Rapid prototyping method and radiation-curable composition for use therein

• US 7,815,835 B2
• Filed: 06/29/2006
• Issued: 10/19/2010
• Est. Priority Date: 06/30/2005
• Status: Expired due to Fees

• Current Assignee: Technische Universitã¤T Wien
• Original Assignee: Technische Universitã¤T Wien
• Inventors: Inführ, Robert, Lichtenegger, Helga, Liska, Robert, Gruber, Heinrich, Stampfl, Jürgen
• Primary Examiner(s): Gupta; Yogendra N
• Assistant Examiner(s): Brown, II; David N
• Application Number:
  US11/922,747
• Publication Number:
  US 20090224438A1
• Time in Patent Office: 1,573 Days
• Field of Search: 264/401, 264/425, 264/227, 264/221, 430/269, 522/182, 522/181
• US Class Current: 264/221
• CPC Class Codes: B29C 33/3842 Manufacturing moulds, e.g. shaping the mould surface by machining
• CPC Class Codes: B29C 64/106 using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
• 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: B33Y 80/00 Products made by additive manufacturing
• CPC Class Codes: C08F 2/48 by ultraviolet or visible light
• CPC Class Codes: G03F 7/0017 for the production of embossing, cutting or similar devices; for the production of casting means
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/0755 Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence
• CPC Class Codes: G03F 7/42 Stripping or agents therefor
• CPC Class Codes: G03F 7/423 containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
• CPC Class Codes: G03F 7/425 containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
• CPC Class Codes: G03F 7/426 containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides

Abstract

The invention relates to a method for producing three-dimensional objects, comprising producing a three-dimensional structure by sequential selective curing of layers of a composition curable with visible and/or ultraviolet light into a solid polymeric material by sequential exposure of the individual layers to UV and/or visible light, whereafter a three-dimensional object is produced by use of the three-dimensional structure thus formed, followed by removing the three-dimensional structure from or of the three-dimensional object, characterized in that removing the three-dimensional structure is accomplished by chemically cleaving the polymeric material as well as simultaneously or subsequently dissolving the material in a solvent or mixed solvent and/or melting the material.

Claims

1. A method for producing three-dimensional objects, comprising:

producing a three-dimensional structure by sequential selective curing of layers of a composition curable with visible and/or ultraviolet light into a solid polymeric material by sequential exposure of the individual layers of said polymeric material to UV and/or visible light,

producing a three-dimensional object on or inside the three-dimensional structure thus formed, and

removing the three-dimensional structure from on or inside the three-dimensional object, by chemically cleaving the polymeric material and, simultaneously or subsequently, dissolving the polymeric material in a solvent or mixed solvent, and/or melting the material.

2. The method of claim 1, wherein the three-dimensional structure forms an original mold wherein or whereon a casting mold representing the three-dimensional object is molded.

3. The method of claim 1, wherein the three-dimensional structure forms a casting mold wherein or whereon the three-dimensional object is molded.

4. The method of claim 1, wherein the polymeric material is dissolved in a solvent, and the solvent is selected from the group consisting of tetrahydrofuran, dioxane, ethyl acetate, toluene, and mixtures of two or more thereof.

5. The method of claim 1, wherein the polymeric material is dissolved in a solvent and the solvent is a substantially anhydrous solvent.

6. The method of claim 1, wherein cleaving the polymeric material is accomplished by use of at least one acid or base.

7. The method of claim 6, wherein the base is selected from the group consisting of butylamine, hexylamine, octylamine, and mixtures of two or more thereof.

8. The method of claim 6, wherein the acid is selected from the group consisting of formic acid, acetic acid, methanesulfonic acid, and mixtures of two or more thereof.

9. The method of claim 1, wherein the composition which is curable with visible and/or ultraviolet light into a solid polymeric material comprises

(a) 20 to 90% by weight of at least one compound of the general formula

CH₂═

C(R′

)—

X

wherein

R′

is hydrogen or a CH₃ group,

X is —

CO—

OR¹, —

CONR¹R², —

O—

CO—

R¹, —

OR¹, —

C₆H₅ or —

Z—

R—

Y,

wherein R¹ and R² independently represent branched alkyl radicals containing 3 to 20 carbon atoms;

6- to 10-membered cycloaliphatic radicals which may be optionally substituted with one or more linear or branched alkyl groups and which may optionally contain one or more heteroatoms, as ring members;

cycloaliphatic radicals containing 6 to 20 carbon atoms, bridged with at least one linear or branched alkylene group;

or aromatic radicals containing 6 to 30 carbon atoms,

Z is —

CO—

O—

or —

CO—

NH—

,

R is a linear or branched alkylene radical containing 1 to 20 carbon atoms;

a cycloaliphatic radical containing 6 to 10 carbon atoms;

or an aromatic radical containing 6 to 30 carbon atoms, and

Y is —

NR¹R², —

O—

CO—

NR¹R², —

NH—

CO—

OR¹, —

NH—

CO—

R¹, —

O—

CO—

R¹, —

CO—

OR¹, —

CO—

NHR¹ or —

OR¹;

(b) 5 to 50% by weight of at least one cleavable crosslinker;

(c) 0.01 to 5% by weight of at least one initiator;

(d) 0 to 5% by weight of at least one co-initiator; and

(e) 0 to 70% by weight of one or more additives, said additives being selected from the group consisting of fillers, stabilizers, viscosity modifiers, and solvents.

10. The method of claim 9, wherein, in constituent (a), X is —

CO—

OR¹ or —

CONR¹R², wherein R¹ and R² independently represent branched alkyl radicals containing 3 to 10 carbon atoms;

6- to 10-membered cycloaliphatic radicals which may optionally contain one or more heteroatoms, as ring members;

cycloaliphatic radicals containing 6 to 16 carbon atoms, bridged with at least one linear or branched alkylene group;

or —

C₆H₅.

11. The method of claim 9 wherein constituent (a) is selected from the group consisting of isobutyl methacrylate, 2-ethylhexylacrylate, cyclohexyl acrylate, isobornyl acrylate, diisobutylacrylamide, cyclohexylacrylamide, isobornylacrylamide, N-acrylpiperidine, and N-methyl-N-cyclohexylacrylamide.

12. The method of claim 9, wherein at least one cleavable crosslinker is selected from the group consisting of methacrylic anhydride, bis(methacryloyloxy)dimethylsilane, bis(methacryloyloxy)tetramethyldisiloxane, and dimethylsilylen-bis(oxyethylene methacrylate).

13. The method of claim 9, wherein the composition is curable into a solid polymeric material soluble in organic solvents.

14. The method of claim 9, wherein the composition is curable into an acid- or base-cleavable polymeric material.

15. The method of claim 9, wherein the composition is curable to a polymeric material that, optionally after chemically cleaving at least one bond of the at least one cleavable crosslinker, is meltable.

16. The method according to claim 9, wherein the 6- to 10-membered cycloaliphatic radical comprising R¹ or R² contains one, two or three heteroatoms.

17. The method according to claim 10, wherein the 6- to 10-membered cycloaliphatic radical comprising R¹ or R² contains one or two heteroatoms.