# US 2017/0283580 A9 · Stabilized matrix-filled liquid radiation curable resin compositions for additive fabrication

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2017/0283580 A9
- Document ID: US20170283580A9
- Status: Published application
- Kind: A9
- Application number: 14/951,743
- Filed: 2015-11-25
- Published: 2017-10-05
- Earliest claimed: 2013-11-05
- Assignees: Dsm IP Assets B.V.
- Applicants: DSM IP Assets B.V.
- Inventors: Mingbo He; Beth Rundlett; Kangtai Ren; Caroline Liu; Tai Yeon Lee
- Web page: https://patentgrep.com/patent/US20170283580A9

## CPC

- C08K 3/36: Silica
- B29C 64/135: the energy source being concentrated, e.g. scanning lasers or focused light sources
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- C08F 2/50: with sensitising agents
- C08L 33/10: Homopolymers or copolymers of methacrylic acid esters
- C09D 5/00: Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced {(electrically insulating plastics, resins or waxes H01B3/30)}; Filling pastes
- C09D 5/02: Emulsion paints {including aerosols}
- G03F 7/0037: {Production of three-dimensional images}
- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- G03F 7/0047: {characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing}
- G03F 7/027: Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence)
- G03F 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021)
- B29K 2063/00: Use of {EP, i.e.} epoxy resins {or derivatives thereof}, as moulding material
- B29K 2105/0088: {Blends of polymers}
- B29K 2105/246: {Uncured, e.g. green}
- B29K 2509/02: Ceramics
- C08F 222/103: {of trialcohols, e.g. trimethylolpropane tri(meth)acrylate}
- C08F 222/106: {Esters of polycondensation macromers}
- C08K 2201/011: Nanostructured additives
- Y10T 428/31511: Of epoxy ether
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- 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)
- 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
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- 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)
- 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)
- 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
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Matrix-filled liquid radiation curable resin compositions for additive fabrication are described and claimed. Such resins include a cationically polymerizable component that is an aliphatic epoxide, a multifunctional (meth)acrylate component, a cationic photoinitiator, a free-radical photo initiator, and a matrix of inorganic fillers, wherein the matrix further constitutes prescribed ratios of at least one microparticle constituent and at least one nanoparticle constituent. Also described and claimed is a process for using the matrix-filled liquid radiation curable resins for additive fabrication to create three dimensional parts, and the three-dimensional parts made from the liquid radiation curable resins for additive fabrication.

## Claims

### Claim at position 1

1-18. (canceled)

### Claim 19

A liquid radiation curable composition for additive fabrication comprising:
(a) a cationically polymerizable component;
(b) a (meth)acrylate component;
(c) a cationic photoinitiator;
(d) a free-radical photoinitiator;
(e) a filled matrix, further comprising
a filled particle dispersion containing
a nanoparticle constituent made up of a plurality of silica nanoparticles having an average particle size of at least about 50 nanometers, and
a solvent, and
a microparticle constituent made up of a plurality of inorganic microparticles;
wherein the ratio by weight of the microparticle constituent to the nanoparticle constituent is from about 1:1 to about 12:1,
wherein the filled particle dispersion has a particle dispersion pH of greater than about 5.5.

### Claim 20 (depends on 19)

The liquid radiation curable composition for additive fabrication of claim 19, wherein
said plurality of silica nanoparticles have ara average particle size of from about 50 nanometers to about 100 nanometers;
said plurality of inorganic microparticles have an average particle size of from about 0.2 microns to 20 microns; and
wherein the particle dispersion pH of the filled particle dispersion is from 6.0 to about 7.5.

### Claim 21 (depends on 20)

The liquid radiation curable composition for additive fabrication of claim 20, wherein the filled matrix is present in an amount by weight, relative to the entire composition, of from about 50 wt % to about 70 wt %.

### Claim 22 (depends on 21)

The liquid radiation curable composition for additive fabrication of claim 21, wherein
the ratio of the average particle size of the inorganic microparticles in the microparticle constituent to the average particle size of the silica nanoparticles in the nanoparticle constituent is from about 6.46:1 to about 100:1; and
the ratio by weight of the microparticle constituent to the nanoparticle constituent is from about 4:1 to about 8:1.

### Claim 23 (depends on 22)

The liquid radiation curable composition for additive fabrication of claim 22, wherein the solvent is selected from one or more of the group consisting of methyl ethyl ketone, isopropanol, an epoxide, an oxetane, and an acrylate.

### Claim 24 (depends on 23)

The liquid radiation curable composition for additive fabrication of claim 23, wherein the solvent is a 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate.

### Claim 25 (depends on 24)

The liquid radiation curable composition for additive fabrication of claim 24, wherein component (c) is an R-substituted aromatic thioether triaryl sulfonium or iodonium tetrakis(pentafluorophenyl) borate cationic photoinitiator with a tetrakis(pentafluorophenyl)borate anion and a cation of the following formula (I):
wherein Y1, Y2, and Y3 are the same or different and wherein Y1, Y2, or Y3 are R-substituted aromatic thioether with R being an acetyl or halogen group.

### Claim 26 (depends on 24)

The liquid radiation curable composition for additive fabrication of claim 24, wherein component (c) is a fluoroalkyl-substituted fluorophosphate with a cation of the following general formula (II):
wherein R1, R2, R3, R5 and R6 each independently represent an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, R4 represents an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylthio group, a heterocyclic hydrocarbon group, an alkylsulfinyl group, an alkylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, m1 to m6 each represent the number of occurrences of each of R1 to R6, m1, m4, and m6 each represent an integer of 0 to 5, and m2, m3, and m5 each represent an integer of 0 to 4.

### Claim 27 (depends on 1)

The liquid radiation curable composition for additive fabrication of claim 1, wherein the nanoparticle constituent comprising a plurality of nanoparticles is present in a filled particle dispersion further comprising a solvent, wherein the filled particle dispersion has a particle dispersion pH of greater than about 5.5.

### Claim 28 (depends on 27)

The liquid radiation curable composition for additive fabrication of claim 27, wherein said plurality of silica nanoparticles have an average particle size of from about 50 nanometers to about 100 nanometers, wherein said plurality of inorganic microparticles have an average particle size of from about 0.2 microns to 20 microns, and wherein the particle dispersion pH of the filled particle dispersion is from 6.0 to about 7.5.

### Claim 29 (depends on 28)

The liquid radiation curable composition for additive fabrication of claim 28, wherein
the ratio of the average particle size of the inorganic microparticles in the microparticle constituent to the average particle size of the silica nanoparticles in the nanoparticle constituent is from about 6.46:1 to about 100:1; the ratio by weight of the microparticle constituent to the nanoparticle constituent is from about 4:1 to about 8:1, and the filled matrix is present in an amount by weight, relative to the entire composition, of from about 50 wt % to about 70 wt %.

### Claim 30 (depends on 29)

The liquid radiation curable composition for additive fabrication of claim 29, wherein the solvent is selected from one or more of the group consisting of methyl ethyl ketone, isopropanol, an epoxide, an oxetane, and an acrylate.

### Claim 31 (depends on 30)

The liquid radiation curable composition for additive fabrication of claim 30, wherein the solvent is a 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate.

### Claim 32 (depends on 28)

The liquid radiation curable composition for additive fabrication of claim 28, wherein the particle dispersion pH of the filled particle dispersion is alkaline.

### Claim 33 (depends on 19)

The liquid radiation curable composition for additive fabrication of claim 19, wherein the filled matrix further comprises a settling additive.

### Claim 34 (depends on 32)

The liquid radiation curable composition for additive fabrication of claim 32, wherein the settling additive is a fumed silica.

### Claim 35 (depends on 33)

The liquid radiation curable composition for additive fabrication of claim 33, wherein the fumed silica settling additive is hydrophilic.