# US 11,440,244 B2 · Dual precursor resin systems for additive manufacturing with dual cure resins

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- Number: US 11,440,244 B2
- Document ID: US11440244B2
- Status: Granted
- Kind: B2
- Application number: 16/432,352
- Filed: 2019-06-05
- Published: 2019-09-19
- Granted: 2022-09-13
- Earliest claimed: 2015-12-22
- Assignees: Carbon, Inc.
- Applicants: Carbon, Inc.
- Inventors: Jason P. Rolland; Julia D. Cushen
- Web page: https://patentgrep.com/patent/US11440244B2

## CPC

- A43B 13/181: {Resiliency achieved by the structure of the sole}
- B29C 64/129: characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- A42C 2/00: Manufacturing helmets by processes not otherwise provided for
- A43B 13/14: characterised by the constructive form
- A43B 17/02: wedge-like or resilient
- A43B 21/24: characterised by the constructive form
- B29C 64/124: using layers of liquid which are selectively solidified
- B29C 64/135: the energy source being concentrated, e.g. scanning lasers or focused light sources
- B33Y 30/00: Apparatus for additive manufacturing; Details thereof or accessories therefor
- B33Y 50/00: Data acquisition or data processing for additive manufacturing
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C08L 63/00: Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- 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 7/029: Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
- 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)
- G03F 7/16: Coating processes; Apparatus therefor (applying coatings to base materials in general B05; applying photosensitive compositions to base for photographic purposes G03C1/74)
- G03F 7/40: Treatment after imagewise removal, e.g. baking
- B33Y 10/00: Processes of additive manufacturing
- A43B: CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- 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)
- A42C: MANUFACTURING OR TRIMMING HEAD COVERINGS, e.g. HATS
- 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
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- 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)

## Abstract

A method of forming a dual cure three-dimensional object by additive manufacturing may be carried out by mixing a first precursor liquid and a second precursor liquid to produce a polymerizable liquid comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component (e.g., a second reactive component) that is different from the first component (e.g., that does not contain a cationic photoinitiator, or is further solidified by a different physical mechanism, or further reacted, polymerized or chain extended by a different chemical reaction). In the foregoing: (i′) at least one reactant of the second solidifiable component is contained in the first precursor liquid, and (ii′) at least one reactant or catalyst of the second solidifiable component is contained in the second precursor liquid. Once mixed, the three-dimensional object may be formed from the resin by a dual cure additive manufacturing process.

## Claims

### Claim 1

A combination comprising precursor resin compositions which on mixing together produce an epoxy dual cure resin useful for additive manufacturing, said combination comprising:
(a) a first, pseudoplastic, precursor resin composition, comprising:
(i) an organic hardener co-polymerizable with an epoxy resin, said organic hardener in solid particulate form and dispersed in said first precursor resin composition;
(ii) optionally, a first photoinitiator;
(iii) first monomers and/or first prepolymers that are polymerizable by exposure to actinic radiation or light;
(iv) optionally, a first light absorbing pigment or dye;
(v) optionally, a first diluent;
(vi) optionally, a first particulate filler; and
(vii) optionally, a first co-monomer and/or a first co-prepolymer with said epoxy resin;
and
(b) a second precursor resin composition wherein the second precursor resin composition consists essentially of
(i) said epoxy resin that is co-polymerizable with said organic hardener;
(ii) a dual reactive compound having substituted thereon a first reactive group reactive with said first monomers and/or said first prepolymers that are polymerizable by exposure to actinic radiation or light, and a second reactive group reactive with said epoxy resin, wherein said dual reactive compound is present in the second precursor resin composition in amount of 1 to 30 percent by weight;
(iii) optionally, a second photoinitiator that is the same as or different from said first photoinitiator;
(iv) optionally, second monomers and/or second prepolymers that are polymerizable by exposure to actinic radiation or light wherein said second monomers are the same as or different from said first monomers and wherein the second prepolymers are the same as or different from said first prepolymers;
(v) a second light absorbing pigment or dye that is the same as or different from said first light absorbing pigment or dye;
(vi) optionally, a second diluent that is the same as or different from said first diluent;
(vii) optionally, a second particulate filler that is the same as or different from said first particular filler; and
(viii) optionally, a second co-monomer and/or second co-prepolymer with said epoxy resin, wherein said second co-monomer is the same as or different from the first monomer and said second co-prepolymer is the same as or different from said first co-prepolymer,
wherein said first photoinitiator is included in said first precursor resin composition and/or said second photoinitiator is included in said second precursor resin composition.

### Claim 2 (depends on 1)

The combination of claim 1, wherein said epoxy resin comprises a bisphenol A epoxy resin, a bisphenol F epoxy resin, a novolac epoxy resin, an aliphatic epoxy resin, a glycidylamine epoxy resin, an epoxidized vegetable oil, or a combination thereof.

### Claim 3 (depends on 1)

The combination of claim 1, wherein said hardener comprises an amine, and/or
said epoxy resin comprises a catalyzed epoxy resin.

### Claim 4 (depends on 1)

The combination of claim 1, wherein said hardener comprises an acid, a phenol, an alcohol, a thiol, or an anhydride.

### Claim 5 (depends on 1)

The combination of claim 1, wherein said hardener comprises a latent hardener.

### Claim 6 (depends on 1)

The combination of claim 1, wherein said first monomers said first prepolymers, said second monomers, and/or said second prepolymers polymerizable by exposure to actinic radiation or light comprises reactive end groups selected from the group consisting of acrylates, methacrylates, α-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, vinyl ethers, and combinations thereof.

### Claim 7 (depends on 1)

The combination of claim 1, wherein said first light absorbing pigment or dye and/or said second light absorbing pigment or dye is: (i) titanium dioxide, (ii) carbon black, and/or (iii) an organic ultraviolet light absorber.

### Claim 8 (depends on 1)

The combination of claim 1, wherein said first diluent is present in said first precursor resin composition and/or said second diluent is present in said second precursor resin composition and said first diluent and/or second diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, or a combination of two or more of the foregoing.

### Claim 9 (depends on 1)

The combination of claim 1, wherein said first particulate filler is present in said first precursor resin composition and/or said second particulate filler is present in said second precursor resin composition, and said first particulate filler and/or said second particulate filler comprises a core-shell rubber.

### Claim 10 (depends on 1)

The combination of claim 1, wherein upon mixing said first and second precursor resin compositions, is formed a polymerizable liquid comprising:
from 0.1 to 4 percent by weight in total of said first photoinitiator and said second photoinitiator;
from 10 to 90 percent by weight in total of said first monomers and/or first prepolymers that are polymerizable by exposure to actinic radiation or light and said second monomers and/or second prepolymers that are polymerizable by exposure to actinic radiation or light;
from 0.1 to 2 percent by weight in total of said first light absorbing pigment or dye and said second light absorbing pigment or dye;
from 2 to 60 percent by weight of said epoxy resin;
from 1 to 40 percent by weight of said organic hardener;
from 1 to 30 percent by weight of said dual reactive compound;
from 1 to 40 percent by weight in total of said first diluent and said second diluent, when present; and
from 1 to 50 percent by weight in total of said first filler and said second filler, when present.

### Claim 11

A precursor resin composition useful for making a dual cure resin which is, in turn, useful for additive manufacturing, said precursor resin composition consisting essentially of:
(i) from 2 to 60 percent by weight of an epoxy resin co-polymerizable with an organic hardener;
(ii) from 1 to 30 percent by weight of a dual reactive compound having substituted thereon a first reactive group reactive with monomers and/or prepolymers that are polymerizable by exposure to actinic radiation or light, and a second reactive group reactive with said epoxy resin;
(iii) from 0.1 to 4 percent by weight of a photoinitiator;
(iv) from 10 to 90 percent by weight of monomers and/or prepolymers that are polymerizable by exposure to actinic radiation or light;
(v) from 0.1 to 2 percent by weight of a light absorbing pigment or dye;
(vi) from 1 to 40 percent by weight of a diluent; and
(vii) optionally, from 1 to 50 percent by weight of a particulate filler.

### Claim 12 (depends on 11)

The precursor resin composition of claim 11, wherein said epoxy resin comprises a bisphenol A epoxy resin, a bisphenol F epoxy resin, a novolac epoxy resin, an aliphatic epoxy resin, a glycidylamine epoxy resin, an epoxidized vegetable oil, or a combination thereof.

### Claim 13 (depends on 11)

The precursor resin composition of claim 11, wherein said monomers and/or prepolymers polymerizable by exposure to actinic radiation or light comprise reactive end groups selected from the group consisting of acrylates, methacrylates, α-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, vinyl ethers, and combinations thereof.

### Claim 14 (depends on 11)

The precursor resin composition of claim 11, wherein said light absorbing pigment or dye is: (i) titanium dioxide, (ii) carbon black, and/or (iii) an organic ultraviolet light absorber.

### Claim 15 (depends on 11)

The precursor resin composition of claim 11, wherein said diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, or a combination of two or more of the foregoing.

### Claim 16 (depends on 11)

The precursor resin composition of claim 11, wherein said particulate filler is present and comprises a core-shell rubber.

### Claim 17 (depends on 1)

The combination of claim 1, wherein said second precursor resin consists essentially of:
from 2 to 60 percent by weight of said epoxy resin;
from 1 to 30 percent by weight of said dual reactive compound;
from 0.1 to 4 percent by weight of said second photoinitiator;
from 10 to 90 percent by weight of said second monomers and/or second prepolymers that are polymerizable by exposure to actinic radiation or light;
from 0.1 to 2 percent by weight of said second light absorbing pigment or dye;
from 1 to 40 percent by weight of said second diluent; and
from 1 to 50 percent by weight of said second particulate filler when present.