Methods and compositions related to stereolithography

• US 5,639,413 A
• Filed: 03/30/1995
• Issued: 06/17/1997
• Est. Priority Date: 03/30/1995
• Status: Expired due to Fees

• Current Assignee: James Vincent Crivello
• Original Assignee: James Vincent Crivello
• Inventors: Crivello, James Vincent
• Primary Examiner(s): Chiesa, Richard L.
• Application Number:
  US08/413,258
• Time in Patent Office: 810 Days
• Field of Search: 425/174.4, 264/401, 430/280.1
• US Class Current: 264/401
• CPC Class Codes: B29C 64/135 the energy source being concentrated, e.g. scanning lasers or focused light sources
• CPC Class Codes: B29K 2995/0073 smooth
• 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: C08G 59/306 containing silicon
• CPC Class Codes: C08G 59/3254 containing atoms other than carbon, hydrogen, oxygen or nitrogen
• 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 7/075 Silicon-containing compounds
• 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 7/0757 Macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence

Abstract

An improved system for producing a three-dimensional object from a fluid medium is described. The fluid medium includes an epoxy-functional silicon-containing monomer or oligomer, and a suitable cationic photoinitiator. The medium is used in a stereolithographic apparatus, which converts computer-generated data for the desired part to a real three-dimensional part, via the directed action of a laser beam or similar energy form on the liquid medium. This invention also embraces a method for producing the three-dimensional object from the liquid medium, utilizing a family of epoxy-functional silicon-containing materials.

Claims

1. An improved system for producing a three-dimensional object from a fluid medium, comprising the following components:

(a) a body of fluid medium capable of solidification when subjected to prescribed stimulation, said fluid medium itself comprising;

(i) at least one monomer or oligomer containing at least one epoxycyclohexyl group which is bonded directly or indirectly to a group containing at least one silicon atom, and

(ii) a cationic photoinitiator for component (i);

(b) object support means immersed within said fluid medium for supporting a three-dimensional object to be formed;

(c) translational means for selectively moving said object support means progressively away from a designated surface of said fluid medium; and

(d) reaction means capable of altering the physical state of the fluid medium, and operating in a prescribed pattern upon said designated surface of the medium to provide a thin solid lamina at the surface, representing a corresponding cross-sectional lamina of the three-dimensional object to be formed;

whereby successive adjacent laminae are provided to form the three-dimensional object on the object support means as the translational means moves the support means away from the designated surface.

2. The system of claim 1, wherein component a(i) comprises a linear, branched or cyclic epoxy-functional silicone monomer or oligomer.

3. The system of claim 2, wherein the linear epoxy-functional silicone monomer or oligomer comprises multifunctional siloxane units having a formula selected from the group consisting of:

##STR13## wherein each R group is, independently, a monovalent substituted or unsubstituted C_1-12 alkyl, C_1-12 cycloalkyl, or phenyl radical;

each R¹ group is, independently, R, a monovalent C_2-12 alkyl radical, or a monovalent epoxy-functional group having about 2 to 10 carbon atoms, with the proviso that at least one of the R¹ groups is epoxy-functional;

R² is an alkylene or alkylene ether group containing about 2 to about 20 carbon atoms;

n is about 1 to about 10; and

m is 1 to 4.

4. The system of claim 3, wherein the epoxy-functional silicone monomer is bis[2-(3{7-oxabicyclo[4.1.0]heptyl})ethyl]-1,1,3,3-tetramethyldisiloxane, or bis[2-{2,3-epoxybicyclo[2.2.1]heptyl})ethyl]-1,1,3,3-tetramethyldisiloxane

5. The system of claim 2, wherein component a(i) comprises an oligomeric polysiloxane containing pendant epoxycyclohexyl groups.

6. The system of claim 1, wherein component a(i) comprises a silicon-containing epoxy monomer having the formula ##STR14## wherein each R group is, independently, a monovalent substituted or unsubstituted C_1-12 alkyl, C_1-12 cycloalkyl, or phenyl radical;

each R¹ group is, independently, R, a monovalent C_2-12 alkyl radical, or a monovalent epoxy-functional group having about 2 to 10 carbon atoms, with the proviso that at least one of the R¹ groups is epoxy-functional; and

m is 1 to 4.

7. The system of claim 6, wherein the silicon monomer is methylphenyl-di(epoxy cyclohexylethyl)silane.

8. The system of claim 1, wherein component a(i) is a cyclic epoxy-functional silicone monomer or oligomer comprising siloxane units of the formula ##STR15## wherein each R group is independently selected from the group consisting of monovalent C_1-12 alkyls, C_1-12 cycloalkyls, and phenyl radicals;

each R¹ group is independently selected from the group consisting of R, monovalent C_2-12 radicals, and a monovalent epoxy-functional group having about 2 to 10 carbon atoms, with the proviso that at least one of the R¹ groups is epoxy-functional; and

n is from 3 to about 10.

9. The system of claim 8, wherein R is methyl, R¹ is a methyl or cycloaliphatic epoxy-functional group having about 2 to 10 carbon atoms, and n is 4.

10. The system of claim 8, wherein R is a monovalent halogen-substituted C_1-12 alkyl radical or a C_1-12 cycloalkyl radical.

11. The system of claim 1, wherein the cationic photoinitiator of component a(ii) comprises an onium salt photocatalyst selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, aryldiazonium salts, ferrocenium salts, diarylsulfoxonium salts, diaryliodoxonium salts, triarylsulfoxonium salts, dialkylphenacylsulfonium salts, dialkylhydroxyphenylsulfonium salts, phenacyltriarylphosphonium salts, and phenacyl salts of heterocyclic nitrogen-containing compounds.

12. The system of claim 1, wherein component (a) further includes an acrylate or methacrylate monomer and an appropriate free radical photoinitiator for the acrylate or methacrylate monomer.

13. The system of claim 12, wherein the amount of the acrylate or methacrylate monomer and free radical photoinitiator present is in the range of about 0.1% by weight to about 35% by weight, based on the total weight of component (a).

14. The system of claim 12, wherein the acrylate or methacrylate monomer is selected from the group consisting of hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, neopentylglycol dimethacrylate, the diacrylic acid adduct to bisphenol A, and the diacrylic acid adduct to bisphenol A diglycidyl ether.

15. The system of claim 12, wherein the free radical photoinitiator is selected from the group consisting of benzoin butyl ether;

2,2-diethoxyacetophenone;

2-chloroacetophenone;

1-benzoylcyclohexanol; and

benzoyldiphenyl phosphine oxide.

16. The system of claim 1, wherein component (a) further includes a cationically-polymerizable vinyl or 1-propenyl ether monomer.

17. The system of claim 16, wherein the amount of the cationically-polymerizable vinyl or 1-propenyl ether monomer present is in the range of about 0.1% by weight to about 35% by weight, based on the total weight of component (a).

18. The system of claim 1, wherein component (a) further includes at least one additional epoxy resin.

19. The system of claim 18, wherein the epoxy resin is selected from the group consisting of 3,4-epoxycyclohexylmethyl 3'"'"',4'"'"'-epoxycyclohexane carboxylate;

bisphenol-A diglycidyl ether;

epoxidized polybutadiene;

1,4-cyclohexanedimethanol diglycidyl ether;

epoxidized linseed oil;

epoxidized soybean oil;

an epoxidized methyl ester of linoleic acid;

limonene dioxide;

dicyclopentadiene dioxide;

epoxy cresol novolac resins;

epoxy phenol novolac resins;

1,7-diepoxyoctane;

vinyl cyclohexene monoxide;

1,4-butanediol diglycidyl ether; and

diglycidylphthalate.

20. The system of claim 1, wherein component (a) further includes at least one polyol resin.

21. The system of claim 20, wherein the polyol resin is selected from the group consisting of polyether polyols, polyester polyols, polycaprolactone polyols, and hydroxyl-terminated polyolefins.

22. The system of claim 1, wherein component (a) further includes a copper co-catalyst.

23. The system of claim 1, wherein component (a) further includes at least one photosensitizer.

24. The system of claim 23, wherein the photosensitizer is selected from the group consisting of anthracene, naphthalene, perylene, pyrene, phenothiazine;

9,10-phenanthrenequinone;

bianthrone;

anthrone;

9-butoxyanthracene;

1-ethyl-9,10-dimethoxyanthracene;

acridine orange;

benzoflavin;

phosphine R;

1-ethyl-9-ethoxyanthracene;

1-ethyl-9,10-dimethoxyanthracene;

2-isopropylthioxanthone; and

2-chlorothioxanthone.

25. The system of claim 24, wherein the amount of photosensitizer present is in the range of about 0.05% by weight to about 10% by weight, based on the total weight of component (a).

26. The system of claim 1, wherein component (a) further includes effective amounts of at least one additive selected from the group consisting of adhesion agents, wetting agents, flatting agents, flow control agents, stabilizers, pigments, dyes, and fillers.

27. The system of claim 1, further including programmed control means for varying the graphic pattern of said reaction means operating upon the designated surface of the fluid medium.

28. The system of claim 1, wherein the reaction means of component (d) includes a beam of light having a wavelength in the range of about 200 nm to about 700 nm.

29. The system of claim 1, wherein the reaction means of component (d) includes a beam of ultraviolet light.

30. A stereolithographic system for producing a three-dimensional object from a fluid medium capable of solidification when subjected to prescribed stimulation, wherein the medium comprises the following components:

(i) at least one monomer or oligomer containing at least one epoxycyclohexyl group which is bonded directly or indirectly to a group containing at least one silicon atom, and

(ii) a cationic photoinitiator for component (i).

31. A method for producing a three-dimensional object from a medium capable of solidification when subjected to prescribed radiation, comprising the following steps:

(I) containing a body of the medium, which itself comprises the following components;

(i) at least one monomer or oligomer containing at least one epoxycyclohexyl group which is bonded directly or indirectly to a group containing at least one silicon atom, and

(ii) a cationic photoinitiator for component (i);

(II) drawing upon and forming successive cross-sectional laminae of the object at a two-dimensional interface of the medium defining a designated working surface, said laminae including a first cross-sectional layer of structure at the working surface;

(III) automatically coating over the entire first cross-sectional layer of structure with a body of the medium, in preparation for formation of a second cross-sectional layer of structure adhered to the first cross-sectional layer; and

(IV) moving said cross-sectional layers as they are formed, and building up the object from a plurality of successively adhered layers of structure in stepwise fashion, whereby a three-dimensional object is extracted from a substantially two-dimensional surface.

32. The method of claim 31, wherein the three-dimensional object prepared in step (IV) is post-cured after it has been subjected to the prescribed radiation.

33. A method for directly producing a three-dimensional object as it is designed by a computer, comprising the following steps:

(I) deriving graphic image output from the computer, said graphic image output defining successive adjacent cross-sections of the three-dimensional object designed by the computer;

(II) containing a medium capable of solidification;

said medium itself comprising the following components;

(i) at least one monomer or oligomer containing at least one epoxycyclohexyl group which is bonded directly or indirectly to a group containing at least one silicon atom, and

(ii) a cationic photoinitiator for component (i);

(III) drawing upon and forming successive layer cross-sections, corresponding to the computer-designed cross-sections of the object, at a two-dimensional interface of the medium defining a working surface, said layer cross-sections including a first cross-sectional layer of structure at said working surface;

(IV) automatically coating over the entire first cross-sectional layer of structure with a body of the medium, in preparation for formation of a second cross-sectional layer of structure adhered to the first cross-sectional layer;

(V) moving the cross-sectional layers as they are formed, and building up the object from a plurality of successively-adhered layers in a stepwise fashion, whereby the three-dimensional object designed by the computer is automatically extracted from a substantially two-dimensional surface.

34. In a stereolithographic method for producing a three-dimensional object from a fluid medium capable of solidification when subjected to prescribed stimulation, the improvement comprising the following steps:

utilizing as the fluid medium a composition which itself comprises the following components;

(i) at least one monomer or oligomer containing at least one epoxycyclohexyl group which is bonded directly or indirectly to a group containing at least one silicon atom, and

(ii) a cationic photoinitiator for component (i).