Resin composition and process for investment casting using stereolithography

• US 5,391,460 A
• Filed: 07/12/1993
• Issued: 02/21/1995
• Est. Priority Date: 07/12/1993
• Status: Expired due to Term

• Current Assignee: OL Security LLC (Intellectual Ventures LLC)
• Original Assignee: Hughes Aircraft Company (Rtx Corporation)
• Inventors: Dougherty, Thomas K., Elias, William E., Thelander, Timothy C., Bhavnani, Mahesh N.
• Primary Examiner(s): McCamish, Marion E.
• Assistant Examiner(s): Chapman, Mark A.
• Application Number:
  US08/089,544
• Time in Patent Office: 589 Days
• Field of Search: 522/79, 164/526, 164/527, 430/269
• US Class Current: 430/269
• CPC Class Codes: B22C 1/08 for decreasing shrinkage of the mould, e.g. for investment casting
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/0048 characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents

Abstract

A resin composition for investment casting contains a moderate boiling temperature liquid inert diluent, having a boiling point in the range of about 200° to 300° C. The presence of the liquid inert diluent allows the resin to be used as a pattern, or model, in investment casting by preventing breaking of the mold during burnout of the resin. Any of the conventional resins suitable for stereolithography may be employed in the practice of the invention. To the resin is added a moderate boiling point solvent in the amount of about 5 to 30 wt %. Use of the moderate boiling point solvent in conjunction with the resin allows the pattern to shrink and crack at moderate temperature before final burnout. The shrinkage occurs faster and at a lower temperature as compared to the prior art.

Claims

1. A stereolithographic resin for investment casting comprising;

(a) at least one light-curable, ethylenically unsaturated liquid resin;

(b) at least one photoinitiator, ranging in concentration from about 2 to 10%, and

(c) at least one solvent having a boiling point of about 200°

to 300°

C., inert to said light-curable, ethylenically unsaturated liquid resin and soluble in said resin, wherein said solvent is present in the amount of about 5 to 30 weight percent.

2. The stereolithographic resin of claim 1 wherein said moderate boiling point solvent is selected from the group consisting of propylene carbonate, phenol, glycerol, ethylene glycol, diglyme, benzylethyl ether, phenylether, veratrole, ethylene glycol diacetate, benzyl acetate, benzyl alcohol, methylbenzoate, ethylbenzoate, butyrolactone, ethyl malonate, butyl phosphate, trichlorotrifluoroethane, chloronaphthalene, nitrobenzene, succinonitrile, tolunitrile, octanitrile, benzonitrile, aniline, toluidine, and quinoline.

3. The stereolithographic resin of claim 1 wherein said light-curable, ethylenically unsaturated liquid resin is selected from the group consisting of vinyls, acrylates, methacrylates, and vinyl ethers.

4. The stereolithographic resin of claim 1 wherein said photoinitiator comprises a photoactivated free radical initiator selected from the group consisting of benzyl and phenyl ketones, benzyl and phenyl ketals, benzoin ethers, acetophenones, benzoyl oximes, acylphosphines, xanthones, and quinones.

5. The stereolithographic resin of claim 1 further including a multifunctional crosslinker.

6. The stereolithographic resin of claim 5 wherein said multifunctional crosslinker is present in an amount ranging from about 2 to 20%.

7. A stereolithographic resin for investment casting comprising:

(a) at least one light-curable, ethylenically unsaturated liquid selected from the group consisting of vinyls, acrylates, and methacrylates;

(b) at least one photoinitiator, ranging in concentration from about 2 to 10%;

(c) at least one solvent inert to said light-curable, ethylenically unsaturated liquid, soluble therein, and having a boiling point ranging from about 200°

to 300°

C.; and

(d) at least one multifunctional crosslinker, ranging in concentration from about 2 to 20%.

8. The stereolithographic resin of claim 7 wherein said solvent is selected from the group consisting of propylene carbonate,-phenol, glycerol, ethylene glycol, diglyme, benzylethyl ether, phenylether, veratrole, ethylene glycol diacetate, benzyl acetate, benzyl alcohol, methylbenzoate, ethylbenzoate, butyrolactone, ethyl malonate, butyl phosphate, trichlorotrifluoroethane, chloronaphthalene, nitrobenzene, succinonitrile, tolunitrile, octanitrile, benzonitrile, aniline, toluidine, and quinoline.

9. The stereolithographic resin of claim 8 wherein said inert solvent comprises propylene carbonate.

10. A method of investment casting comprising the steps of:

(a) investing a three-dimensional pattern in a mold material, said pattern being constituted by a cross-linked polymeric matrix constituted by a light-cured ethylenically unsaturated material having dissolved therein a solvent having a boiling point ranging from about 200°

to 300°

C., being non-reactive with said ethylenically unsaturated material, and being soluble therein; and

(b) heating said mold material with said pattern to burn said pattern out of said mold, said solvent shrinking and cracking said pattern during the heating operation to prevent the thermal expansion of said pattern from cracking said mold.

11. The method of claim 10 wherein said moderate boiling point solvent is selected from the group consisting of propylene carbonate, phenol, glycerol, ethylene glycol, diglyme, benzylethyl ether, phenylether, veratrole, ethylene glycol diacetate, benzyl acetate, benzyl alcohol, methylbenzoate, ethylbenzoate, butyrolactone, ethyl malonate, butyl phosphate, trichlorotrifluoroethane, chloronaphthalene, nitrobenzene, succinonitrile, tolunitrile, octanitrile, benzonitrile, aniline, toluidine, and quinoline.

12. The method of claim 10 wherein said light-curable, ethylenically unsaturated liquid is selected from the group consisting of vinyls, acrylates, methacrylates, and vinyl ethers.

13. The method of claim 10 wherein said photoinitiator comprises a photoactivated free radical initiator selected from the group consisting of benzyl and phenyl ketones, benzyl and phenyl ketals, benzoin ethers, acetophenones, benzoyl oximes, acylphosphines, xanthones, and quinones.

14. The method of claim 10 wherein said burnout is performed under the following conditions:

(a) slowly heating said mold material with said pattern therein to a temperature within the range of about 80°

to 120°

C. at a rate of about 2°

to 10°

C. per hour;

(b) holding at that temperature for 4 to 12 hours for breakage and shrinkage of said pattern to occur;

(c) heating to a temperature within the range of about 140°

to 160°

C. at a rate of about 1°

to 5°

C. per minute and holding at that temperature for about 2 to 8 hours to complete shrinkage of said pattern; and

(d) heating to an elevated temperature in the range of about 750°

to 1,000°

C. at a rate of about 1°

to 5°

C. per minute and holding at that temperature for about 2 to 8 hours to complete removal of said pattern.

15. A method of investment casting comprising the steps of:

(a) forming a first thin layer of a light-curable liquid formulation comprising

(1) at least one light-curable, ethylenically unsaturated liquid resin selected from the group consisting of vinyls, acrylates, and methacrylates,

(2) at least one photoinitiator, ranging in concentration from about 2 to 10%,

(3) about 5 to 30 wt % of at least one inert solvent having a boiling point ranging from about 200°

to 300°

C. and being essentially non-reactive with said light-curable, ethylenically unsaturated liquid and soluble therein, and

(4) a multifunctional crosslinker, ranging in concentration from about 2 to 20%;

(b) exposing said first thin layer of said light-curable liquid formulation to a light source to cause polymerization of selected portions of said layer and form a first polymerized layer;

(c) covering said first polymerized layer with a second thin layer of said light-curable liquid formulation;

(d) exposing said second thin layer to said light source to polymerize selected portions of said layer upon said first polymerized layer and form a second polymerized layer;

(e) repeating steps (b) and (c) at least once to produce a specimen;

(f) completing the cure of said specimen to produce a pattern;

(g) investing said pattern in a mold material; and

(h) heating said mold material with said pattern in it to fuse the material of said mold and to burn said pattern out of said mold to produce a mold.

16. The method of claim 15 wherein said inert solvent comprises propylene carbonate.

17. The method of claim 15 wherein said light-curable liquid formulation is exposed to a light source having a wavelength in the range of about 200 to 600 nm.

18. The method of claim 15 wherein said burnout is performed under the following conditions:

(a) slowly heating said mold material with said pattern therein to a temperature within the range of about 80°

to 120°

C. at a rate of about 2°

to 10°

C. per hour;

(b) holding at that temperature for 4 to 12 hours for breakage and shrinkage of said pattern to occur;

(c) heating to a temperature within the range of about 140°

to 160°

C. at a rate of about 1°

to 5°

C. per minute and holding at that temperature for about 2 to 8 hours to complete shrinkage of said pattern; and

(d) heating to an elevated temperature in the range of about 750°

to 1,000°

C. at a rate of about 1°

to 5°

C. per minute and holding at that temperature for about 2 to 8 hours to complete removal of said pattern.