# US 11,299,569 B2 · Material for 3D printing, process for preparing the same and article thereof

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- Number: US 11,299,569 B2
- Document ID: US11299569B2
- Status: Granted
- Kind: B2
- Application number: 15/507,670
- Filed: 2015-04-24
- Published: 2017-09-07
- Granted: 2022-04-12
- Earliest claimed: 2014-04-30
- Assignees: Institute of Chemistry, Chinese Academy of Sciences
- Applicants: Institute of Chemistry, Chinese Academy of Sciences
- Inventors: Heng Shen; Jing Guo; Tang Zhu; Ning Zhao; Jian Xu; Wenhua Sun; Jinyong Dong; Chuncheng Li; Wenxin Fu; Xuechun Lin; Yongmei Ma
- Web page: https://patentgrep.com/patent/US11299569B2

## CPC

- C08F 220/1803: {C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate}
- B28B 1/001: {Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material (selective deposition modelling of metallic powder B22F10/00; rapid manufacturing of 3D objects in general and in particular of plastics B29C64/00)}
- B29C 64/106: using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C 64/165: using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
- 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
- C08F 2/44: Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
- C08F 2/48: by ultraviolet or visible light
- C08F 2/50: with sensitising agents
- C08F 220/1802: {C2-(meth)acrylate, e.g. ethyl (meth)acrylate}
- C08F 220/1807: {C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate}
- C08J 3/12: Powdering or granulating
- C08J 3/203: {Solid polymers with solid and/or liquid additives}
- C08K 3/011: Crosslinking or vulcanising agents, e.g. accelerators
- C08K 3/013: Fillers, pigments or reinforcing additives
- C08K 3/08: Metals
- C08F 220/1804: {C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate}
- C08F 220/1812: {C12-(meth)acrylate, e.g. lauryl (meth)acrylate}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B28B: SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER (foundry moulding B22C; working stone or stone-like material B28D; shaping of substances in a plastic state, in general B29C; making layered products not composed wholly of these substances B32B)
- 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
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

The present invention provides a composition for 3D printing, a process for preparing the same and an article thereof. By the solidifying method of UV irradiation, 3D printing is implemented. During said implementation, there is no need of high temperature heating, thus energy consumption is reduced, and there is no need for special solvent, thus harm to the environment is reduced. Meanwhile, the present invention uses micro-nano powder as the main material and polymer resin as adhesive, and at the same time, adds irradiation sensitizer. After electron beam irradiation, the polymer resin forms three-dimensional crosslinked network, thereby the strength, heat resistance and chemical resistance are improved after resin adhesion. Additionally, the present invention, by the addition of UV crosslinking agent, and by UV irradiation, cross-links the unsaturated resin after extrusion in 3D printing to form three-dimensional network structure, thus greatly improves the heat resistance, chemical resistance and mechanical strength of the shaping material, and makes the unsaturated resin have broader application prospects in 3D printing material.

## Claims

### Claim 1

A composition for 3D printing comprising:
benzyl methacrylate of 100 parts by weight,
α,α-diethoxyacetophenone of 2 parts by weight,
ZrO2 powder of 15 parts by weight,
trimethylolpropane triacrylate of 30 parts by weight,
liquid polysulfide rubber of 10 parts by weight, and
cadmium red of 10 parts by weight,
wherein the trimethylolpropane triacrylate crosslinks with the benzyl methacrylate, and
the ZrO2 powder has a particle size between 1 μm and 10 μm, and is modified by a surface modifier that is dopamine or a silane coupling agent.

### Claim 2 (depends on 1)

The composition for 3D printing of claim 1, further comprising 0.1 to 0.5 parts by weight of an antioxidant selected from pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,3′-bis(3,5-di-tert-butyl-4-hydroxyphenyl)-N,N′-hexamethylenedipropionamide, tris [2,4-di-tert-butylphenyl] phosphite, and mixtures thereof.

### Claim 3

A composition for 3D printing, consisting of benzyl methacrylate of 100 parts by weight, α,α-diethoxyacetophenone of 2 parts by weight, ZrO2 powder of 15 parts by weight, trimethylolpropane triacrylate of 30 parts by weight, liquid polysulfide rubber of 10 parts by weight, and cadmium red of 10 parts by weight.

### Claim 4 (depends on 3)

The composition for 3D printing of claim 3, wherein the ZrO2 powder has a particle size between 1 μm and 10 μm, and is modified by a surface modifier that is dopamine or a silane coupling agent.