 1 having a Tg >300° C. with high elongation after post cure.",
    "24. The resin composition of claim 1 comprising epoxy hardeners for use in semiconductor polishing pad applications.",
    "25. The resin composition of claim 1 comprising a photo-initiator, and a thermal catalyst; wherein Component A is a photo-curable/peroxide curable/electron beam (EB)/or cationic curable group, and wherein Component B is a cyanate ester, unsaturated vinyl ester or vinyl ester hybrid, bismaleimide resin (BMI), polyimide, benzoxazine, phthalonitrile resin, silicone and epoxy.",
    "26. The resin composition of claim 25, wherein following pre-reaction a polymerization initiator is added.",
    "27. The resin composition of claim 26, wherein a thermal catalyst is added.",
    "28. The resin composition of claim 1, wherein said first stage cure is carried out for x time period and said second stage cure is carried out for y time period; wherein x≦y and y is ≦about four hours; and wherein said resin composition has a Tg >150° after said second stage cure.",
    "29. A high performance and high temperature resin composition for three dimensional printing formed from a two stage cure, comprising a first stage curable group (Component A), and a second stage curable group cured by thermal/heat cure (Component B); wherein Component A is selected from a photo-curable group, a peroxide curable group, a EB curable group, a cationic curable group, an IR curable group, an addition cure group, a condensation reactive group, and/or a chemical additive curable group; wherein Component A further comprises a second reactive group pre-reacted with Component B to generate a homogenous resin at room temperature having viscosity as low as about 100 mPA·s; wherein Component B is selected from a cyanate ester, bismaleimide (BMI), benzoxazine, polyimide, phthalonitrile resin (PN), bismaleimide triazine (BT), silicone resin, epoxy, cyanate epoxy and mixtures thereof; first stage cure is carried out for x time period and said second stage cure is carried out for y time period; wherein y is ≦about four hours.",
    "30. The resin composition of claim 29, wherein said resin composition has a Tg >150° C. after said second stage cure.",
    "31. The resin composition of claim 29, wherein x is ≦y."
  ],
  "description_excerpt": "This invention relates to thermosetting resin compositions that are useful as high performance and high temperature three-dimensional (“3-D”) printing materials suitable for objects requiring temperature performance >100 C but can be cured at room temperature by photo polymerization or other low temperature curing methods.\n\n3-D printing technology, including materials, printers and software, continue to advance as digital manufacturing is expected to grow. This shift of digital manufacturing would be an alternative to traditional manufacturing with a fraction of cost. Two powerful technology trends, 3-D printing and cloud computing, are coming together to bring low cost manufacturing bases to the United States and other advanced countries. Small companies implementing 3-D printing technology would more readily be capable of getting into the manufacturing business without the need for large capital investment.\n\nAdditive manufacturing process (“AM”) defines a process wherein digital 3-D design data is utilized to deposit materials one layer at a time to build up a component. The term “3-D printing” is frequently used as a synonym for AM. 3-D printing techniques are considered AM processes because they involve the application of successive layers of materials. Current commercial 3-D printers can selectively extrude thermoplastic, cure photosensitive resins, and sinter metallic, ceramic or polymer powders can be drawn with a computer-aided design program. The material selection combined with hardware (printer) and software is key for rapid prototyping and cost effective manufacturing.",
  "cpc": [
    "C08G 59/1477",
    "B29C 67/00",
    "B33Y 70/00",
    "B33Y 80/00",
    "C08G 14/06",
    "C08G 59/4014",
    "C08G 63/91",
    "C08G 65/485",
    "C08G 73/128",
    "C08J 2361/14",
    "C08J 2361/34",
    "C08J 2463/10",
    "C08J 3/243",
    "C08K 5/1539",
    "C08L 61/14",
    "C08L 61/34",
    "C08L 63/00",
    "C08L 65/02",
    "C08L 79/08",
    "C08L 79/085",
    "C08L 85/02"
  ],
  "ipc": [
    "B33Y 70/00",
    "C08F 2/46",
    "C08F 2/50",
    "C08G 59/14",
    "C08G 61/04",
    "C08G 63/91",
    "C08G 73/12"
  ],
  "assignees": [
    "NOVOSET LLC"
  ],
  "inventors": [
    "Sajal Das",
    "Christopher N. Das",
    "Patrick Shipman",
    "Benjamin G. Baxter"
  ],
  "filing_date": "2017-02-16",
  "publication_date": "2018-01-23",
  "grant_date": "2018-01-23",
  "priority_date": "2015-06-18",
  "application_number": "US-201715434613-A",
  "family_id": "57586888",
  "cited_by_count": 47,
  "citations": [
    "US5021519A",
    "US6632893B2",
    "US20030083397A1",
    "US20090061215A1",
    "US20080103226A1",
    "US20120172483A1",
    "US8603612B2",
    "WO2012015604A1",
    "US20140065378A1",
    "WO2014077848A1",
    "US20140239527A1",
    "US20150064299A1",
    "US9708440B2"
  ]
}