# US 5,707,780 A · Photohardenable epoxy composition > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,707,780 A - Document ID: US5707780A - Status: Granted - Kind: A - Application number: 08/612,509 - Filed: 1996-03-07 - Granted: 1998-01-13 - Earliest claimed: 1995-06-07 - Assignees: E. I. Du Pont de Nemours and Company - Inventors: John Alan Lawton; William John Nebe; Glen Anthony Thommes; Jonathan V. Caspar - Web page: https://patentgrep.com/patent/US5707780A ## CPC - G03F 7/032: with binders - B29C 41/003: {characterised by the choice of material} - B29C 64/135: the energy source being concentrated, e.g. scanning lasers or focused light sources - G03F 7/0037: {Production of three-dimensional images} - G03F 7/027: Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence) - G03F 7/028: with photosensitivity-increasing substances, e.g. photoinitiators - G03F 7/029: Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur - B29K 2995/0073: smooth - Y10S 430/146: Laser beam - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract A photohardenable composition especially suitable for use in solid imaging. The compositions are characterized by their improved photospeed in combined with excellent initial green strength. The compositions allows for the production of articles by solid imaging processing techniques that show little or no distortion, high accuracy, excellent clarity. The compositions are low in toxicity and have low sensitivity to water. ## Claims ### Claim 1 In an improved photohardenable composition composed of a cationically polymerizable and free radical polymerizable organic substance, a photo-generated acid precursor, a sensitizer for the photo-generated acid precursor and a free radical polymerization initiator wherein the improvement comprises: a) a mixture of photopolymerizable resins consisting essentially of at least two epoxy resins one of which polymerizes at a slower rate and has a higher neat viscosity than at least one other epoxy resin present and the epoxy resins are present at a concentration in the mixture of from 5 to 25% by weight, and at least one monoacrylic monomer and at least one multi-acrylic monomer wherein the concentration of the monoacrylic monomer is from 0.12 to 0.90 parts by weight that of the multiacrylic monomer and wherein the ratio of the weight of the epoxy resins to that of the acrylic monomers is between 3 to 10; and b) a combination of a free radical initiator and a photo-generating acid precursor characterized by optical molar extinction coefficients and optimized for use with a multi-wavelength argon ion laser operating in the UV and producing two major wavelengths of 351 nm and 364 nm such that a normalized ratio of the extinction coefficients of the precursor and the initiator at one major wavelength is less than 3 times the ratio of extinction coefficient at a second major wavelength. ### Claim 2 A method for accurately fabricating an integral three dimensional article having improved green strength by controlling the diffusion of photoactivated molecular species in the regions of a photohardenable liquid composition exposed to actinic radiation, the method comprising the steps of: (a) forming a layer of the photohardenable liquid composition; (b) imagewise exposing areas of at least a portion of the layers to actinic radiation at wavelengths of 351 nm and 364 nm; (c) introducing a new layer of liquid on to the layer previously exposed imagewise in step (b); (d) imagewise exposing at least a portion of the new liquid layer to actinic radiation, wherein the improvement comprises use of photohardenable liquid composition comprising: a) a mixture of photopolymerizable resins consisting essentially of at least two epoxy resins one of which polymerizes at a slower rate and has a higher neat viscosity than at least one other epoxy resin present and the epoxy resins are present at a concentration in the mixture of from 5 to 25% by weight, and at least one monoacrylic monomer and at least one multi acrylic monomer wherein the concentration of the monoacrylate monomer is from 0.12 to 0.90 parts by weight that of the multi-acrylate monomer and wherein the ratio of the weight of the epoxy resins to that of the acrylic monomers is between 3 to 10; and b) a combination of a free radical initiator and a photo-generating acid precursor characterized by optical molar extinction coefficients and optimized for use with a multi-wavelength argon ion laser operating in the UV and producing two major wavelengths of 351 nm and 364 nm such that a normalized ratio of the extinction coefficients of the precursor and the initiator at one major wavelength is less than 3 times the ratio of extinction coefficient at a second major wavelength.