Huntsman Advanced Materials Americas LLC

3D Systems, Inc.

Imation Corporation

Ranjana Changanbhai Patel

Yong Zhao

Richard John Peace

John Wai Fong

Richard Noel Leyden

David L Johnson

Frank Tran

Carole Chapelat

Laurence Messe

Michael Rhodes

Jeremy Powell

Peggy Studer

Yonetatsu Matsumoto

Loic Messe

Jonathan C Vogel

Stefan Barny

A fully curable jettable composition having a viscosity less than 30 cps at a temperature within the range of 15&#xb0; C.-180&#xb0; C. comprising (i) at least one low viscosity reactive resin; (ii) at least one higher viscosity resin having a viscosity greater than twice that of the low viscosity resin and a functionality of greater than or equal to 2; (iii) at least one curable toughener, (iv) at least one initiator for the polymerization of the resins, and (v) at least one stabilizer for delaying the curing of the resins of the composition. The composition can be jetted from piezo electric printing heads under the control of a computer program to form a multi-layered article, for example, a three dimensional article, in which the adjacent droplets merge and are cured homogeneously together.

Jettable compositions

The present invention provides a low viscosity photocurable composition including (i) a cationically curable component (ii) a free radically active component (iii) an antimony-free cationic photoinitiator (v) a free radical photoinitiator, and (vi) a toughening agent. The photocurable composition can be cured using rapid prototyping techniques to form three-dimensional articles which can be used in various aerospace and investment casting applications.

Antimony-free photocurable resin composition and three dimensional article

The present invention provides a clear, low viscosity photocurable composition including (i) a cationically curable compound (ii) an acrylate-containing compound (iii) a polyol-containing mixture (iv) a cationic photoinitiator and (v) a free radical photoinitiator. The photocurable composition can be cured using rapid prototyping techniques to form opaque-white three-dimensional articles having ABS-like properties.

Photocurable compositions for preparing ABS-like articles

An optical moulding process is disclosed comprising the sequential steps of: (a)(y) forming a layer of a photocurable composition; and (bXz) irradiating selected areas of the composition in the layer with radiation from a radiation source, thereby curing the composition in said selected areas and repeating the steps a) and b) on top of an earlier cured layer to form a three dimensional structure, wherein the radiation source used in step b) is a non-coherent source of radiation and wherein the photocurable composition comprises at least two curable components: (i) 45%-95% (and preferably at least 50%, more preferably at least 60%, e.g. at least 70%) by weight of the total curable components in the composition is a first component that is photocurable and that is such that, when cured in the presence of a photocuring initiator by exposure to UV radiation having an energy of 30 mJ/cm, at least 90% of the component is cured within 50 milliseconds; and (ii) 5% to 55% (and preferably 10-40%, more preferably 15 to 30%, e.g. about 20%) by weight of the total curable components in the composition is a second component that results in the composition, on curing, shrinking, in a linear direction, by less than 3% and preferably that results in the composition having, after cure, a Tof greater than 50&#xb0; C., preferably at least 100&#xb0; C. and more preferably at least 120&#xb0; C.

Photocurable compositions

The present invention is directed to a photoinitiator composition comprising two different cationic photoinitiators and a photocurable composition comprising said photoinitiator composition. Moreover, the present invention relates to the use of the photoinitiator composition and the photocurable composition. Furthermore, the present invention relates to a process for producing a three dimensional article.

Dual photoinitiator, photocurable composition, use thereof and process for producing a three dimensional article

A process for forming a three-dimensional article in sequential layers in accordance with a digital model of the article. The process comprises the steps of defining a layer of powder material, applying a liquid reagent to the powder layer in a pattern corresponding to the digital model, and repeating these steps to form successive layers. The powder comprises a first reactive component and the liquid includes a second active component capable of reacting with the first reactive component so that the article is built up in layers.

Three-dimensional structured printing

A photocurable composition comprising cationically curable compound, an acrylate-containing compound; a hydroxyl-containing compound; a cationic photoinitiator; and a free radical photoinitiator; wherein said composition has less than 0.54 equivalents of cationically curable groups, less than 0.10 equivalents of acrylate groups and less than 0.10 equivalents of hydroxyl 0groups per 100 grams of said composition.

Photocurable compositions for articles having stable tensile properties

A fully curable jettable composition having a viscosity less than 30 cps at a temperature within the range of 15-180&#xb0; C., more preferably at a temperature of 15-100&#xb0; C., e.g. 60-80&#xb0; C. the composition comprising: (A) at least one low viscosity reactive resin selected from the group consisting of compounds containing an oxetane ring, cycloaliphatic epoxy resins, tetrahydrofurans, hexahydropyrans and mono-functional (meth)acrylates, said resin having a molecular weight of not greater than 300 Daltons, e.g. 250 Daltons or less, and a viscosity at a temperature in the said range of less than 30 cps, e.g. 5 to 15 cps; (B) at least one higher viscosity resin selected from the group consisting of epoxy resins, compounds containing an oxetane ring and acrylates, which resin acts to thicken the low viscosity resin and strengthen a jetted deposit of the composition, the higher viscosity resin having: a viscosity greater than twice that of the low viscosity resin at the said temperature in the range stated above, and a functionality of greater than or equal to 2; (C) at least one curable toughener, preferably having a functionality of at least 2, such as hydroxy, epoxy, acrylic or other reactive functionalised polymer/oligomer (e.g. derived by functionalising poly(tetrahydrofuran), polycaprolactone, polycarbonate diol, or a dendrimeric polyol; (D) at least one initiator for the polymerisation of the resins, and (E) at least one stabilizer for delaying the curing of the resins of the composition; wherein the low viscosity resin is slower to react than the higher viscosity resin and acts to solvate the higher viscosity resin prior to curing and at least partly during curing and wherein at least 30% of the components A and B are cationically curable resins. The composition can be jetted from piezo electric printing heads under the control of a computer program to form a multi-layered article, e.g. a three dimensional article, in which the adjacent droplets merge and are cured homogeneously together.

A process for forming a three-dimensional article in sequential layers in accordance with a digital model of the article. The process comprises the steps of defining a layer of powder or liquid material, applying a liquid reagent to the layer in a pattern corresponding to the digital model, and repeating these steps to form successive layers. The powder or liquid material comprises a first reactive component and the applied liquid includes a second active component capable of reacting with the first reactive component so that the article is built up in layers. The characteristics of the layers vary across those layers and/or the properties vary from layer to layer.

A method is described of producing thin layers (below 10 &#x3bc;m in thickness) by directing droplets (preferably by inkjet printing techniques) onto precise locations on a substrate, the liquid of the droplets having a viscosity such that the droplets, on impact with the substrate, spread out to form relics on the substrate that are at least 1.4 times the diameter of the droplets in flight, adjacent droplets merging to form a continuous layer on the substrate. The droplets may have different compositions to form images within the layer. Successive layers may be added to built up a three dimensional structure whose properties can be tailored by the compositions used to build up a composite.

Production of composites articles composed of thin layers

A photocurable composition comprising cationically curable compound, an acrylate-containing compound; a hydroxyl-containing compound; a cationic photoinitiator; and a free radical photoinitiator; wherein said composition has less than 0.54 equivalents of cationically curable groups, less than 0.10 equivalents of acrylate groups and less than 0.10 equivalents of hydroxyl groups per 100 grams of said composition.

An infrared laser addressable imaging element comprising a substrate bearing a first layer comprising a reducible light-insensitive silver salt and a binder; and a second layer comprising an infrared absorber, a reducing agent for said silver salt and a binder; wherein said binder of said first layer is a polymeric medium having a glass transition temperature of at least 80.degree. C.

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Little Hallingbury, United Kingdom

Ranjana Changanbhai Patel