Process for forming a colored three-dimensional article

• US 6,133,336 A
• Filed: 08/30/1996
• Issued: 10/17/2000
• Est. Priority Date: 09/09/1995
• Status: Expired due to Term

• Current Assignee: Zeneca Incorporated (Astrazeneca PLC)
• Original Assignee: Zeneca Incorporated (Astrazeneca PLC)
• Inventors: Edwards, Martin Russell, Popat, Ajay Haridas
• Primary Examiner(s): Nguyen, Nam
• Assistant Examiner(s): VerSteeg, Steven H.
• Application Number:
  US08/705,846
• Time in Patent Office: 1,509 Days
• Field of Search: 522/25, 522/64, 522/4, 522/18, 522/44, 522/31, 522/15, 427/574, 427/570, 430/269, 430/284.1, 430/294, 430/357, 430/327, 430/334, 430/394, 430/374, 430/335, 430/340, 430/332, 430/346, 430/914, 430/921, 264/401, 264/497, 264/494
• US Class Current: 522/31
• CPC Class Codes: B29C 64/135 the energy source being concentrated, e.g. scanning lasers or focused light sources
• CPC Class Codes: B29K 2995/002 Coloured
• 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 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence

Abstract

Process for forming a selectively colored polymeric layer, or a three-dimensional article made of polymeric layers, wherein a photocurable, photocolorable composition is irradiated with a low dose of light to cure and a different, preferably higher, dose of light to color. The process is particularly useful for preparing selectively colored ornamental and industrial articles and models of plant and animal parts, especially medical models.

Claims

1. A process for forming a three-dimensional article having selectively coloured regions from a photocurable, photocolourable composition comprising the steps:

a) curing a layer of the composition using light thereby forming a polymeric layer;

b) irradiating selected areas of the polymeric layer resulting from step a) or of a layer of the composition with a higher dose of light than used in step a) thereby forming selectively coloured areas;

c) repeating steps a) and b) on a previously formed polymeric layer until the desired three-dimensional article having selectively coloured regions is formed;

wherein the wavelength(s) of light used in each of steps a) and b) is or are the same.

2. A process according to claim 1 wherein the selectively coloured areas are formed by colour formation, colour change or photobleaching.

3. A process according to claim 1 wherein the light used in each of step a) and step b) has a wavelength below 700 nm.

4. A process according to claim 1 wherein the light used in each of step a) and step b) is from a single source.

5. A process according to claim 1 wherein the dose light used in step b) is at least 2 times higher than the dose of light used in step a).

6. A process according to claim 1 wherein the photocurable, photocolourable composition comprises:

(i) a light-curable resin;

(ii) a compound which is convertible by a photochemical reaction into a developer; and

(iii) a compound which forms colour or changes colour on contact with said developer.

7. A process according to claim 6 wherein the composition comprises:

(a) 100 parts in total of (meth)acrylate monomers and/or oligomers;

(b) 0.01 to 10 parts in total of photoinitiator;

(c) 0.01 to 4 parts in total of a compound which is convertible by a photochemical reaction into a developer;

(d) 0.01 to 4 parts of a compound which forms colour or changes colour on contact with said developer; and

(e) 0 to 2 parts of a peroxide;

wherein all parts are by weight.

8. A process according to claim 7 wherein the composition contains a peroxide.

9. A process according to claim 7 wherein the composition comprises at least one member of the group consisting of acrylate and methacrylate oligomers and monomers;

a mixed triaryl sulphonium phosphate salt; and

a triaryl methane-, diphenyl methane-, thiazine-, Spiro-, lactam- or fluoran-based colour former.

10. A process according to claim 6 wherein the compound which is convertible by a photochemical reaction into a developer is at least one compound selected from the group consisting of an aryl phosphine oxide, an aryl phosphine sulphide, and a compound which generates acid when irradiated.

11. A process according to claim 10 wherein the compound which generates acid when irradiated is an onium salt, a latent-sulphonic acid, a halomethyl-s-triazine, a metallocene or a chlorinated acetophenone.

12. A process according to claim 6 wherein the compound which forms colour or changes colour on contact with said developer is a triaryl methane-, diphenyl methane-, thiazine-, spiro-, lactam- or fluoran-based colour former.

13. A process according to claim 1 wherein the process uses a stereolithography apparatus.

14. A process according to claim 1 wherein the composition contains more than one compound which forms colour or changes colour on contact with a developer.

15. A process according to claim 1 which comprises a further step of coating the three-dimensional article resulting from step c) with a visually transparent layer which absorbs the wavelength of light used in step b).

16. A photocurable, photocolourable composition comprising:

(a) 100 parts of (meth)acrylate monomers and/or oligomers;

(b) 0.01 to 10 parts of a photoinitiator;

(c) 0.01 to 4 parts in total of a compound which is convertible by a photochemical reaction into a developer;

(d) 0.01 to 4 parts in total of a compound which forms colour or changes colour on contact with said developer; and

(e) 0 to 2 parts of a peroxide;

wherein all parts are by weight and the compound which is convertible by a photochemical reaction into a developer comprises an acylphosphine oxide, acylphosphine sulphide, onium salt, latent sulphonic acid or metallocene.

17. A composition according to claim 16 which contains from 0.05 to 2% by weight of a peroxide.

18. A composition according to claim 16 wherein the compound which is convertible by a photochemical reaction into a developer comprises an acyl phosphine oxide or an acyl phosphine sulphide.

19. A composition according to claim 16 which is free from compounds which generate acid when irradiated and which further contains 0.1 to 20 parts of a phenolic compound.

20. A process for forming a three-dimensional article having selectively coloured regions from a photocurable, photocolourable composition comprising the steps:

a) curing a layer of the composition using light thereby forming a polymeric layer;

b) irradiating selected areas of the polymeric layer resulting from step a) or of a layer of the composition with a higher dose of light than used in step a) thereby forming selectively coloured areas;

c) repeating steps a) and b) on a previously formed polymeric layer until the desired three-dimensional article having selectively coloured regions is formed;

wherein said three-dimensional article is a model of a plant or animal part or a model of an automobile mechanical part.

21. A process according to claim 20 wherein the three-dimensional article is a model of an animal part selected from bones, organs, tissues and combinations thereof.

22. A process according to claim 20 wherein the three-dimensional article is a model of a body part subject to cancer wherein cancerous cells are coloured differently from healthy tissue.

23. A process for forming a three-dimensional article having selectively coloured regions from a photocurable, photocolourable composition comprising the steps:

a) curing a layer of the composition using light thereby forming a polymeric layer;

b) irradiating selected areas of the polymeric layer resulting from step a) or of a layer of the composition with a higher dose of light than used in step a) thereby forming selectively coloured areas; and

c) repeating steps a) and b) on a previously formed polymeric layer until the desired three-dimensional article having selectively coloured regions is formed;

wherein the light used in each of step a) and b) is from a single source.

24. A process for forming a three-dimensional article having coloured regions from a photocurable, photocolourable composition comprising the steps:

a) curing a layer of the composition using light thereby forming a polymeric layer;

b) irradiating selected areas of the polymeric layer resulting from step a) or of a layer of the composition with a different dose of light than used in step a) thereby forming selectively coloured areas; and

c) repeating steps a) and b) on a previously formed polymeric layer until the desired three-dimensional article having selectively coloured regions is formed; and

d) coating the three-dimensional article with a visually transparent layer which absorbs the wavelength of light used in step b).