Photosensitive diacrylate and dimethacrylate compositions

• US 6,783,809 B2
• Filed: 09/17/2001
• Issued: 08/31/2004
• Est. Priority Date: 01/27/1992
• Status: Expired due to Fees

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: Huntsman Advanced Materials Americas, Inc.
• Inventors: Hunziker, Max, Schulthess, Adrian, Steinmann, Bettina
• Primary Examiner(s): Robertson, Jeffrey B.
• Application Number:
  US09/953,250
• Publication Number:
  US 20020068801A1
• Time in Patent Office: 1,079 Days
• Field of Search: 427/508, 427/517, 522/68, 522/120, 522/121, 522/123, 430/281.1, 430/269, 264/401, 264/446, 264/494, 525/529, 525/530, 525/531, 525/922
• US Class Current: 427/508
• 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: C07C 69/54 Acrylic acid esters; Methacrylic acid esters
• 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: Y10S 525/922 Polyepoxide polymer having been reacted to yield terminal ethylenic unsaturation

Abstract

A photosensitive composition of (a) a compound of formula (Ia) or (Ib) and (b) a bifunctional acrylate or methacrylate.

Claims

1. A photosensitive composition comprising

(a) 5-65% by weight of a compound of formula (Ia) or (Ib),

 

wherein the substituents R₁ are each independently of the other hydrogen or methyl,

 

R₂ is an unsubstituted C₁-C₂₀alkyl group or a C₁-C₂₀ alkyl group which is substituted by one or more than one substituent selected from the group consisting of hydroxy, C₆-C₁₄aryl and halogen, an unsubstituted phenyl group or a phenyl group which is substituted by one or more than one substituent selected from the group consisting of C₁-C₆alkyl, hydroxy or halogen, or is a radical of formula —

CH₂—

OR₃, wherein R₃ is an unsubstituted C₁-C₂₀alkyl group or a C₁-C₂₀alkyl group which is substituted by one or more than one substituent selected from the group consisting of hydroxy, C₆-C₁₄aryl and halogen, an unsubstituted phenyl group or a phenyl group which is substituted by one or more than one substituent selected from the group consisting of C₁-C₆alkyl, hydroxy and halogen, or is a C₂-C₆alkenyl group, a C₂-C₂₀acyl group or an unsubstituted cyclohexylcarbonyl group or a cyclohexylcarbonyl group which is substituted by one or more than one substituent selected from the group consisting of C₁-C₆alkyl, hydroxy and halogen,

Z is a group of formulae (IIa)-(IIe)

wherein Y is a direct bond, C₁-C₆alkylene, —

S—

, —

O—

, —

SO—

, —

SO₂—

or —

CO—

, and R₁ is hydrogen or methyl, and wherein the aromatic and cycloaliphatic rings of formulae (IIa)-(IIe) are unsubstituted or substituted by one or more than one substituent selected from the group consisting of C₁-C₆alkyl, chloro and bromo,

(b) 15-70% by weight of one or more than one bifunctional acrylate or methacrylate having a molecular weight in the range from 150 to 450 and differing from the compound of formula (Ia) or (Ib),

(c) 0-40% by weight of one or more than one monomeric polyfunctional acrylate or methacrylate having a functionality of not less than 3 and a molecular weight of not more than 600,

(d) 0-10% by weight of at least one monofunctional acrylate or methacrylate,

(e) 0-10% by weight of N-vinylpyrrolidone or N-vinylcaprolactam,

(f) 2-10% by weight of at least one photoinitiator, and

(g) 0-60% by weight of at least one urethane acrylate or methacrylate having a functionality of 2-4 and a molecular weight in the range from 500-10000.

2. A composition according to claim 1, wherein component (b) is a diacrylate or dimethacrylate of ethoxylated bisphenol A.

3. A composition according to claim 1, wherein component (c) is trimethylpropane triacrylate or trimethylolpropane trimethacrylate.

4. A composition according to claim 1, wherein component (d) is phenoxyethyl acrylate.

5. A composition according to claim 1, wherein component (f) is 1-hydroxycyclohexyl phenyl ketone.

6. A composition according to claim 1, wherein in the compound of formula (Ia) or (Ib) R₂ is C₁-C₂₀alkyl, phenyl, C₁-C₂₀alkoxymethyl, phenoxymethyl or cyclohexylcarbonyloxymethyl.

7. A composition according to claim 1, wherein in the compound of formula (Ia) or (Ib) R₂ is n-butyl, phenyl, n-butoxymethyl, phenoxymethyl or cyclohexylcarbonyloxymethyl.

8. A composition according to claim 1, wherein in the compound of formula (Ia) or (Ib) R₂ is n-butoxymethyl.

9. A composition according to claim 1, wherein in the compound of formula (Ia) or (Ib) Z is a group of formula (IIc) or (IIe).

10. A composition according to claim 1, wherein in the compound of formula (Ia) or (Ib) Z is

11. A process for the production of a three-dimensional object from a photosensitive composition according to claim 1 by stereolithography, wherein the composition forms a first layer having a first surface, comprising

irradiating the first layer over the entire first surface or in a predetermined pattern with a UV/VIS light source, such that within the irradiated areas a layer solidifies in a desired layer thickness,

coating a new layer of the composition on the solidified layer, wherein the new layer has a second surface,

irradiating the new layer over the entire second surface or in a predetermined pattern, and such that a three-dimensional object is formed from a plurality of solidified layers which adhere to one another by repeated coating and irradiation.