Actinic radiation curable polymeric mixtures, cured polymeric mixtures and related processes

{
  "publication_number": "US10683381B2",
  "country": "US",
  "kind": "B2",
  "title": "Actinic radiation curable polymeric mixtures, cured polymeric mixtures and related processes",
  "abstract": "The present disclosure is directed to actinic radiation curable polymeric mixtures, cured polymeric mixtures, tires and tire components made from the foregoing, and related processes.",
  "claims": [
    "1. A process for producing a cured polymeric product, comprising providing an additive manufacturing device comprising a source of actinic radiation, an exterior support structure, an interior tank capable of containing a liquid mixture, and an interior support structure, providing a liquid mixture comprising an actinic radiation curable polymeric mixture comprising: (a) a polyfunctionalized diene monomer-containing polymer (i) having monomers selected from at least one of: 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, farnescene, and substituted derivatives of each of the foregoing, (ii) meeting at least one of the following: having a Mn of about 3,000 to about 135,000 grams/mole (polystyrene standard) or a Tg of about −105 to about −10° C., (iii) and having the formula: [P][F] n where P represents a diene polymer chain, F represents a functional group comprising an acrylate or methacrylate, n is 2 to about 15, and each F can be the same or different; (b) optionally a chain extender based upon F or reactive with F; (c) at least one actinic radiation sensitive photoinitiator comprising at least one of: a benzophenone, an aromatic α-hydroxyketone, a benzilketal, an aromatic α-aminoketone, a phenylglyoxalic acid ester, a mono-acylphosphinoxide, a bis-acylphosphinoxide, and a tris-acylphosphinoxide; (d) optionally, a photosensitizer; and (e) a polyfunctional crosslinker reactive with F and selected from the group consisting of polyol (meth)acrylates prepared from an aliphatic diol, triol, or tetraol containing 2-100 carbon atoms; polyallylic compounds prepared from an aliphatic diol, triol or tetraol containing 2-100 carbon atoms; polyfunctional amines; or combinations thereof to the interior tank, repeatedly forming upon a support structure a layer from the liquid mixture, and using actinic radiation to cure each layer, thereby producing the cured polymeric product, wherein at least one of the following is met: (ai) the polyfunctionalized diene monomer-containing polymer (a) is present in an amount of 1-100 parts and (b) is present in an amount of 0-99 parts; (aii) the at least one actinic sensitive photoinitiator (c) is present in an amount of about 1 part to about 10 parts (per 100 total parts of (a) and (b)); or (aiii) the photosensitizer (d) is present in an amount of about 0.1 parts to about 5 parts (per 100 total parts of (a) and (b)).",
    "2. The process of claim 1 wherein at least one of the following is met: (i) each layer has a thickness of about 0.01 mm to about 1 mm; (ii) the forming comprises solidifying each layer by using the actinic radiation to trace a pattern in the liquid material; (iii) the forming comprises dispensing the mixture from a printing head having a set of nozzles; (iv) the forming comprises using the actinic radiation to provide at least one pattern on the liquid material; (v) the forming comprises using the actinic radiation to project at least one image on the liquid material; (vi) the actinic radiation comprises UV or Visible light; (vii) the actinic radiation comprises light having a wavelength of about 320 to less than 500 nm; (viii) the interior tank is capable of receiving a liquid mixture from at least one cartridge; (ix) the liquid material is provided in at least one cartridge; or (x) at least two cartridges are utilized with one cartridge comprising (a) and (b) and a second cartridge comprising (b) in combination with (c).",
    "3. The process of claim 2, wherein (i), at least one of (ii)-(v), at least one of (vi) or (vii), and at least one of (viii)-(x) are met.",
    "4. The process of claim 1, wherein the actinic radiation curable polymeric mixture has a total amount of (a) and (b) of 100 parts and (c) is present in a total amount of at least about 0.1 parts based upon 100 parts of (a) and (b).",
    "5. The process of claim 1, wherein (ai) and at least one of (aii) and (aiii) are met.",
    "6. The process of claim 1, wherein each of (ai)-(aiii) is met.",
    "7. The process of claim 1, wherein each F comprises acrylate.",
    "8. The process of claim 1, wherein the chain extender is present and comprises an acrylate-based chain extender, and the crosslinker is present and comprises a poly acrylate-based crosslinker.",
    "9. The process of claim 1, wherein the polyfunctionalized diene monomer-containing polymer has a Mn of 10,000 to 135,000 grams/mole (polystyrene standard) and a Tg of −105 to −10° C.",
    "10. The process of claim 1, wherein the diene polymer chain comprises monomers selected from 1,3-butadiene or isoprene.",
    "11. The process of claim 10, wherein the diene polymer chain further comprises at least one vinyl aromatic monomer.",
    "12. The process of claim 1, wherein the polyfunctional crosslinker (e) is selected from polyol (meth)acrylates prepared from an aliphatic diol, triol, or tetraol containing 2-100 carbon atoms.",
    "13. The process of claim 12, wherein the polyfunctional crosslinker (e) is selected from at least one of: Trimethylolpropane tri(meth)acrylate, Pentaerythritol tetraacrylate, Pentaerythritol triacrylate, Trimethylolpropane ethoxylate triacrylate, Acrylated epoxidized soybean oil, Ditrimethylol Propane Tetraacrylate, Di-pentaerythritol Polyacrylate, Di-pentaerythritol Polymethacrylate, Di-pentaerythritol triacrylate, Di-pentaerythritol trimethacrylate, Di-pentaerythritol tetracrylate, Di-pentaerythritol tetramethacrylate, Di-pentaerythritol pent(meth)acrylate, Di-pentaerythritol hexa(meth)acrylate, Pentaerythritol Poly(meth)acrylate, Pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Pentaerythritol penta(meth)acrylate, Pentaerythritol hexa(meth)acrylate, Ethoxylated glycerine triacrylate, ε-Caprolactone ethoxylated isocyanuric acid triacrylate and Ethoxylated isocyanuric acid triacrylate, Tris(2-acryloxyethyl) Isocyanulate, Propoxylated glyceryl Triacrylate, ethyleneglycol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol di(meth)acrylate, ethyleneglycol dimethacrylate (EDMA), polyethyleneglycol di(meth)acrylates, polypropyleneglycol di(meth)acrylates, polybutyleneglycol di(meth)acrylates, 2,2-bis(4-(meth)acryloxyethoxyphenyl) propane, 2,2-bis(4-(meth)acryloxydiethoxyphenyl) propane, di(trimethylolpropane) tetra(meth)acrylate, and combinations thereof.",
    "14. The process of claim 1, wherein the chain extender (b) is present and comprises an (meth)acrylate monomer selected from C2 to about C18 alkyl functionalized (meth)acrylates.",
    "15. The process of claim 14, wherein the chain extender has a Tg of about −65 to about 10° C. and the chain extender has a Mw of about 72.06 to about 135,000 grams/mole.",
    "16. The process of claim 1, wherein the photosensitizer (d) is present and comprises at least one of a ketocoumarin, a xanthone, a thioxanthone, a polycyclic aromatic hydrocarbon, and an oximester derived from aromatic ketone.",
    "17. The process of claim 1, wherein the photoinitiator (c) comprises a benzophenone.",
    "18. The process of claim 1, wherein the photoinitiator (c) comprises an aromatic α-hydroxyketone, a benzilketal, or an aromatic α-aminoketone.",
    "19. The process of claim 1, wherein the actinic radiation curable polymeric mixture further comprises at least one filler.",
    "20. The process of claim 19, wherein at least one of the following is met: a. the at least one filler is present in an amount of up to about ⅔ of the total volume of the actinic radiation curable polymeric mixture; or b. the at least one filler is present in an amount of about 40 to about 80 parts (based upon 100 total parts of (a) and (b)).",
    "21. The process of claim 1, wherein the actinic radiation curable polymeric mixture has a viscosity at 25° C. of about 100 to about 5,000 cps.",
    "22. The process of claim 1, wherein the cured polymeric product that is produced is a tire component.",
    "23. The process of claim 22, wherein the tire component comprises a tread comprising at least one of the following: a closed hollow void, an undercut void, or an overhung tread.",
    "24. A process for producing a cured polymeric product, comprising providing an additive manufacturing device comprising a source of actinic radiation, an exterior support structure, an interior tank capable of containing a liquid mixture, and an interior support structure, providing a liquid mixture comprising an actinic radiation curable polymeric mixture comprising: (a) a polyfunctionalized diene monomer-containing polymer (i) having monomers selected from at least one of: 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, farnescene, and substituted derivatives of each of the foregoing, (ii) meeting at least one of the following: having a Mn of about 3,000 to about 135,000 grams/mole (polystyrene standard) or a Tg of about −105 to about −10° C., (iii) and having the formula: [P][F] n where P represents a diene polymer chain, F represents a functional group comprising an acrylate or methacrylate, n is 2 to about 15, and each F can be the same or different; (b) optionally a chain extender based upon F or reactive with F; (c) at least one actinic radiation sensitive photoinitiator comprising at least one of: a benzophenone, an aromatic α-hydroxyketone, a benzilketal, an aromatic α-aminoketone, a phenylglyoxalic acid ester, a mono-acylphosphinoxide, a bis-acylphosphinoxide, and a tris-acylphosphinoxide; (d) optionally, a photosensitizer; and (e) a polyfunctional crosslinker reactive with F and selected from the group consisting of polyol (meth)acrylates prepared from an aliphatic diol, triol, or tetraol containing 2-100 carbon atoms; polyallylic compounds prepared from an aliphatic diol, triol or tetraol containing 2-100 carbon atoms; polyfunctional amines; or combinations thereof to the interior tank, repeatedly forming upon a support structure a layer from the liquid mixture, and using actinic radiation to cure each layer, thereby producing the cured polymeric product, wherein the polyfunctionalized diene monomer-containing polymer (a) is present in an amount of 1-100 parts and (b) is present in an amount of 0-99 parts.",
    "25. The process of claim 24, wherein the actinic radiation curable polymeric mixture further comprises at least one filler in an amount of about 40 to about 80 parts (based upon 100 total parts of (a) and (b)).",
    "26. The process of claim 24, wherein the cured polymeric product that is produced is a tire component.",
    "27. The process of claim 24, wherein the tire component comprises a tread comprising at least one of the following: a closed hollow void, an undercut void, or an overhung tread.",
    "28. The process of claim 25, wherein the cured polymeric product that is produced is a tire component.",
    "29. The process of claim 25, wherein the tire component comprises a tread comprising at least one of the following: a closed hollow void, an undercut void, or an overhung tread.",
    "30. The process of claim 24, wherein the at least one actinic sensitive photoinitiator (c) is present in an amount of about 1 part to about 10 parts (per 100 total parts of (a) and (b)); and the photosensitizer (d) is present in an amount of about 0.1 parts to about 5 parts (per 100 total parts of (a) and (b))."
  ],
  "cpc": [
    "C08F 290/048",
    "B29C 64/10",
    "B29C 64/106",
    "B29C 64/124",
    "B29C 64/129",
    "B29C 64/135",
    "B29K 2009/00",
    "B29K 2105/0002",
    "B29K 2105/24",
    "B29L 2030/002",
    "B33Y 10/00",
    "B33Y 70/00",
    "B33Y 80/00",
    "B60C 1/00",
    "B60C 1/0016",
    "C08F 2/50",
    "C08F 222/1006",
    "C08K 3/013",
    "G03F 7/0037",
    "G03F 7/027",
    "G03F 7/029",
    "G03F 7/031",
    "G03F 7/033",
    "G03F 7/038"
  ],
  "assignees": [
    "BRIDGESTONE AMERICAS TIRE OPERATIONS LLC"
  ],
  "filing_date": "2015-12-17",
  "publication_date": "2020-06-16",
  "grant_date": "2020-06-16",
  "priority_date": "2014-12-23",
  "application_number": "US-201515539007-A",
  "family_id": "55182557",
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