(Meth)acrylates containing urethane groups

• US 5,658,712 A
• Filed: 11/03/1995
• Issued: 08/19/1997
• Est. Priority Date: 08/09/1993
• 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): Raymond, Richard L.
• Application Number:
  US08/552,643
• Time in Patent Office: 655 Days
• Field of Search: 430/325, 526/301
• US Class Current: 430/325
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 2601/16 the ring being unsaturated
• CPC Class Codes: C07C 2603/70 containing only six-membered rings
• CPC Class Codes: C07C 271/12 to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
• CPC Class Codes: C07C 271/24 with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
• CPC Class Codes: C07C 271/28 to a carbon atom of a non-condensed six-membered aromatic ring
• CPC Class Codes: C07C 271/34 with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
• CPC Class Codes: C07C 271/36 with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
• CPC Class Codes: C07C 271/38 with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
• CPC Class Codes: C07D 303/16 by esterified hydroxyl radicals
• CPC Class Codes: C08F 20/36 containing oxygen in addition to the carboxy oxygen , e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• CPC Class Codes: C08F 222/1065 of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
• CPC Class Codes: C08G 18/675 Low-molecular-weight compounds
• CPC Class Codes: C08G 59/1494 followed by a further chemical treatment thereof
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• 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

Novel (meth)acrylates which also contain urethane groups and other polymerizable groups in one and the same molecule and can be polymerized either by means of free radicals and/or cationically are used for the production of coatings, adhesives, photoresists, solder masks or in stereolithography. The mouldings produced therefrom contain a coherent, homogeneous network and have high strength properties, in particular mechanical properties.

Claims

1. A composition comprising

a) from 5 to 99% by weight of a monomeric, polymerizable (meth)acrylate of the formula I containing urethane groups, ##STR31## in which R is a divalent group of the formula ##STR32## R₁ is a cationically polymerizable group or a free-radical-polymerizable group, with the exception of the acrylate and allyl groups,

R₂ is an aliphatic, cycloaliphatic or aromatic radical,

R₃ is hydrogen or CH₃,

R₄ is the radical of an aliphatic, cycloaliphatic or aromatic diglycidyl compound after removal of the diglycidyl radical, or is the radical of a cycloaliphatic diepoxide, and

R₅ is a cycloaliphatic bridge,

b) from 1 to 10% by weight of a free-radical photoinitiator,

c) from 0 to 20% by weight of conventional additives,

d) from 0 to 80% by weight of one or more mono-, di- or polyfunctional (meth)acrylates or mixtures thereof,

e) from 0 to 80% by weight of a di- or polyfunctional epoxide, or mixtures thereof,

f) from 0 to 50% by weight of an OH-terminated polyether or polyester, or mixtures thereof,

g) from 0 to 5% by weight of a cationic photoinitiator, and

h) from 0 to 80% by weight of one or more mono-, di- or polyfunctional vinyl ethers, where the proportion of components a) to h) together is 100% by weight.

2. A composition according to claim 1, in which R₁ is a cationically polymerizable group of the formula ##STR33## or a free-radical-polymerizable group of the formula ##STR34## in which x is an integer from 2 to 20, and y is an integer from 1 to 20.

3. A composition according to claim 2, in which R₁ is a cationically polymerizable group.

4. A composition according to claim 1, in which R₂ end R₄, independently of one another, are a C₄ -C₂₀ aliphatic bridge, which may be interrupted by at least one ether, ester, urethane, amide or arylene group, and furthermore are a cycloaliphatic or aromatic bridge.

5. A composition according to claim 4, in which R₂ is a C₄ -C₂₀ aliphatic or an aromatic bridge or a plurality of aromatic groups interrupted by aliphatic groups.

6. A composition according to claim 4, in which R₄ is a C₄ -C₂₀ aliphatic bridge interrupted by at least one ether or ester group, or is an aromatic bridge.

7. A composition according to claim 2, in which x and y are integers from 1 to 6.

8. A method for the production of coating compositions, adhesives, photoresists and solder masks which comprises mixing components a) and b) of a composition according to claim 1 in a vessel, optionally, in the absence of light and at an elevated temperature.

9. A process for the polymerization of a composition according to claim 1 comprising irradiating the composition with actinic light.

10. A process for the production of three-dimensional objects from a composition according to claim 1 by a lithographic process, where the surface of a layer of this composition is irradiated over the entire area or in a predetermined pattern with a UV and/or VIS light source so that a layer solidifies in the desired layer thickness in the irradiated areas, a new layer of this composition is then formed on the solidified layer and is likewise irradiated over the entire area or in a predetermined pattern, and where three-dimensional objects comprising a plurality of mutually adherent, solidified layers are obtained by repeated coating and irradiation.

11. A process according to claim 10, in which the light source used is a laser beam.

12. A method according to claim 8 wherein the composition is mixed in a vessel in the absence of light.

13. A method according to claim 12 wherein the composition is mixed in a vessel at an elevated temperature of from about 50°

to 70°

C.

14. A process according to claim 11, in which the light source is a computer-controlled laser beam.