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, consisting of 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 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 first stage and second stage cure is completed in a time period of less than 5 minutes.

3. The resin composition of claim 1, wherein said high performance and high temperature resin composition has a Tg >300 C and is adapted for use with fibers for racing car body parts.

4. The resin composition of claim 1, wherein said resin composition meets requirements of 14 CFR Part 25.853 for use in aircraft ducting, oil tank, water tank, waste tank and toilet parts.

5. The resin composition of claim 1, wherein said resin composition is adapted for use for high temperature composite wheels.

6. The resin composition of claim 1 comprising phthalonitrile resin (PN) or modified PN resin as component B and silica used in encapsulation application for power devices.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) The invention will be more fully understood and further advantages will become apparent when reference is had to the following detailed description of the preferred embodiments of the invention and the accompanying drawing, in which:

(2) FIG. 1 illustrates a flow chart showing the general process steps in formation of the thermosetting resin compositions; and

(3) FIG. 2 illustrates a flow chart in formation of an embodiment of a thermosetting resin composition.

DETAILED DESCRIPTION OF THE INVENTION

(4) The subject invention provides thermosetting resin compositions having applications as high performance and high temperature 3-D printing materials. The thermosetting resin compositions are suitable for any object that requires thermal performance >100 C. but can be cured at room temperature by photo-polymerization or other low temperature curing methods.

(5) Most of thermosetting 3-D printing materials today are made with UV curable epoxy resins, acrylate resins, elastomeric rubber materials, polybutadiene, polyester acrylate, etc. However, none of the current thermoset materials can effectively tolerate high temperature use over extended periods of time and therefore cannot be utilized for 3-D objects that are subjected to high temperature utility. The present invention addresses the utility of high temperature usage of 3-D printing materials. Many applications such as, including but not limited to: aerospace engine blades, automotive parts (such as muffler, and/or parts close to the engine), oil and gas, aircraft ducting systems, high temperature printed circuit boards, chip mounting, robotic hands, molding compounds for electric cars, battery storage enclosures of electric cars, high temperature molds to make tap faucets, air-condition vents, require parts that are capable of withstanding high temperatures (>150 C.) for extended periods of time.

(6) The thermosetting resin compositions of the subject invention provide high performance, high temperature compositions using Cyanate esters, Bismaleimide, benzoxazine, polyimide, Phthalonitrile resin (PN) and silicone resins. The thermosetting resin compositions further address low or room temperature curing temperatures of the compositions to adapt to current 3-D printing hardware, and followed by further curing the object in a free standing oven to achieved high Tg or a high ultimate use temperature. Preferably, the first stage and second stage cure is completed in a time period of less than 5 minutes.

(7) The thermosetting resin compositions of the subject invention can be utilized with Stereolithographic apparatus' (SLA; See U.S. Pat. No. 5,236,637), Selective laser Sintering (SLS), Multijet and Continuous liquid Interface Production (CLIP-US; See U.S. Patent No. 2015/0097315) and combinations of processes thereof to make 3-D structures and parts.

(8) In another embodiment, the subject resin composition is formulated with carbon, glass, synthetic fiber of high tensile strength (such as that sold under the trade name Kevlar from DuPont), ultra-high-molecular-weight polyethylene (UHMWPE) fiber (such as that sold under the trade name Spectra from Honeywell), and/or other fibers to make composite parts.

(9) The subject resin composition may be formulated with pigment, coloring, light sensitive conductive materials, amorphous thermoplastic polyetherimide (PEI) resins (such as that sold under the trade name Ultem from Sabic), Polyethylene terephthalate (PET), and flame retardant additives.

(10) In another embodiment the subject resin composition is formulated with carbon, glass and/or synthetic fiber of high tensile strength (such as that sold under the trade name Kevlar from DuPont) and flame retardant materials suitable of structural composites with excellent mechanical and thermal properties and conforming to flammability requirements of 14 CFR Part 25.853 and finished parts compliance with smoke density (Ds) requirements of 14 CFR part 25.853(d) [for example: 14 CFR Ch. I (1-1-12 Edition)(b) Acceptance Criteria. The specific optical smoke density (Ds), which is obtained by averaging the reading obtained after 4 minutes with each of the three specimens, shall not exceed 200; See 14 CFR Ch. I (1-1-12 Edition) found at http://www.gpo.gov/fdsys/pkg/CFR-2012-title14-vol1/pdf/CFR-2012-title14-vol1-part25-appF.pdf].

(11) For example, 14 CFR Part 25.853 currently requires, inter alia, compartment materials for Aeronautics and Space via: Material Test Criteria-(1) interior compartment occupied by crew or passengers. (i) interior ceiling panels, interior wall panels, partitions, galley structure, large cabinet walls, structural flooring, and materials used in the construction of stowage compartments (other than under seat stowage compartments and compartments for stowing small items such as magazines and maps) must be self-extinguishing when tested vertically in accordance with the applicable portions of the regulation. The average burn length may not exceed 6 inches and the average flame time after removal of the flame source may not exceed 15 seconds. Drippings from the test specimen may not continue to flame for more than an average of 3 seconds after falling. See 14 CFR 25.853compartment interiors, found at http://www.gpo.gov/fdsys/granule/cfr-1999-title14-vol1/cfr-1999-title14-vol1-sec25-853/content-detail.html, for example. The composition has particular application for use in aircraft ducting, oil tank, water tank, waste tank and toilet structures. Preferably, the resin composition has a Tg >300 C so that it can be used with fibers for racing car body parts, and/or for use in high temperature composites wheels.

(12) The resin may include Phthalonitrile resin (PN) or modified PN resin as component B and silica used in encapsulation application for power devices. The resin composition may include epoxy hardeners/polyurethane chain extenders for advanced two component polyurethane cast and spray applications, such as that sold under the trade name Lonzacure from Lonza (M-DEA, M-MIPA, CAF, M-CDEA) for use in semiconductor polishing pad applications. Component B may be Cyanate esters with low dielectric properties for use in flexible and rigid circuit (PCB) boards applications.

(13) FIG. 1 illustrates a flow chart showing the general process steps in formation of the thermosetting resin compositions, shown generally at 100. A high performance and high temperature resin composition for three dimensional printing is provided that is formed from a two stage cure. The first stage cure 101 may be ultraviolet radiation (UV), cationic, electron beam (EB), peroxide, and/or chemical additive cure. The second stage cure 102 is preferably a thermal post cure to finish curing the resin. The resin composition preferably comprises a first stage curable group (Component A), a second stage curable group cured by thermal/heat cure (Component B), a photo-initiator, and a thermal catalyst. The resin composition's Component A may be selected from a photo-curable group, a peroxide curable group, an EB curable group, and/or a cationic curable group. Component A may be selected from a group consisting of vinyl, acrylate, methacrylate, and acrylonitrile. Alternatively, Component A may be selected from a group consisting of monomers, oligomers, and polymers. Component B is preferably a cyanate ester, isocyanate, benzoxazine, polyimide, Phthalonitrile resin (PN), bismaleimide, silicone resin, BT, epoxy and mixture thereof.

(14) In an alternative embodiment, Component A may further comprise a second reactive group. The second reactive group is preferably selected from a group consisting of OH, NH, SH, COOH, epoxy, amine and anhydride. This second reactive group is capable of reacting with Component B.

(15) Components A and B can be pre-reacted to generate a high viscosity material that at elevated temperatures has a viscosity suitable for three-dimensional printers. Following pre-reaction a polymerization initiator is preferably added. Also, an optional thermal catalyst may be added.

(16) In another embodiment, Component A comprises an elastomeric material that reacts with special aromatic amines to initiate reaction at room temperature or react with Cyanate ester or Isocyanate to cure at room temperature. The 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.

(17) Preferably, the resin composition's Component A makes up between 10-90%; Component B makes 10-90% of the composition. Photo-initiator and catalyst are used in the range of 0.1-10%. An ionic liquid catalyst may be used in the range of 0.3-5%.

(18) Resultant resin compositions preferably have a Tg of final product after post cure >200 C. and high modulus. Alternatively, resultant resin compositions preferably have a Tg >300 C. with high elongation.

(19) FIG. 2 illustrates a flow chart in formation of an embodiment of a thermosetting resin composition, shown generally at 200. At 201, Component A (first stage curable group) and Component B (second stage curable group) are heated for a reaction time period until the reaction is deemed complete. [See Example 1 below: 2,2-bis (4-Cyanatophenyl) isopropyidene (Primaset BADCy (Lonza) (70%) [Component B] and acrylate epoxy resin (30% from Archema) [Component A] were reacted at 150 C. for 45 min. The reaction is cooled and photo-initiator added at 202. Upon cooling a photo-initiator (Irgacure 2022) was added (0.3-3%). At 203 the Cure Stage I: First Cure is initiated by way of Irradiation (365 nm light for x time period) forming a gel material 204. This resin can achieve hard cure with irradiation of 365 nm light for 15 min. At 205 the Cure Stage II: Second Cure is initiated by thermal post cure. The UV cured material/gel 204 is post cured (2 hours at 150 C. and 1 hour at 210 C.) to generate a material with glass transition temperature of 201 C. A high performance, high temperature resin formed is formed at 206, having a glass transition temperature >150 C. so that the resin can be utilized to form high temperature tolerant objects for high heat applications.

Examples 1-21

(20) The following examples are presented to provide a more complete understanding of the invention. The specific techniques, conditions, materials, proportions and reported data set forth to illustrate the principles and practice of the invention are exemplary and should not be construed as limiting the scope of the invention.

Example 1

(21) 70 wt. % 2,2-Bis(4-cyanatophenyl)propane (Primaset BADCy from Lonza) and 30 wt. % acrylated epoxy resin (cn104z from sartomer) were reacted at 150 C. for 45 min. Upon cooling a photo-initiator (Irgacure 2022 from BASF) was added (3 wt. %). This resin achieve hard cure with irradiation of 365 nm light for 15 min. This UV cured material can be further post cured (2 hours at 150 C. and 1 hour at 210 C.) to generate a material with glass transition temperature of 201 C.

Example 2

(22) 70 wt. % 2,2-Bis(4-cyanatophenyl)propane (Primaset BADCy from Lonza) and 30 wt. % acrylated epoxy resin (cn104z from sartomer), 0.64 wt. % Novocure-200 (available from Novoset LLC) and a photo-initiator 0.33 wt. % (Irgacure 819 from BASF) were combined and warmed to 90 C., the mixture was irradiated at 365 nm for 30 min to achieve a hard cure. This material can be post cured thermally (20 min at 150 C.) to generate a material with a high Tg 236 C.

Example 3

(23) 70 wt. % 2,2-Bis(4-cyanatophenyl)ethane (Primaset LECY from Lonza) and 30 wt. % acrylated epoxy resin (cn104z from sartomer) and a photo-initiator 0.63% (Irgacure 2022 from BASF) were mixed and irradiated at 365 nm for 1 hour to give a tacky gelled material. This material is further cured thermally to produce a solid material with a tan d above 316 C.

Example 4

(24) 70 wt. % 2,2-Bis(4-cyanatophenyl)ethane (Primaset LECY from Lonza) and 30 wt. % acrylated epoxy resin (cn154 from Sartomer) were blended with a photo-initiator. 3.0 wt. % (Irgacure 2022 from BASF). Irradiation at 365 nm light provides a hard cured resin that is post cured thermally to give a material with a tan d of 221 C.

Example 5

(25) 35 wt. % 1,1-Bis(4-cyanatophenyl)ethane (Primaset LECy from Lonza), 35 wt. % Phthalonitrile resin and 30 wt. % acrylate epoxy resin (cn104z from Sartomer) were combined and heated to mix together. A photo-initiator 3.0 wt. % (Irgacure 2022 from BASF) was added to give a material with a viscosity of 9050 mPa*s at 60 C. This resin can be hard cured with irradiation of 365 nm light for 15 min. This material can be further post cured to give a hard material with at Tg=172 C.

Example 6

(26) 56 wt. % Polyphenol cyanate ester (Primaset PT-30 from Lonza), 22.75 wt. % acrylated epoxy resin (cn104z from Sartomer), 19.81 wt. % 2-(methacryloyloxy)ethyl acetoacetate (AAEMA from Lonza) were warmed together and mixed. 3.37 wt. % photo-initiator (Irgacure 2022 from BASF) was added to give a material with a viscosity=3130 mPa*s at 30 C. This material could be photo-cured and then thermally post cured (2 hours at 150 C.; 2 hours at 235 C., 1 hour at 250 C.) to give a Tg=238 C.

Example 7

(27) 61 wt. % 1,1-Bis(4-cyanatophenyl)ethane (Primaset LECy from Lonza) and 39 wt. % modified polyphenylene oxide (SA-9000 from Sabic) was warmed to 95 C. and mixed until homogenous. This mixture gave a viscosity of 1905 mPa*s at 95 C. To this mixture was added 3% photo-initiator (Igracure 2022 from BASF), the mixture was then exposed to 365 nm light and cured to give a solid material.

Example 8

(28) 60 wt. % 2,2-Bis(4-cyanatophenyl)propane (Primaset BADCy from Lonza) and 40 wt. % modified polyphenylene oxide (SA-9000 from Sabic) was warmed to 95 C. and mixed until homogenous. This mixture gave a viscosity of 4885 mPa*s at 95 C. To this mixture was added 3% photo-initiator (Igracure 2022 available from BASF, the mixture was then exposed to 365 nm light and cured to give a solid material.

Example 9

(29) 57 wt. % 1,1-Bis(4-cyanatophenyl)ethane (Primaset LECy from Lonza) and 23 wt. % modified bismaleimide (BMPI) were warmed and stirred until homogenous. To this was added 21 wt. % modified vinyl ester resin (polylite 35070-00 from Reichhold) this was mixed until homogenous and gave a viscosity of 379 mPa*s at 40 C. To this mixture was added 3.41% photo-initiator (Irgacure 2022 from BASF) and the mixture was irradiated for 30 min at 365 nm to cure. This was post cured (2 hours at 150 C.; 2 hours at 235 C.) to give a material with a Tg=235 C.

Example 10

(30) 95 wt. % 1,1-Bis(4-cyanatophenypethane (Primaset LECy from Lonza) and 5 wt. % Lonzacure CAF (from Lonza) were combine and gently warmed to 70 C. to dissolve the Lonzacure. This gave a mixture with a viscosity of 46.24 mPa*s at 40 C. This material was cured at 120 C. for 1 hour and 10 min to give a solid material. Post-curing (2 hours at 150 C.; 2 hours at 235 C.) of this material gave a Tg=301 C.

Example 11

(31) 95 wt. % 1,1-Bis(4-cyanatophenyl)ethane (Primaset LECy from Lonza) and 5 wt. % Lonzacure m-DEA (from Lonza) were combine and gently warmed to 70 C. to dissolve the Lonzacure. This gave a mixture with a viscosity of 39.02 mPa*s at 40 C. This material was cured at 120 C. for 15 min to give a solid material. Post-curing (2 hours at 150 C.; 2 hours at 235 C.) of this material gave a Tg=279 C.

Example 12

(32) 95 wt. % 1,1-Bis(4-cyanatophenyl)ethane (Primaset LECy from Lonza) and 5 wt. % Lonzacure m-mipa (from Lonza) were combine and gently warmed to 70 C. to dissolve the Lonzacure. This gave a mixture with a viscosity of 50.26 mPa*s at 40 C. This material was cured at 120 C. for 15 min to give a solid material. Post-curing (2 hours at 150 C.; 2 hours at 235 C.) of this material gave a Tg=267 C.

Example 13

(33) 43 wt. % 2,2-Bis(4-cyanatophenyl)propane (Primaset BADCy from Lonza), 12 wt. % hydroxyl terminated-polycaprolactone (CAPA-2100 from Perstorp) and 41 wt. % modified vinyl ester resin (polylite 35070-00 from Reichhold) were combined and warmed to mix. This gave a material with a viscosity of 3345 mPa*s at 95 C. To this was added 3 wt. % photo-initiator (Irgacure 2022 from BASF) and the material was irradiated at 365 nm to give a solid material. The material was post-cured (2 hours at 150 C.; 2 hours at 235 C.) to give Tg=166 C.

Example 14

(34) 47 wt. % HTL-300 (from Lonza), 34 wt. % modified vinyl ester resin (polylite 35070-00 from Reichhold) and 18 wt. % 1,1-Bis(4-cyanatophenyl)ethane (Primaset LECy from Lonza) were combined and warmed to mix. This gave a material with a viscosity of 172 mPa*s at 95 C. To this was added 3 wt. % photo-initiator (Irgacure 2022 from BASF) and the material was irradiated at 365 nm to give a solid material. The material was post-cured (2 hours at 150 C.; 2 hours at 235 C.) to give Tg=166 C.

Example 15

(35) 41 wt. % Multi-functional cyanate ester resin (Primaset PT-15 from Lonza), 19 wt. % bisphenol F epoxy resin (PY306) and 31 wt. % polyphenol phosphate (AFLAMMIT PLF-140 from THOR) are warmed to 60 C. and mixed to form a homogenous resin material.

Example 16

(36) 57 wt. % Polyphenyl cyanate resin (Primaset PT-15 from Lonza), 19 wt. % bisphenol A epoxy resin (GY240, from Huntsman) and 8 wt. % polyphenol phosphate (Fyrol PMP, From ICL) and 16 wt. % cyclic anhydride (MTHPA, from Broadview Technologies) are warmed to 60 C. and mixed to form a homogenous resin material.

Example 17

(37) 49 wt. % Polyphenyl cyanate ester resin (Primaset PT-30, from Lonza), 25 wt. % aliphatic epoxy (heloxy 68, from Momentive), 25 wt. % cyclic anhydride (MTHPA, from broadview technologies) were mixed at room temperature to give a homogenous resin having viscosity as low as 137.71 mPa*s at 40 C.

Example 18

(38) 37 wt. % Polyphenyl cyanate ester resin (LVT-50, from cyalume), 19 wt. % modified bisphenol A epoxy (RIMR 935, From Momentive), 37 wt. % polyphosphazene (SPB-100, from Otsuka), 6 wt. % aliphatic amine (RIMR 936H, from Momentive). Warm to 50 C. and mix to form a homogenous resin.

Example 19

(39) 36 wt. % Polyphenyl cyanate ester resin (Primaset PT-30, from Lonza), 13 wt. % modified bisphenol A epoxy (RIMR 935 from Momentive), 12 wt. % cyclic anhydride (MTHPA, from Broadview technologies) and 39 wt. % bismaleimide resin were warmed to 90 C. and mixed give a homogenous resin having viscosity as low as 712 mPa*s at 40 C.

Example 20

(40) Part A: 50 wt. % 1,1-Bis(4-cyanatophenyl)propane (Primaset BADCy from Lonza) and 50 wt. % methylene diphenyl diisocyanate prepolymer (Rubinate M, from Huntsman) was warmed to 95 C. and mixed until homogenous.

(41) Part B: 85.17 wt. % Linear hydroxylated polybutadiene (LBH-2000P, from Total) and 14.83 wt. % Lonzacure m-Mipa 2.2510 g (from Lonza) were combined and warmed to make homogenous.

(42) These solutions Part A and Part B were mixed in a 66.13% and 33.87% respectively at room temperature. The mixture reacted at room temperature to form a gummy material that can then be post cured.

Example 21

(43) 72 wt. % 1,1-Bis(4-cyanatophenyl) ethane (Primaset LECy from Lonza, 72%) and 28 wt. % (3,4-Epoxycyclohexane)methyl 3,4-epoxycyclohexylcarboxylate (Celloxide 2021P from Diacel, 28%) were combined and mixed until homogenous at room temperature to give a viscosity of 34.45 mPa*s at 40 C. To this was added 3 wt % of Irgacure 250 and the solution was irradiated to give a cured material. This cured material could be further post cured to achieve high Tg.

(44) This gave a mixture with a viscosity of 50.26 mPa*s at 40 C. This material was cured at 120 C for 15 min to give a solid material. Post-curing (2 hours at 150 C.; 2 hours at 235 C.) of this material gave a Tg=267 C.

(45) Having thus described the invention in rather full detail, it will be understood that such detail need not be strictly adhered to, but that additional changes and modifications may suggest themselves to one skilled in the art, all falling within the scope of the invention as defined by the subjoined claims.