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Patent · US10449714B2 · B2 · US

Process for producing an object from a precursor and use of a free-radically crosslinkable resin in an additive manufacturing process

(11) Publication number
US10449714B2
(21) Application number
15/812,116
(22) Filing date
2017-11-14
(30) Priority date
2016-11-14
(43) Publication date
2019-10-22
(45) Date of grant
2019-10-22
(51) IPC
B29C 64/124; B33Y 10/00; B33Y 70/00; C08G 18/10; C08G 18/67; C08G 18/81; C08G 18/02; C08G 18/04; C08G 18/22; C08G 18/62; C08G 18/72; C08G 18/73; C08G 18/79
(52) CPC
  • 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: 64/124, 39/006, 64/112, 64/129, 64/209, 64/214, 64/245, 64/264, 64/295
  • 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: 2075/00
  • B33Y 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: 10/00, 30/00, 70/00
  • C08F Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds: 120/36, 220/36, 283/008
  • C08G Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds: 18/022, 18/04, 18/10, 18/1816, 18/225, 18/246, 18/48, 18/6229, 18/672, 18/6755, 18/728, 18/73, 18/755, 18/792, 18/8125, 18/8175
  • C08J Working-up; general processes of compounding; after-treatment not covered by subclasses C08B, C08C, C08F, C08G or C08H: 3/244
  • C08K Use of inorganic or non-macromolecular organic substances as compounding ingredients: 7/14
  • C09D Coating compositions, e.g. paints, varnishes or lacquers; filling pastes; chemical paint or ink removers; inks; correcting fluids; woodstains; pastes or solids for colouring or printing; use of materials therefor: 175/14
  • C09J Adhesives; non-mechanical aspects of adhesive processes in general; adhesive processes not provided for elsewhere; use of materials as adhesives: 175/14, 2475/00, 5/00
(73) Assignee
Covestro Deutschland AG
(72) Inventors
Dirk Achten; Thomas Büsgen; Jörg Tillack; Michael Ludewig; Christoph Tomczyk; Roland Wagner
(54) Title
Process for producing an object from a precursor and use of a free-radically crosslinkable resin in an additive manufacturing process
(57) Abstract

A process for producing an object from a precursor comprises the steps of: depositing a free-radically crosslinked resin atop a carrier to obtain a ply of a construction material joined to the carrier which corresponds to a first selected cross section of the precursor; depositing a free-radically crosslinked resin atop a previously applied ply of the construction material to obtain a further ply of the construction material which corresponds to a further selected cross section of the precursor and which is joined to the previously applied ply; repeating step II) until the precursor is formed; wherein the depositing of a free-radically crosslinked resin at least in step II) is effected by exposure and/or irradiation of a selected region of a free-radically crosslinkable resin corresponding to the respectively selected cross section of the object and wherein the free-radically crosslinkable resin has a viscosity (23° C., DIN EN ISO 2884-1) of ≥5 mPas to ≤100000 mPas. In the process the free-radically crosslinkable resin comprises a curable component in which NCO groups and olefinic C═C double bonds are present, wherein in the curable component the molar ratio of NCO groups to olefinic C═C double bonds is in a range from ≥1:5 to ≤5:1.

Full text
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Claims (12)

  1. A process for producing an object from a precursor, comprising the steps of: I) depositing a free-radically crosslinked resin atop a carrier to obtain a ply of a construction material joined to the carrier which corresponds to a first selected cross section of the precursor; wherein the carrier is arranged inside a container and is vertically raisable counter to the direction of the gravitational force, and the container provides the free-radically crosslinkable resin, II) depositing a free-radically crosslinked resin atop a previously applied ply of the construction material to obtain a further ply of the construction material which corresponds to a further selected cross section of the precursor and which is joined to the previously applied ply; wherein before each step II) the carrier is raised by a predetermined distance so that below the lowermost ply of the construction material viewed in the vertical direction a layer of the free-radically crosslinkable resin is formed, III) repeating step II) until the precursor is formed; wherein the depositing of a free-radically crosslinked resin at least in step II) is effected by exposure and/or irradiation of a selected region of a free-radically crosslinkable resin corresponding to the respectively selected cross section of the precursor and wherein the free-radically crosslinkable resin has a viscosity (23° C., DIN EN ISO 2884-1) of ≥5 mPas to ≤100000 mPas, wherein the free-radically crosslinkable resin has a curable component in which NCO groups and olefinic C═C double bonds are present, wherein in the curable compound the molar ratio of NCO groups to olefinic C═C double bonds is in a range from ≥1:5 to ≤5:1, and wherein, after step III), step IV) is further performed: IV) treating the precursor obtained after step III) under conditions sufficient to at least partially trimerize to isocyanurate groups NCO groups present in the free-radically crosslinked resin of the obtained precursor to obtain the object.
  2. The process according to claim 1, wherein isocyanurate groups are further present in the curable component, wherein the molar ratio of NCO groups to isocyanurate groups is in a range from ≤100:1 to ≥1:2 and in the curable component the molar ratio of olefinic C═C double bonds to isocyanurate groups is in a range from ≤100:1 to ≥1:5.
  3. The process according to claim 1 wherein the curable component comprises a curable compound comprising isocyanurate groups, NCO groups and olefinic C═C double bonds, wherein in the curable compound the molar ratio of NCO groups to isocyanurate groups is in a range from ≤100:1 to ≥1:2, and in the curable compound the molar ratio of olefinic C═C double bonds to isocyanurate groups is in a range from ≤100:1 to ≥1:5.
  4. The process according to claim 1 wherein the free-radically crosslinkable resin further comprises a free-radical starter and/or an isocyanate trimerization catalyst.
  5. The process according to claim 1 wherein at least one free-radical starter is selected from the group: α-hydroxyphenylketone, benzyldimethylketal, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(4-methoxybenzoyl)diethylgermanium and any combination of at least two thereof and/or the isocyanurate trimerization catalyst is selected from: potassium acetate, potassium acetate in combination with a crown ether, potassium acetate in combination with a polyethylene glycol, potassium acetate in combination with a polypropylene glycol, tin octoate, sodium phenoxide, potassium hydroxide, trioctyl phosphine and/or tributyltin oxide.
  6. The process according to claim 1 wherein in the resin the molar ratio of NCO groups to Zerewitinoff-active H atoms is ≥500.
  7. The process according to claim 1 wherein the curable component has a number-average molecular weight M n of ≥200 g/mol to ≤5000 g/mol.
  8. The process according to claim 1 wherein in step IV) the treating of the precursor obtained after step III) under conditions sufficient to at least partially trimerize to isocyanurate groups NCO groups present in the free-radically crosslinked resin of the obtained precursor comprises a heating of the body to a temperature of ≥60° C.
  9. The process according to claim 1 wherein the surface of the precursor obtained after step III) and/or of the object obtained after step IV) is contacted with a compound comprising Zerewitinoff-active H atoms, wherein water occurring as natural atmospheric humidity in the atmosphere surrounding the precursor and/or the object is excluded.
  10. The process according to claim 1 wherein: the carrier is arranged inside a container and is vertically lowerable in the direction of the gravitational force, the container contains the free-radically crosslinkable resin in an amount sufficient to cover at least the carrier and crosslinked resin deposited atop the carrier, before each step II) the carrier is lowered by a predetermined distance so that above the uppermost ply of the construction material viewed in the vertical direction a layer of the free-radically crosslinkable resin is formed and in step II) an energy beam exposes and/or irradiates the selected region of the layer of the free-radically crosslinkable resin corresponding to the respectively selected cross section of the precursor.
  11. The process according to claim 1 wherein: in step II) a plurality of energy beams simultaneously expose and/or irradiate the selected region of the layer of the free-radically crosslinkable resin corresponding to the respectively selected cross section of the precursor.
  12. The process according to claim 1 wherein: in step II) the free-radically crosslinkable resin is applied from one or more printing heads corresponding to the respectively selected cross section of the precursor and is subsequently exposed and/or irradiated.

Description

The present invention relates to a process for producing an object from a precursor, comprising the steps of:

The invention further relates to the use of a free-radically crosslinkable resin having a viscosity (at 23° C. measured with a Wells/Brookfield cone-plate viscometer according to DIN EN ISO 2884-1) of ≥5 mPas to ≤100000 mPas in an additive manufacturing process, wherein the resin comprises a curable compound having isocyanurate groups, NCO groups and olefinic C═C double bonds. The invention finally relates to a polymer obtainable by crosslinking such a resin.

Polymers having a polyisocyanurate structure are known for their high thermal stability and flame resistance. Polyisocyanurate-containing foams (PUR/PIR-foams) based on aromatic 4,4′-diphenylmethane diisocyanate (MDI) and polyether polyols and polyepoxides are widely used on account of their very low thermal conductivity for example, in particular as high-performance insulating materials.

Polyisocyanurates also find practical application as crosslinking agents in paint chemistry, the production of which involves stopping the trimerization reaction at low conversions and removing excess unreacted monomeric diisocyanate. Thus, in the production of crosslinking agents based on isocyanurates proceeding from aliphatic and mixed aliphatic and aromatic monomeric diisocyanates, DE 31 00 263; GB 952 931, GB 966 338; U.S. Pat. No. 3,211,703 or 3,330,828 envisage performing the reaction either in dilute conditions or only up to low conversion values with very precise temperature control.

Citations (32)

  • GB809809A
  • GB952931A
  • GB966338A
  • US3211703A
  • US3330828A
  • GB1386399A
  • GB1391066A
  • US4145544A
  • US4128537A
  • US4159376A
  • US4265798A
  • US4379905A
  • US4487928A
  • US4604418A
  • EP0100129A1
  • DE3240613A1
  • US4663377A
  • US4870152A
  • EP0347610A2
  • GB2221465A
  • GB2222161A
  • US5252696A
  • US6133397A
  • US6335381B1
  • US20010038917A1
  • US6500876B2
  • US20060051591A1
  • US20080145624A1
  • US20110089610A1
  • US20140017460A1
  • US9157007B2
  • US20150158966A1
Record as JSON 
{
  "publication_number": "US10449714B2",
  "country": "US",
  "kind": "B2",
  "title": "Process for producing an object from a precursor and use of a free-radically crosslinkable resin in an additive manufacturing process",
  "abstract": "A process for producing an object from a precursor comprises the steps of: depositing a free-radically crosslinked resin atop a carrier to obtain a ply of a construction material joined to the carrier which corresponds to a first selected cross section of the precursor; depositing a free-radically crosslinked resin atop a previously applied ply of the construction material to obtain a further ply of the construction material which corresponds to a further selected cross section of the precursor and which is joined to the previously applied ply; repeating step II) until the precursor is formed; wherein the depositing of a free-radically crosslinked resin at least in step II) is effected by exposure and/or irradiation of a selected region of a free-radically crosslinkable resin corresponding to the respectively selected cross section of the object and wherein the free-radically crosslinkable resin has a viscosity (23° C., DIN EN ISO 2884-1) of ≥5 mPas to ≤100000 mPas. In the process the free-radically crosslinkable resin comprises a curable component in which NCO groups and olefinic C═C double bonds are present, wherein in the curable component the molar ratio of NCO groups to olefinic C═C double bonds is in a range from ≥1:5 to ≤5:1.",
  "claims": [
    "1. A process for producing an object from a precursor, comprising the steps of: I) depositing a free-radically crosslinked resin atop a carrier to obtain a ply of a construction material joined to the carrier which corresponds to a first selected cross section of the precursor; wherein the carrier is arranged inside a container and is vertically raisable counter to the direction of the gravitational force, and the container provides the free-radically crosslinkable resin, II) depositing a free-radically crosslinked resin atop a previously applied ply of the construction material to obtain a further ply of the construction material which corresponds to a further selected cross section of the precursor and which is joined to the previously applied ply; wherein before each step II) the carrier is raised by a predetermined distance so that below the lowermost ply of the construction material viewed in the vertical direction a layer of the free-radically crosslinkable resin is formed, III) repeating step II) until the precursor is formed; wherein the depositing of a free-radically crosslinked resin at least in step II) is effected by exposure and/or irradiation of a selected region of a free-radically crosslinkable resin corresponding to the respectively selected cross section of the precursor and wherein the free-radically crosslinkable resin has a viscosity (23° C., DIN EN ISO 2884-1) of ≥5 mPas to ≤100000 mPas, wherein the free-radically crosslinkable resin has a curable component in which NCO groups and olefinic C═C double bonds are present, wherein in the curable compound the molar ratio of NCO groups to olefinic C═C double bonds is in a range from ≥1:5 to ≤5:1, and wherein, after step III), step IV) is further performed: IV) treating the precursor obtained after step III) under conditions sufficient to at least partially trimerize to isocyanurate groups NCO groups present in the free-radically crosslinked resin of the obtained precursor to obtain the object.",
    "2. The process according to claim 1, wherein isocyanurate groups are further present in the curable component, wherein the molar ratio of NCO groups to isocyanurate groups is in a range from ≤100:1 to ≥1:2 and in the curable component the molar ratio of olefinic C═C double bonds to isocyanurate groups is in a range from ≤100:1 to ≥1:5.",
    "3. The process according to claim 1 wherein the curable component comprises a curable compound comprising isocyanurate groups, NCO groups and olefinic C═C double bonds, wherein in the curable compound the molar ratio of NCO groups to isocyanurate groups is in a range from ≤100:1 to ≥1:2, and in the curable compound the molar ratio of olefinic C═C double bonds to isocyanurate groups is in a range from ≤100:1 to ≥1:5.",
    "4. The process according to claim 1 wherein the free-radically crosslinkable resin further comprises a free-radical starter and/or an isocyanate trimerization catalyst.",
    "5. The process according to claim 1 wherein at least one free-radical starter is selected from the group: α-hydroxyphenylketone, benzyldimethylketal, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(4-methoxybenzoyl)diethylgermanium and any combination of at least two thereof and/or the isocyanurate trimerization catalyst is selected from: potassium acetate, potassium acetate in combination with a crown ether, potassium acetate in combination with a polyethylene glycol, potassium acetate in combination with a polypropylene glycol, tin octoate, sodium phenoxide, potassium hydroxide, trioctyl phosphine and/or tributyltin oxide.",
    "6. The process according to claim 1 wherein in the resin the molar ratio of NCO groups to Zerewitinoff-active H atoms is ≥500.",
    "7. The process according to claim 1 wherein the curable component has a number-average molecular weight M n of ≥200 g/mol to ≤5000 g/mol.",
    "8. The process according to claim 1 wherein in step IV) the treating of the precursor obtained after step III) under conditions sufficient to at least partially trimerize to isocyanurate groups NCO groups present in the free-radically crosslinked resin of the obtained precursor comprises a heating of the body to a temperature of ≥60° C.",
    "9. The process according to claim 1 wherein the surface of the precursor obtained after step III) and/or of the object obtained after step IV) is contacted with a compound comprising Zerewitinoff-active H atoms, wherein water occurring as natural atmospheric humidity in the atmosphere surrounding the precursor and/or the object is excluded.",
    "10. The process according to claim 1 wherein: the carrier is arranged inside a container and is vertically lowerable in the direction of the gravitational force, the container contains the free-radically crosslinkable resin in an amount sufficient to cover at least the carrier and crosslinked resin deposited atop the carrier, before each step II) the carrier is lowered by a predetermined distance so that above the uppermost ply of the construction material viewed in the vertical direction a layer of the free-radically crosslinkable resin is formed and in step II) an energy beam exposes and/or irradiates the selected region of the layer of the free-radically crosslinkable resin corresponding to the respectively selected cross section of the precursor.",
    "11. The process according to claim 1 wherein: in step II) a plurality of energy beams simultaneously expose and/or irradiate the selected region of the layer of the free-radically crosslinkable resin corresponding to the respectively selected cross section of the precursor.",
    "12. The process according to claim 1 wherein: in step II) the free-radically crosslinkable resin is applied from one or more printing heads corresponding to the respectively selected cross section of the precursor and is subsequently exposed and/or irradiated."
  ],
  "description_excerpt": "The present invention relates to a process for producing an object from a precursor, comprising the steps of:\n\nThe invention further relates to the use of a free-radically crosslinkable resin having a viscosity (at 23° C. measured with a Wells/Brookfield cone-plate viscometer according to DIN EN ISO 2884-1) of ≥5 mPas to ≤100000 mPas in an additive manufacturing process, wherein the resin comprises a curable compound having isocyanurate groups, NCO groups and olefinic C═C double bonds. The invention finally relates to a polymer obtainable by crosslinking such a resin.\n\nPolymers having a polyisocyanurate structure are known for their high thermal stability and flame resistance. Polyisocyanurate-containing foams (PUR/PIR-foams) based on aromatic 4,4′-diphenylmethane diisocyanate (MDI) and polyether polyols and polyepoxides are widely used on account of their very low thermal conductivity for example, in particular as high-performance insulating materials.\n\nPolyisocyanurates also find practical application as crosslinking agents in paint chemistry, the production of which involves stopping the trimerization reaction at low conversions and removing excess unreacted monomeric diisocyanate. Thus, in the production of crosslinking agents based on isocyanurates proceeding from aliphatic and mixed aliphatic and aromatic monomeric diisocyanates, DE 31 00 263; GB 952 931, GB 966 338; U.S. Pat. No. 3,211,703 or 3,330,828 envisage performing the reaction either in dilute conditions or only up to low conversion values with very precise temperature control.",
  "cpc": [
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    "B29C 64/112",
    "B29C 64/129",
    "B29C 64/209",
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    "B29C 64/245",
    "B29C 64/264",
    "B29C 64/295",
    "B29K 2075/00",
    "B33Y 10/00",
    "B33Y 30/00",
    "B33Y 70/00",
    "C08F 120/36",
    "C08F 220/36",
    "C08F 283/008",
    "C08G 18/022",
    "C08G 18/04",
    "C08G 18/10",
    "C08G 18/1816",
    "C08G 18/225",
    "C08G 18/246",
    "C08G 18/48",
    "C08G 18/6229",
    "C08G 18/672",
    "C08G 18/6755",
    "C08G 18/728",
    "C08G 18/73",
    "C08G 18/755",
    "C08G 18/792",
    "C08G 18/8125",
    "C08G 18/8175",
    "C08J 3/244",
    "C08K 7/14",
    "C09D 175/14",
    "C09J 175/14",
    "C09J 2475/00",
    "C09J 5/00"
  ],
  "ipc": [
    "B29C 64/124",
    "B33Y 10/00",
    "B33Y 70/00",
    "C08G 18/10",
    "C08G 18/67",
    "C08G 18/81",
    "C08G 18/02",
    "C08G 18/04",
    "C08G 18/22",
    "C08G 18/62",
    "C08G 18/72",
    "C08G 18/73",
    "C08G 18/79"
  ],
  "assignees": [
    "Covestro Deutschland AG"
  ],
  "inventors": [
    "Dirk Achten",
    "Thomas Büsgen",
    "Jörg Tillack",
    "Michael Ludewig",
    "Christoph Tomczyk",
    "Roland Wagner"
  ],
  "filing_date": "2017-11-14",
  "publication_date": "2019-10-22",
  "grant_date": "2019-10-22",
  "priority_date": "2016-11-14",
  "application_number": "US-201715812116-A",
  "family_id": "57354125",
  "cited_by_count": 10,
  "citations": [
    "GB809809A",
    "GB952931A",
    "GB966338A",
    "US3211703A",
    "US3330828A",
    "GB1386399A",
    "GB1391066A",
    "US4145544A",
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    "US6500876B2",
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    "US20080145624A1",
    "US20110089610A1",
    "US20140017460A1",
    "US9157007B2",
    "US20150158966A1"
  ]
}

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