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Patent · US10259956B2 · B2 · US

Curable ink composition

(11) Publication number
US10259956B2
(21) Application number
15/290,396
(22) Filing date
2016-10-11
(30) Priority date
2016-10-11
(43) Publication date
2019-04-16
(45) Date of grant
2019-04-16
(51) IPC
B29C 67/00; C09D 11/101; C09D 11/104; C09D 135/00; C09D 135/02; B29C 64/00; B29C 64/124; C09D 11/00; C09D 11/10; G03F 7/00
(52) CPC
  • 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: 11/101, 11/00, 11/104, 135/00, 135/02
  • 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: 64/00, 64/124, 67/00
  • 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: 2033/08
  • 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, 70/00, 80/00
  • 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: 7/0037
(73) Assignee
Xerox Corp
(72) Inventors
Naveen Chopra; Gordon Sisler; Saleh Jiddawi; C. Geoffrey Allen; Carolyn Moorlag
(54) Title
Curable ink composition
(57) Abstract

A curable ink composition for forming a three-dimensional (3D) object via a digital additive manufacturing system is provided. The composition may comprise greater than about 30 weight % of one or more oligomers, at least two monomers comprising a lowest viscosity monomer and a highest viscosity monomer, one or more photoinitiators, and optionally, one or more additives. The ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers may be at least about 0.5 and the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer may be at least about 5.

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Claims (19)

  1. A three-dimensional (3D) object curable ink composition for forming a 3D object via a digital additive manufacturing system, the composition comprising: greater than about 30 weight % of one or more oligomers, at least two monomers comprising a lowest viscosity monomer and a highest viscosity monomer, wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and are each characterized by a dynamic viscosity value at about 25° C., one or more photoinitiators, and optionally, one or more additives, wherein the ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers is at least about 0.5, wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is at least about 5, wherein all the oligomers in the composition are selected from a group consisting of oligomers having a dynamic viscosity in the range of about 1,000 cP to about 20,000 cP at about 25° C., and further wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and each have a dynamic viscosity of less than about 50 cP at about 25° C.
  2. The composition of claim 1 comprising at least about 50 weight % of the one or more oligomers.
  3. The composition of claim 1 comprising greater than 50 weight % to about 75 weight % of the one or more oligomers.
  4. The composition of claim 1, wherein the ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers is at least about 0.8.
  5. A three-dimensional (3D) object curable ink composition for forming a 3D object via a digital additive manufacturing system, the composition comprising: greater than about 30 weight % of one or more oligomers, at least two monomers comprising a lowest viscosity monomer and a highest viscosity monomer, wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and are each characterized by a dynamic viscosity value at about 25° C., one or more photoinitiators, and optionally, one or more additives, wherein the ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers is at least about 0.5, wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is at least about 5, wherein all the oligomers in the composition are selected from a group consisting of oligomers having a dynamic viscosity in the range of about 1,000 cP to about 20,000 cP at about 25° C., and further wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is greater than 7.
  6. The composition of claim 1, wherein the one or more oligomers are urethane meth(acrylate) oligomers.
  7. The composition of claim 1, wherein all the monomers in the composition are selected from monofunctional (meth)acrylates, multifunctional (meth)acrylates, monofunctional urethane (meth)acrylates and combinations thereof.
  8. The composition of claim 1, wherein the composition does not comprise monofunctional urethane (meth)acrylate monomers.
  9. The composition of claim 1, wherein the composition does not comprise a non-oligomeric urethane (meth)acrylate, a urea (meth)acrylate, or an isocyanurate (meth)acrylate.
  10. The composition of claim 1, wherein the composition when cured exhibits one or more of the following characteristics: a storage modulus at 25° C. of from about 1000 MPa to about 2500 MPa; a storage modulus at 65° C. of from about 100 MPa to about 1000 MPa; a tan δ peak temperature of at least about 70° C.; and a tan δ peak value of less than about 0.6.
  11. The composition of claim 10, wherein the composition when cured exhibits each of the characteristics.
  12. The composition of claim 10, wherein the composition when cured exhibits a storage modulus at 25° C. of from about 1000 MPa to about 2000 MPa; a storage modulus at 65° C. of from about 800 MPa to about 900 MPa; a tan δ peak temperature of at least about 100° C.; and a tan δ peak value of less than about 0.5.
  13. A three-dimensional object formed from the composition of claim 1.
  14. A three-dimensional (3D) object curable ink composition for forming a 3D object via a digital additive manufacturing system, the composition comprising: greater than about 30 weight % of one or more urethane (meth)acrylate oligomers, a lowest viscosity monomer, a highest viscosity monomer, and optionally, one or more additional monomers, the lowest viscosity monomer, the highest viscosity monomer and the one or more additional monomers selected from monofunctional (meth)acrylates, multifunctional (meth)acrylates, monofunctional urethane (meth)acrylates and combinations thereof, wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and are each characterized by a dynamic viscosity value at about 25° C., one or more photoinitiators, and optionally, one or more additives, wherein the ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers is at least about 0.5, wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is at least about 5, wherein all the oligomers in the composition are selected from a group consisting of oligomers having a dynamic viscosity in the range of about 1,000 cP to about 20,000 cP at about 25° C., and further wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and each have a dynamic viscosity of less than about 50 cP at about 25° C.
  15. The composition of claim 14 comprising at least about 50 weight % of the one or more urethane (meth)acrylate oligomers.
  16. The composition of claim 15, wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is greater than 7.
  17. The composition of claim 14, wherein the composition does not comprise a non-oligomeric urethane (meth)acrylate, a urea (meth)acrylate, or an isocyanurate (meth)acrylate.
  18. A method of forming a build structure comprising a 3D object and a support matrix, the method comprising: selectively dispensing a 3D object curable ink composition towards a substrate via a digital additive manufacturing system, the curable ink composition comprising greater than about 30 weight % of one or more oligomers, at least two monomers comprising a lowest viscosity monomer and a highest viscosity monomer, wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and are each characterized by a dynamic viscosity value at about 25° C., one or more photoinitiators, and optionally, one or more additives, wherein the ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers is at least about 0.5, wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is at least about 5, wherein all the oligomers in the composition are selected from a group consisting of oligomers having a dynamic viscosity in the range of about 1,000 cP to about 20,000 cP at about 25° C., and further wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and each have a dynamic viscosity of less than about 50 cP at about 25° C.; selectively dispensing a support material towards the substrate via the digital additive manufacturing system to form a support matrix for the 3D object, the 3D object and the support matrix providing a build structure corresponding to image data accessible by a processor of the digital additive manufacturing system; and curing the as-deposited curable ink composition.
  19. The composition of claim 1, wherein the composition consists of oligomers, including the one or more oligomers, selected from the group consisting of oligomers having a dynamic viscosity in the range of about 1,000 cP to about 20,000 cP at about 25° C.; monomers, including the lowest viscosity monomer and the highest viscosity monomer, wherein all the monomers in the compositions are selected from monofunctional (meth)acrylates, multifunctional (meth)acrylates and combinations thereof; photoinitiators, including the one or more photoinitiators; and optionally, additives, including the one or more additives, wherein all the additives in the composition are selected from sensitizing agents, polymerization inhibitors and antioxidant agents.

Description

The present disclosure is directed to curable ink compositions for use, e.g., in digital additive manufacturing techniques such as multi jet modeling (MJM).

Multi jet modeling (MJM) is a digital additive manufacturing technique for forming a three-dimensional (3D) object in which successive layers of a curable ink (e.g., via ultraviolet radiation) are jetted in a shape consistent with computer-accessible image data associated with the 3D object. A sacrificial support material is typically co-jetted with the curable ink to stabilize and support the 3D object during formation. In a post-processing step, the sacrificial support material is removed, e.g., by heating the composite structure in a convection oven or by washing with hot water. Unfortunately, 3D objects often undergo dimensional changes such as warping, rounded edges, etc., during such post-processing steps.

The present disclosure, which enables the post-processing of three-dimensional (3D) objects with improved fidelity to the intended structure, accordingly provides illustrative examples of curable ink compositions which may be used to form such 3D objects using digital additive manufacturing techniques.

In one aspect, curable ink compositions for forming a 3D object via a digital additive manufacturing system are provided. In embodiments, the composition comprises greater than about 30 weight % of one or more oligomers, at least two monomers comprising a lowest viscosity monomer and a highest viscosity monomer, one or more photoinitiators, and optionally, one or more additives.

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Record as JSON 
{
  "publication_number": "US10259956B2",
  "country": "US",
  "kind": "B2",
  "title": "Curable ink composition",
  "abstract": "A curable ink composition for forming a three-dimensional (3D) object via a digital additive manufacturing system is provided. The composition may comprise greater than about 30 weight % of one or more oligomers, at least two monomers comprising a lowest viscosity monomer and a highest viscosity monomer, one or more photoinitiators, and optionally, one or more additives. The ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers may be at least about 0.5 and the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer may be at least about 5.",
  "claims": [
    "1. A three-dimensional (3D) object curable ink composition for forming a 3D object via a digital additive manufacturing system, the composition comprising: greater than about 30 weight % of one or more oligomers, at least two monomers comprising a lowest viscosity monomer and a highest viscosity monomer, wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and are each characterized by a dynamic viscosity value at about 25° C., one or more photoinitiators, and optionally, one or more additives, wherein the ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers is at least about 0.5, wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is at least about 5, wherein all the oligomers in the composition are selected from a group consisting of oligomers having a dynamic viscosity in the range of about 1,000 cP to about 20,000 cP at about 25° C., and further wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and each have a dynamic viscosity of less than about 50 cP at about 25° C.",
    "2. The composition of claim 1 comprising at least about 50 weight % of the one or more oligomers.",
    "3. The composition of claim 1 comprising greater than 50 weight % to about 75 weight % of the one or more oligomers.",
    "4. The composition of claim 1, wherein the ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers is at least about 0.8.",
    "5. A three-dimensional (3D) object curable ink composition for forming a 3D object via a digital additive manufacturing system, the composition comprising: greater than about 30 weight % of one or more oligomers, at least two monomers comprising a lowest viscosity monomer and a highest viscosity monomer, wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and are each characterized by a dynamic viscosity value at about 25° C., one or more photoinitiators, and optionally, one or more additives, wherein the ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers is at least about 0.5, wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is at least about 5, wherein all the oligomers in the composition are selected from a group consisting of oligomers having a dynamic viscosity in the range of about 1,000 cP to about 20,000 cP at about 25° C., and further wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is greater than 7.",
    "6. The composition of claim 1, wherein the one or more oligomers are urethane meth(acrylate) oligomers.",
    "7. The composition of claim 1, wherein all the monomers in the composition are selected from monofunctional (meth)acrylates, multifunctional (meth)acrylates, monofunctional urethane (meth)acrylates and combinations thereof.",
    "8. The composition of claim 1, wherein the composition does not comprise monofunctional urethane (meth)acrylate monomers.",
    "9. The composition of claim 1, wherein the composition does not comprise a non-oligomeric urethane (meth)acrylate, a urea (meth)acrylate, or an isocyanurate (meth)acrylate.",
    "10. The composition of claim 1, wherein the composition when cured exhibits one or more of the following characteristics: a storage modulus at 25° C. of from about 1000 MPa to about 2500 MPa; a storage modulus at 65° C. of from about 100 MPa to about 1000 MPa; a tan δ peak temperature of at least about 70° C.; and a tan δ peak value of less than about 0.6.",
    "11. The composition of claim 10, wherein the composition when cured exhibits each of the characteristics.",
    "12. The composition of claim 10, wherein the composition when cured exhibits a storage modulus at 25° C. of from about 1000 MPa to about 2000 MPa; a storage modulus at 65° C. of from about 800 MPa to about 900 MPa; a tan δ peak temperature of at least about 100° C.; and a tan δ peak value of less than about 0.5.",
    "13. A three-dimensional object formed from the composition of claim 1.",
    "14. A three-dimensional (3D) object curable ink composition for forming a 3D object via a digital additive manufacturing system, the composition comprising: greater than about 30 weight % of one or more urethane (meth)acrylate oligomers, a lowest viscosity monomer, a highest viscosity monomer, and optionally, one or more additional monomers, the lowest viscosity monomer, the highest viscosity monomer and the one or more additional monomers selected from monofunctional (meth)acrylates, multifunctional (meth)acrylates, monofunctional urethane (meth)acrylates and combinations thereof, wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and are each characterized by a dynamic viscosity value at about 25° C., one or more photoinitiators, and optionally, one or more additives, wherein the ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers is at least about 0.5, wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is at least about 5, wherein all the oligomers in the composition are selected from a group consisting of oligomers having a dynamic viscosity in the range of about 1,000 cP to about 20,000 cP at about 25° C., and further wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and each have a dynamic viscosity of less than about 50 cP at about 25° C.",
    "15. The composition of claim 14 comprising at least about 50 weight % of the one or more urethane (meth)acrylate oligomers.",
    "16. The composition of claim 15, wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is greater than 7.",
    "17. The composition of claim 14, wherein the composition does not comprise a non-oligomeric urethane (meth)acrylate, a urea (meth)acrylate, or an isocyanurate (meth)acrylate.",
    "18. A method of forming a build structure comprising a 3D object and a support matrix, the method comprising: selectively dispensing a 3D object curable ink composition towards a substrate via a digital additive manufacturing system, the curable ink composition comprising greater than about 30 weight % of one or more oligomers, at least two monomers comprising a lowest viscosity monomer and a highest viscosity monomer, wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and are each characterized by a dynamic viscosity value at about 25° C., one or more photoinitiators, and optionally, one or more additives, wherein the ratio of the weight % of the total amount of oligomers to the weight % of the total amount of monomers is at least about 0.5, wherein the ratio of the weight % of the lowest viscosity monomer to the weight % of the highest viscosity monomer is at least about 5, wherein all the oligomers in the composition are selected from a group consisting of oligomers having a dynamic viscosity in the range of about 1,000 cP to about 20,000 cP at about 25° C., and further wherein the lowest viscosity monomer and the highest viscosity monomer are liquids at room temperature and each have a dynamic viscosity of less than about 50 cP at about 25° C.; selectively dispensing a support material towards the substrate via the digital additive manufacturing system to form a support matrix for the 3D object, the 3D object and the support matrix providing a build structure corresponding to image data accessible by a processor of the digital additive manufacturing system; and curing the as-deposited curable ink composition.",
    "19. The composition of claim 1, wherein the composition consists of oligomers, including the one or more oligomers, selected from the group consisting of oligomers having a dynamic viscosity in the range of about 1,000 cP to about 20,000 cP at about 25° C.; monomers, including the lowest viscosity monomer and the highest viscosity monomer, wherein all the monomers in the compositions are selected from monofunctional (meth)acrylates, multifunctional (meth)acrylates and combinations thereof; photoinitiators, including the one or more photoinitiators; and optionally, additives, including the one or more additives, wherein all the additives in the composition are selected from sensitizing agents, polymerization inhibitors and antioxidant agents."
  ],
  "description_excerpt": "The present disclosure is directed to curable ink compositions for use, e.g., in digital additive manufacturing techniques such as multi jet modeling (MJM).\n\nMulti jet modeling (MJM) is a digital additive manufacturing technique for forming a three-dimensional (3D) object in which successive layers of a curable ink (e.g., via ultraviolet radiation) are jetted in a shape consistent with computer-accessible image data associated with the 3D object. A sacrificial support material is typically co-jetted with the curable ink to stabilize and support the 3D object during formation. In a post-processing step, the sacrificial support material is removed, e.g., by heating the composite structure in a convection oven or by washing with hot water. Unfortunately, 3D objects often undergo dimensional changes such as warping, rounded edges, etc., during such post-processing steps.\n\nThe present disclosure, which enables the post-processing of three-dimensional (3D) objects with improved fidelity to the intended structure, accordingly provides illustrative examples of curable ink compositions which may be used to form such 3D objects using digital additive manufacturing techniques.\n\nIn one aspect, curable ink compositions for forming a 3D object via a digital additive manufacturing system are provided. In embodiments, the composition comprises greater than about 30 weight % of one or more oligomers, at least two monomers comprising a lowest viscosity monomer and a highest viscosity monomer, one or more photoinitiators, and optionally, one or more additives.",
  "cpc": [
    "C09D 11/101",
    "B29C 64/00",
    "B29C 64/124",
    "B29C 67/00",
    "B29K 2033/08",
    "B33Y 10/00",
    "B33Y 70/00",
    "B33Y 80/00",
    "C09D 11/00",
    "C09D 11/104",
    "C09D 135/00",
    "C09D 135/02",
    "G03F 7/0037"
  ],
  "ipc": [
    "B29C 67/00",
    "C09D 11/101",
    "C09D 11/104",
    "C09D 135/00",
    "C09D 135/02",
    "B29C 64/00",
    "B29C 64/124",
    "C09D 11/00",
    "C09D 11/10",
    "G03F 7/00"
  ],
  "assignees": [
    "Xerox Corp"
  ],
  "inventors": [
    "Naveen Chopra",
    "Gordon Sisler",
    "Saleh Jiddawi",
    "C. Geoffrey Allen",
    "Carolyn Moorlag"
  ],
  "filing_date": "2016-10-11",
  "publication_date": "2019-04-16",
  "grant_date": "2019-04-16",
  "priority_date": "2016-10-11",
  "application_number": "US-201615290396-A",
  "family_id": "59955393",
  "cited_by_count": 9,
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