# US 8,569,398 B2 · Jettable compositions

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- Number: US 8,569,398 B2
- Document ID: US8569398B2
- Status: Granted
- Kind: B2
- Application number: 12/964,083
- Filed: 2010-12-09
- Published: 2011-04-07
- Granted: 2013-10-29
- Earliest claimed: 2002-05-24
- Assignees: 3D Systems, Inc.
- Applicants: Ranjana C. Patel; Yong Zhao; Richard John Peace
- Inventors: Ranjana C. Patel; Yong Zhao; Richard John Peace
- Web page: https://patentgrep.com/patent/US8569398B2

## CPC

- C09D 11/36: based on non-aqueous solvents
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C09D 11/101: Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
- B33Y 40/20: Post-treatment, e.g. curing, coating or polishing
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING

## Abstract

A fully curable jettable composition having a viscosity less than 30 cps at a temperature within the range of 15° C.-180° 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.

## Claims

### Claim 1

A curable jettable composition having a viscosity less than 30 cps at a temperature within the range of 15° C.-180° C. comprising:
(a) at least one low viscosity reactive resin consisting of one or more oxetane compounds, wherein the low viscosity reactive resin has a molecular weight of not greater than 300 Daltons and a viscosity of less than 30 cps at a temperature within the range of 15° C.-180° C.;
(b) 40%-50% by weight of a high viscosity resin epoxy resin component wherein the epoxy resin component is a cycloaliphatic epoxy resin selected from 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate and bis-(3,4-epoxycyclohexyl)adipate and wherein the high viscosity resin has a functionality of greater than or equal to 2 and a viscosity greater than twice the viscosity of the low viscosity reactive resin at a temperature within the range of 15° C.-180° C.;
(c) at least one curable toughener comprising a polymer or oligomer having a hydroxy, or acrylic group;
(d) at least one initiator;
(e) at least one stabilizer and optionally
(f) a vinyl ether curable co-diluent and
(g) one or more additives
and wherein the low viscosity reactive resin is slower to react than the high viscosity resin.

### Claim 2 (depends on 1)

The jettable composition of claim 1 wherein when 50% of the high viscosity resin has polymerized, less than 10% of the low viscosity reactive resin has polymerized.

### Claim 3 (depends on 1)

The jettable composition of claim 1 wherein when 90% of the high viscosity resin has polymerized, less than 75% of the low viscosity resin has polymerized.

### Claim 4 (depends on 1)

The jettable composition of claim 1 wherein the low viscosity reactive resin has a viscosity of less than 75% of the viscosity of the high viscosity resin at a jetting temperature ranging between 20° C. and 80° C.

### Claim 5 (depends on 1)

The jettable composition of claim 1 wherein the low viscosity reactive resin has a viscosity of less than 50% of the viscosity of the high viscosity resin at a jetting temperature ranging between 20° C. and 80° C.

### Claim 6 (depends on 1)

The jettable composition of claim 1 wherein the curable toughener is a functionalized polycaprolactone.

### Claim 7 (depends on 1)

The jettable composition of claim 1 wherein the curable toughener is selected from the group consisting of a functionalized poly(tetrahydrofuran), a functionalized dendrimerie polyol, and a functionalized polycaprolactone.

### Claim 8

A curable jettable composition having a viscosity less than 30 cps at a temperature within the range of 15° C.-180° C. comprising:
(a) 25% to 80% by weight of at least one low viscosity reactive resin consisting of one or more oxetane compounds, wherein the low viscosity resin has a molecular weight of not greater than 300 Daltons and a viscosity of less than 30 cps at a temperature within the range of 15° C.-180° C.;
(b) 40% to 50% by weight of a high viscosity epoxy resin component wherein the epoxy resin component is a cycloaliphatic epoxy resin selected from 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate and bis-(3,4-epoxycyclohexyl)adipate and wherein the high viscosity resin has a functionality of greater than or equal to 2 and a viscosity greater than twice the viscosity of the low viscosity reactive resin at a temperature within the range of 15° C.-180° C.;
(c) 2% to 25% by weight of at least one curable toughener comprising a polymer or oligomer having a hydroxy, or acrylic group and a functionality of at least 2;
(d) 0.5% to 10% by weight of at least one initiator;
(e) 0.02% to 0.5% by weight of at least one stabilizer;
(f) 0 to 10% by weight of a vinyl ether curable co-diluent; and
(g) 0 to 25% by weight of one or more additives
and wherein the low viscosity reactive resin is slower to react than the high viscosity resin.