Phase change solid imaging material

• US 6,395,811 B1
• Filed: 04/11/2000
• Issued: 05/28/2002
• Est. Priority Date: 11/11/1999
• Status: Expired due to Term

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Inventors: Nguyen, My T., Bui, Loc V., Kwo, Kelly, Doan, Vu
• Primary Examiner(s): Szekely, Peter
• Application Number:
  US09/547,160
• Time in Patent Office: 777 Days
• Field of Search: 523/160,161 524/198,199,230,270,272,487,507,514
• US Class Current: 524/198
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C08G 18/2825 having at least 6 carbon atoms
• CPC Class Codes: C08G 18/3821 Carboxylic acids; Esters thereof with monohydroxyl compounds
• CPC Class Codes: C08G 18/71 Monoisocyanates or monoisothiocyanates
• CPC Class Codes: C08G 69/34 using polymerised unsaturated fatty acids
• CPC Class Codes: C08J 3/00 Processes of treating or compounding macromolecular substances
• CPC Class Codes: C08K 5/0008 Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• CPC Class Codes: C08K 5/205 Compounds containing groups, e.g. carbamates
• CPC Class Codes: C08K 5/29 Compounds containing one or more carbon-to-nitrogen double bonds
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 11/34 Hot-melt inks

Abstract

A component to control the viscosity of phase change material formulations is made by reacting selected nucleophiles, including fatty acid/alcohol reactants with an isocyanate, is disclosed. The addition of the isocyanate and the different nucleophiles will create a viscosity modifying component of low viscosity that can be formulated with higher molecular weight polyamide resins to achieve increased toughness in phase change solid imaging materials and carrier compositions used to make phase change ink jet inks.

Claims

1. A formulation for use in jetting from a print head comprising:

(a) a component to control the viscosity of the formulation, the component being a linear alkyl urethane;

(b) a component to promote adhesion to a substrate;

(c) a component to impart toughness to the formulation; and

(d) a component to control shrinkage of the jetted formulation.

2. The formulation according to claim 1 wherein the linear alkyl urethane is a linear alkyl carbamate defined by the structure

wherein R₁ is an isocyanate having a carbon chain length of from about C₄ to about C₆₀ and R₂ is an alcohol having a carbon chain length of from about C₄ to about C₆₀.

3. The formulation according to claim 1 wherein the component to control shrinkage of the jetted formulation is selected from the group consisting of a urethane wax, an amide wax, alkyl wax and combinations thereof.

4. The formulation according to claim 1 wherein the component to impart toughness is a polyamide resin.

5. The formulation according to claim 2 wherein the linear alkyl carbamate is selected from the group consisting of octadecyl, octadecyl carbamate;

dodecyl, octadecyl carbamate;

hexadecyl, octadecyl carbamate; and

hexyl, octadecyl carbamate.

6. The formulation according to claim 1 wherein the component to control adhesion to a substrate is selected from the group consisting of a rosin carbamate, a rosin ester, glycerin rosin ester, hydrogenated pentaerythritol ester, hydrogenated glycerin ester, modified tall oil rosin, a polymerized rosin, an aromatic hydrocarbon rosin, an aliphatic hydrocarbon rosin and combinations thereof.

7. The formulation according to claim 1 wherein the component to promote adhesion to a substrate is a rosin carbamate tackifier selected from the group consisting of butyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate;

hexyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate;

octyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate;

dodecyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate; and

octadecyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate.

8. The formulation according to claim 4 wherein the component to impart toughness to the formulation further includes a tetra-amide.

9. The formulation according to claim 3 wherein the urethane wax is the reaction product of a monohydric alcohol and a mono-isocyanate.

10. The formulation according to claim 9 wherein the monohydric alcohol is selected from the group consisting of an aliphatic alcohol, an aliphatic/aromatic alcohol, an aromatic alcohol, and a fused ring alcohol and combinations thereof.

11. The formulation according to claim 10 wherein the monohydric alcohol is selected from the group consisting of butyl alcohol, hexyl alcohol, octyl alcohol, dodecyl alcohol, hexadecyl alcohol, octadecyl alcohol, and behenyl alcohol.

12. The formulation according to claim 1 wherein the formulation further includes an anti-oxidant.

13. The formulation according to claim 4 wherein the polyamide resin has a weight average molecular weight in the range of from about 3,000 to about 32,000.

14. A solid imaging material for use in three-dimensional model rapid prototyping comprising:

a component to control the viscosity of the material, the component being a linear alkyl urethane;

a component to promote adhesion to a substrate;

a component to impart toughness to the material; and

a component to control thermal runaway in a three-dimensional build object formed of the jetted material.

15. The material according to claim 14 wherein the linear alkyl urethane is a linear alkyl carbamate defined by the structure

wherein R₁ is an isocyanate having a carbon chain length of from about C₄ to about C₆₀ and R₂ is an alcohol having a carbon chain length of from about C₄ to about C₆₀.

16. The material according to claim 14 wherein the component to control thermal runaway of the jetted material is selected from the group consisting of a urethane wax, an amide wax, alkyl wax and combinations thereof.

17. The material according to claim 14 wherein the component to impart toughness is a polyamide resin.

18. The material according to claim 17 wherein the polyamide resin has a weight average molecular weight in the range of from about 3,000 to about 32,000.

19. The material according to claim 15 wherein the linear alkyl carbamate is selected from the group consisting of octadecyl, octadecyl carbamate;

dodecyl, octadecyl carbamate;

hexadecyl, octadecyl carbamate; and

hexyl, octadecyl carbamate.

20. The material according to claim 14 wherein the component to control adhesion to a substrate is selected from the group consisting of a rosin carbamate, a rosin ester, glycerin rosin ester, hydrogenated pentaerythritol ester, hydrogenated glycerin ester, modified tall oil rosin, a polymerized rosin, an aromatic hydrocarbon rosin, an aliphatic hydrocarbon rosin and combinations thereof.

21. The material according to claim 14 wherein the component to promote adhesion to a substrate is a rosin carbamate tackifier selected from the group consisting of butyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate;

hexyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate;

octyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate;

dodecyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate; and

octadecyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate.

22. The material according to claim 14 wherein the component to impart toughness to the material further includes a tetra-amide.

23. The material according to claim 16 wherein the urethane wax is the reaction product of a monohydric alcohol and a mono-isocyanate.

24. The material according to claim 23 wherein the monohydric alcohol is selected from the group consisting of an aliphatic alcohol, an aliphatic/aromatic alcohol, an aromatic alcohol, and a fused ring alcohol and combinations thereof.

25. The material according to claim 24 wherein the monohydric alcohol is selected from the group consisting of butyl alcohol, hexyl alcohol, octyl alcohol, dodecyl alcohol, hexadecyl alcohol, octadecyl alcohol, and behenyl alcohol.

26. The material according to claim 14 wherein the material further includes an anti-oxidant.

27. A formulation for use in jetting from a print head comprising:

(a) a component to impart toughness to the formulation;

(b) a component to promote adhesion;

(c) a component to control shrinkage of the jetted formulation; and

(d) a component to control the viscosity of the formulation, the component being compatible with the components in a, b, and c above and having a viscosity of less than about 5 cPs.

28. The formulation according to claim 27 wherein the component to control the viscosity of the formulation is a linear alkyl urethane.

29. The formulation according to claim 28 wherein the linear alkyl urethane is a linear alkyl carbamate defined by the structure

wherein R₁ is an isocyanate having a carbon chain length of from about C₄ to about C₆₀ and R₂ is an alcohol having a carbon chain length of from about C₄ to about C₆₀.

30. The formulation according to claim 29 wherein the linear alkyl carbamate is selected from the group consisting of octadecyl, octadecyl carbamate;

dodecyl, octadecyl carbamate;

hexadecyl, octadecyl carbamate; and

hexyl, octadecyl carbamate.

31. The formulation according to claim 27 wherein the component to impart toughness is a polyamide resin.

32. The formulation according to claim 31 wherein the polyamide resin has a weight average molecular weight in the range of from about 3,000 to about 32,000.

33. The formulation according to claim 27 wherein the component to control thermal runaway of the jetted formulation is selected from the group consisting of a urethane wax, an amide wax, alkyl wax and combinations thereof.

34. The formulation according to claim 27 wherein the component to control adhesion to a substrate is selected from the group consisting of a rosin carbamate, a rosin ester, glycerin rosin ester, hydrogenated pentaerythritol ester, hydrogenated glycerin ester, modified tall oil rosin, a polymerized rosin, an aromatic hydrocarbon rosin, an aliphatic hydrocarbon rosin and combinations thereof.

35. The formulation according to claim 34 wherein the component to promote adhesion to a substrate is a rosin carbamate tackifier selected from the group consisting of butyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate;

hexyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate;

octyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate;

dodecyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate; and

octadecyl [3-({[(7-isopropyl-1,4a-dimethyltetradecahydro-1-phenanthrenyl)methoxy]carbonyl}amino)-1,4,4-trimethylcyclohexyl]methyl carbamate.

36. The formulation according to claim 27 wherein the component to impart toughness to the formulation further includes a tetra-amide.

37. The formulation according to claim 33 wherein the urethane wax is the reaction product of a monohydric alcohol and a mono-isocyanate, the monohydric alcohol further being selected from the group consisting of an aliphatic alcohol, an aliphatic/aromatic alcohol, an aromatic alcohol, and a fused ring alcohol and combinations thereof.

38. The formulation according to claim 37 wherein the alcohol is selected from the group consisting of butyl alcohol, hexyl alcohol, octyl alcohol, dodecyl alcohol, hexadecyl alcohol, octadecyl alcohol, and behenyl alcohol.

39. The formulation according to claim 27 wherein the formulation further includes an anti-oxidant.