Photosensitive compositions

• US 5,476,748 A
• Filed: 12/14/1993
• Issued: 12/19/1995
• Est. Priority Date: 12/21/1992
• Status: Expired due to Term

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Wolf, Jean-Pierre, Schulthess, Adrian, Hunziker, Max, Steinmann, Bettina
• Primary Examiner(s): McCamish, Marion E.
• Application Number:
  US08/166,767
• Time in Patent Office: 735 Days
• Field of Search: 430/280, 430/269, 522/162, 522/170
• US Class Current: 430/269
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C08F 283/00 Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
• CPC Class Codes: C08F 283/10 on to polymers containing more than one epoxy radical per molecule C08F283/004 takes precedence
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021

Abstract

The invention relates to photosensitive compositions comprising

A) from 40 to 80% by weight of at least one liquid epoxy resin having an epoxy functionality of equal to or greater than 2,

B) from 0.1 to 10% by weight of at least one cationic photoinitiator for component A),

C) from 5 to 40% by weight of at least one liquid cycloaliphatic or aromatic diacrylate,

D) from 0 to 15% by weight of at least one liquid poly(meth-)acrylate having a (meth-)acrylate functionality of greater than 2, the proportion of component D) constituting a maximum of 50% by weight of the total (meth-)acrylate content,

E) from 0.1 to 10% by weight of at least one radical photoinitiator for component C) and, where appropriate, D) and

F) from 5 to 40% by weight of at least one OH-terminated polyether, polyester or polyurethane,

which are especially suitable, for example, for the manufacture of photopolymerized layers, especially of three-dimensional objects.

Claims

1. A photosensitive composition comprising

A) from 40 to 80% by weight of at least one liquid epoxy resin having an epoxy functionality of equal to or greater than 2,

B) from 0.1 to 10% by weight of at least one cationic photoinitiator for component A),

C) from 5 to 40% by weight of at least one liquid cycloaliphatic or aromatic diacrylate,

D) from 0 to 15% by weight of at least one liquid poly(meth-)acrylate having a (meth-)acrylate functionality of greater than 2, the proportion of component D) constituting a maximum of 50% by weight of the total (meth-)acrylate content,

E) from 0.1 to 10% by weight of at least one radical photoinitiator for component C) and, where appropriate, component D) and

F) from 5 to 40% by weight of at least one OH-terminated polyether, polyester or polyurethane.

2. A photosensitive composition according to claim 1 wherein the proportion of component D) constitutes a maximum of 40% by weight of the total (meth)acrylate content.

3. A photosensitive composition according to claim 1 comprising

A) from 50 to 75% by weight of at least one liquid epoxy resin having an epoxy functionality of equal to or greater than 2,

B) from 0.2 to 5% by weight of at least one cationic photoinitiator for component A),

C) from 5 to 20% by weight of at least one liquid cycloaliphatic or aromatic diacrylate,

D) from 0 to 10% by weight of at least one liquid polyacrylate having an acrylate functionality of greater than 2, the proportion of component D) constituting a maximum of 50% by weight of the total acrylate content,

E) from 0.2 to 5% by weight of at least one radical photoinitiator for component C) and, where appropriate, component D) and

F) from 10 to 40% by weight of at least one OH-terminated polyether, polyester or polyurethane.

4. A photosensitive composition according to claim 1 wherein component A) comprises at least 50% by weight of a cycloaliphatic diepoxide.

5. A photosensitive composition according to claim 4 wherein the cycloaliphatic diepoxide is bis(4-hydroxycyclohexyl)methane diglycidyl ether, 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, di-(3,4-epoxycyclohexylmethyl)hexanedioate, di-(3,4-epoxy-6-methyl-cyclohexylmethyl)hexanedioate, ethylenebis(3,4-epoxycyclohexanecarboxylate), ethanediol di-(3,4-epoxycyclohexylmethyl)ether or 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,3-dioxane.

6. A photosensitive composition according to claim 1 comprising as component B) a compound of the formula I, II or III ##STR11## wherein R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are each independently of the others C₆ -C₁₈ aryl that is unsubstituted or substituted by suitable radicals,

L is boron, phosphorus, arsenic or antimony,

Q is a halogen atom or some of the radicals Q in an anion LQ_m^- may also be hydroxy groups, and

m is an integer that corresponds to the valency of L plus 1.

7. A photosensitive composition according to claim 1 comprising as component B) a compound of formula IV ##STR12## wherein c is 1 or 2,

d is 1, 2, 3, 4 or 5,

X is a non-nucleophilic anion, especially PF₆^-, AsF₆^-, SbF₆^-, CF₃ SO₃^-, C₂ F₅ SO₃^-, n-C₃ F₇ SO₃^-, n-C₄ F₉ SO₃^-, n-C₆ F₁₃ SO₃^- or n-C₈ F₁₇ SO₃^-,

R₈ is a π

-arene and

R₉ is an anion of a π

-arene, especially a cyclopentadienyl anion.

8. A photosensitive composition according to claim 6 comprising as component B) a compound of formula III wherein R₅, R₆ and R₇ are aryl.

9. A photosensitive composition according to claim 1 comprising as component C) a compound of formula V, VI, VII or VIII ##STR13## wherein Y is a direct bond, C₁ -C₆ alkylene, --S--, --O--, --SO--, --SO₂ -- or --CO--,

R₁₀ is a C₁ -C₈ alkyl group, a phenyl group that is unsubstituted or substituted by one or more C₁ -C₄ alkyl groups, hydroxy groups or halogen atoms, or a radical of the formula --CH₂ --OR₁₁, wherein

R₁₁ is a C₁ -C₈ alkyl group or a phenyl group, and

A is a radical of the formula ##STR14## or comprising as component C) a compound of any one of formulae IXa to IXd ##STR15## and the corresponding isomers, ##STR16##

10. A photosensitive composition according to claim 9 wherein in formula V, VI or VII Y as alkylene is --CH₂ -- or --C(CH₃)₂ --.

11. A photosensitive composition according to claim 9 wherein in formula VII R₁₀ is n-butyl, phenyl, n-butoxymethyl or phenoxymethyl.

12. A photosensitive composition according to claim 1 wherein component D) is a tri(meth-)acrylate or a penta(meth-)acrylate.

13. A photosensitive composition according to claim 12 wherein the penta(meth-)acrylate is dipentaerythritol monohydroxypenta(meth-)acrylate.

14. A photosensitive composition according to claim 1 comprising as component E) a 1-hydroxyphenyl ketone.

15. A photosensitive composition according to claim 14 wherein the 1-hydroxyphenyl ketone is 1-hydroxycyclohexyl phenyl ketone.

16. A photosensitive composition according to claim 1 comprising as component F) a linear or branched polyester polyol.

17. A photosensitive composition according to claim 1 comprising as component F) a trifunctional, OH-terminated polycaprolactone.

18. A photosensitive composition according to claim 1 comprising

as component A) a cycloaliphatic diepoxide and an aliphatic polyglycidyl ether,

as component B) triarylsulfonium hexafluoroantimonate,

as component C) a compound of formula VI wherein Y is --CH₂ -- or --C(CH₃)₂ --,

as component D) a tri(meth-)acrylate or a penta(meth-)acrylate,

as component E) a 1-hydroxyphenyl ketone and

as component F) a linear or branched polyester polyol.

19. A process for polymerising the composition according to claim 1 by irradiating it with actinic light.

20. A process for the manufacture of three-dimensional objects from a composition according to claim 1 by means of a lithographic process, wherein the surface of a layer of the said composition, in its entirety or in a predetermined pattern, is irradiated with a UV/VIS light source so that a layer of a desired thickness solidifies in the irradiated areas and then a new layer of that composition is formed on the solidified layer, the new layer likewise being irradiated over the entire surface or in a predetermined pattern, and, by repeated layering and irradiation, three-dimensional objects comprising several solidified layers adhering to one another are obtained.

21. A process according to claim 20, wherein the UV/VIS light source is a laser beam, preferably a computer-controlled laser beam.

22. The use of a composition according to claim 1 in the manufacture of photopolymerised layers, especially in the form of three-dimensional objects that are made up of several solidified layers adhering to one another.