# US 10,568,814 B2 · Photo-curable resin compositions and method of using the same in three-dimensional printing for manufacturing artificial teeth and denture base

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- Number: US 10,568,814 B2
- Document ID: US10568814B2
- Status: Granted
- Kind: B2
- Application number: 15/730,673
- Filed: 2017-10-11
- Published: 2018-02-22
- Granted: 2020-02-25
- Earliest claimed: 2012-12-18
- Assignees: DENTCA, Inc.
- Applicants: DENTCA, Inc.
- Inventors: Jae Sik Lee
- Web page: https://patentgrep.com/patent/US10568814B2

## CPC

- A61C 13/0004: {Computer-assisted sizing or machining of dental prostheses}
- A61C 13/0013: {using stereolithographic techniques}
- A61C 13/01: Palates or other bases or supports for the artificial teeth; Making same
- A61C 13/087: Artificial resin teeth {(A61C13/081 takes precedence; preparations A61K6/80)}
- A61C 13/10: Fastening of artificial teeth to denture palates or the like {(A61C8/0048 takes precedence)}
- A61K 6/15: Compositions characterised by their physical properties
- A61K 6/17: Particle size
- A61K 6/62: Photochemical radical initiators
- A61K 6/82: comprising hafnium oxide
- A61K 6/831: comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K 6/887: Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- A61K 6/889: Polycarboxylate cements; Glass ionomer cements
- A61K 6/893: Polyurethanes
- B29C 35/0805: {using electromagnetic radiation}
- B29C 64/10: Processes of additive manufacturing
- B29C 64/112: using individual droplets, e.g. from jetting heads
- B29C 64/264: Arrangements for irradiation
- B29C 64/386: Data acquisition or data processing for additive manufacturing
- B29C 71/02: Thermal after-treatment {(B29C71/0063 and B29C71/0072 take precedence)}
- B33Y 10/00: Processes of additive manufacturing
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- B33Y 80/00: Products made by additive manufacturing
- C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16}
- B29C 2035/0827: {using UV radiation}
- B29C 2071/022: {Annealing}
- B29K 2033/12: {Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate}
- G16H 20/40: relating to mechanical, radiation or invasive therapies, e.g. surgery, laser therapy, dialysis or acupuncture
- A61C: DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE (non-driven toothbrushes A46B; {tongue scrapers A61B17/24;} preparations for dentistry A61K6/00; preparations for cleaning the teeth or mouth A61K8/00, A61Q11/00)
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- 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
- 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)
- 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
- G16H: HEALTHCARE INFORMATICS, i.e. INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR THE HANDLING OR PROCESSING OF MEDICAL OR HEALTHCARE DATA

## Abstract

Photo-curable compositions for artificial teeth and denture base and a method for manufacturing denture by a three-dimensional printing system are provided. The compositions include photo-curable organic compounds, surface modified nano-sized inorganic filler, photo-initiator, colorant, and stabilizer. The composition is in a viscous liquid state having 1,000-5,200 cps at room temperature and has a low viscosity of 50-500 cps at 70° C. The composition also has an excellent curing rate for three-dimensional printing. Using the compositions, denture having a distinctive denture base and a set of artificial teeth can be manufactured via an inkjet type or digital light process type three-dimensional printing according to Computer Aided Design (CAD) data.

## Claims

### Claim 1

A composition comprising:
about 40 to about 60 weight % of at least one kind of ethoxylated difunctional bisphenol A dimethacrylate;
about 5 to about 20 weight % of at least one kind of multifunctional methacrylate;
about 20 to about 45 weight % of at least one kind of urethane dimethacrylate;
about 0 to about 15 weight % of at least one kind of silica particles having methacrylate functionalization layers and having an average particle size of less than about 200 nm;
about 0.2 to about 5.0 weight % of at least one kind of ultraviolet/visible (UV/Vis) light-photo-polymerization initiator;
at least one colorant; and
at least one stabilizer,
wherein viscosity of a liquid state mixture, including the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate, the at least one kind of multifunctional methacrylate, the at least one kind of urethane dimethacrylate, the at least one kind of silica particles, the at least one kind of UV/Vis light-photo-polymerization initiator, the at least one colorant, and the at least one stabilizer, is from 1000 to 5200 centipoise (cps) at room temperature or 25° C. and from 50 to 500 cps at 70° C.,
wherein the viscosity is adjusted to be within a range from 1000 to 5200 centipoise (cps) at room temperature or 25° C. and from 50 to 500 cps at 70° C. by controlling a ratio of the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate, the at least one kind of multifunctional methacrylate, the at least one kind of urethane dimethacrylate, the at least one kind of silica particles, the at least one kind of UV/Vis light-photo-polymerization initiator, the at least one colorant, and the at least one stabilizer in the mixture, and
wherein weight % of the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate is greater than weight % of the at least one kind of urethane dimethacrylate in the composition including more than 0 weight % of the at least one kind of silica particles.

### Claim 2 (depends on 1)

The composition of claim 1, wherein the viscosity is from 1,100 to 4,000 cps at the room temperature.

### Claim 3 (depends on 1)

The composition of claim 1, wherein at least 45 weight % of the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate is present in the composition when the composition includes at least 3 weight % of the at least one kind of silica particles.

### Claim 4 (depends on 3)

The composition of claim 3, wherein the weight % of the at least one kind of silica particles is about 3 to 6.

### Claim 5 (depends on 3)

The composition of claim 3, wherein the weight % of the at least one kind of silica particles is about 5 to 10.

### Claim 6 (depends on 1)

The composition of claim 1, wherein the weight % of the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate in the composition including more than 0 weight % of the at least one kind of silica particles is increased as an amount of the at least one kind of silica particles increases in the composition.

### Claim 7 (depends on 6)

The composition of claim 6, wherein the weight % of the at least one kind of urethane dimethacrylate in the composition including more than 0 weight % of the at least one kind of silica particles is decreased as the amount of the at least one kind of silica particles increases in the composition.

### Claim 8 (depends on 1)

The composition of claim 1, wherein the at least one kind of silica particles are substantially spherical.

### Claim 9 (depends on 8)

The composition of claim 8, wherein the at least one kind of silica particles are substantially non-porous.

### Claim 10 (depends on 1)

The composition of claim 1, wherein the at least one kind of silica particles comprise fused silica, synthetic silica, alumina silicate, amorphous silica, glass ceramic, soda glass, lithium borosilicate glass, barium glass, strontium glass, zinc glass, fluoroaluminum borosilicate glass, borosilicate glass, crystal quartz, or a mixture thereof.

### Claim 11 (depends on 1)

The composition of claim 1, wherein surfaces of the at least one kind of silica particles are modified.

### Claim 12 (depends on 11)

The composition of claim 11, wherein the surfaces of the at least one kind of silica particles are covered with coatings of an oxide.

### Claim 13 (depends on 12)

The composition of claim 12, wherein the oxide contain a zirconium atom, a silicon atom, and an oxygen atom.

### Claim 14 (depends on 11)

The composition of claim 11, wherein the at least one kind of silica particles are treated with a resin-compatibilizing surface treatment agent.

### Claim 15 (depends on 14)

The composition of claim 14, wherein the resin-compatibilizing surface treatment agent comprises a silane treatment agent.

### Claim 16 (depends on 15)

The composition of claim 15, wherein the silane treatment agent has an acryl group as a functional group.

### Claim 17 (depends on 15)

The composition of claim 15, wherein the silane treatment agent has a methacryl group as a functional group.

### Claim 18 (depends on 15)

The composition of claim 15, wherein the silane treatment agent comprises methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyldichlolorsilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, trimethylbromosilane, or diethylsilane.

### Claim 19 (depends on 1)

The composition of claim 1, wherein the at least one kind of silica particles are methacrylsilane treated silica particles.