DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Objections
Claims 1-13 are objected to because of the following informalities: Claims 1-13 lack claim identifiers. Appropriate correction is required.
Election/Restrictions
Applicant’s election without traverse of Group II in the reply filed on 02/10/2025 is acknowledged. Claims 11-13 are non-elected.
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claim(s) 1-9 is/are rejected under 35 U.S.C. 103 as being unpatentable over Schaedler et al (US11,591,141) in view of Liu et al (WO2021/232,557).
Schaedler sets forth resin compositions for additive manufacturing of metallic components, and methods of making and using such resin compositions in 3D-printing processes
Said formulations comprises from 10-70 vol.% of a photocurable liquid (photosensitive resins and monomer mixtures); from 10 vol % to 70 vol % of metal or metal alloy particles, and from 0.01 vol % to 10 vol % of a photoinitiator—abstract, col. 2, lines 45-55 and col. 6, lines 11-20.
Said photocurable liquid resin comprise monomers, oligomers, and/or polymers [col. 18, line 16]. Said photocurable liquid resin contains an organic resin component in a concentration from about 10 vol % to about 80 vol % of the photocurable liquid resin, wherein the resin component is a photosensitive resin—see col. 2, line 63 to col. 3, line 5. Schaedler sets forth the total monomer component comprises 1-70 vol%, wherein the preferred monomers include photosensitive acrylate monomers having acrylate functionality—see col. 17, lines 58-63. Said photoinitiator is present in a concentration from about 0.1 vol % to about 5 vol %. Said resin liquids may further comprise about 0.01 vol % to about 25 vol % of a UV reflector; about 1 vol % to about 50 vol % of a solvent, about 0.01 vol % to about 5 vol % of a surfactant, about 0.01 vol % to about 25 vol % of a sinter aid; and about 0.01 vol % to about 10 vol % of a 3D-printing resolution agent—see col. 4, lines 3-41. Schaedler sets forth with sufficient specificity a thermal initiator can be added to the composition in amounts up to 10 vol. % when multi-mechanisms of curing the formulation are desired, wherein up to 10 vol. % encompasses applicants claimed range—see col. 15, lines 53-67. Said metal or metal alloy particles contain a metal selected from the group consisting of Ni, Cu, Co, Fe, Mn, V, Cr, Ti, Al, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and combinations thereof having an average particle size from about 0.1 microns to about 500 microns,, wherein it is deemed the metal powders of claim 1 are encompassed—see col. 3, lines 53-62 and col. 14, lines 25-26.
Regarding claims 1-4: It is deemed a skilled artisan could obtain a metal resin formulation comprising from 50 to 70 % of a metal powder, such as iron, copper, aluminum, silver, tin, magnesium, nickel, titanium, vanadium, chromium, manganese, cobalt, nickel, zinc, aluminum alloy, copper alloy, stainless steel alloy, and nickel alloy having an average particle size from about 0.1 microns to about 500 microns; from 1-35 % of a photosensitive resin; from 1-35 wt. % of a photosensitive monomer; from 0.1 to 7 % of a photoinitiator; from 0.1 to 5 % of a thermal initiator; and from 0 to 2 % auxiliary agents from the overall teachings of the reference.
The primary difference is Schaedler does not teach or fairly suggest to a skilled artisan the addition up-conversion materials, such as one or more of NaYF4, BaYF5, NaGdF4, LiYF4. NaYbF4, Na3SeF6, YF3 and GdOF to increase cure depth and reactivity. Schaedler sets forth because of the high metal volume fraction in the resin the penetration depth of UV light or cure depth is decreased which hinders the 3D-printing process. Schaedler sets forth the decrease in cure depth may be counteracted by optimizing the particle size, particle surface functionality, autocatalytic nature of metal-organic resin molecules, and/or the photoinitiator, wherein the UV light penetration or cure depth may be improved with a high light reflectivity of the particle surface at the curing wavelength. Larger particle sizes are preferred because the UV light can then penetrate between particles.
As a result of the problem of the low degree of depth while curing with UV light, as used in three-dimensional printing, it is known in the prior art to add up-conversion particles to photocurable resin formulations used in 3D printing methods, as suggested by Liu. Liu sets forth material processing and three-dimensional printing, in particularly to a direct ink writing three-dimensional printing based. Liu teaches compositions comprising a photopolymerizable resin, a photopolymerizable monomer, a photoinitiator, an up-conversion material, a thixotropic agent, and a filler, wherein said composition comprises 0-80 wt. % photopolymerizable resin, 0-80 wt. % photopolymerizable monomer, 0.5-6 wt. % photoinitiator, 0.5-5 wt. % up conversion material, 0-30 wt. % thixotropic agent, 2-30 wt. % fillers, wherein said up-conversion materials include one or more of NaYF4, BaYF5, NaGdF4, LiYF4, NaYbF4, Na3ScF6, YF3, and GdOF. By example Liu sets forth direct writing of a curable resin composition comprising 1.0 wt. % initiator (Irgacure 784), 1.0 wt. % NaYF4 up-conversion nanoparticles, 13.0 wt. % thixotropic agent (Aerosil, Evonik TS100), 42.5 wt. % epoxy acrylate resin and 42.5 wt. % monomer (trimethylolpropane triacrylate) achieved a 3D structure having a full depth cure—see example 1 and figure 3.
Schaedler and Liu are analogous art since they are concerned with the same problem, depth cure in 3D printing object. Therefore, it would have been obvious to a skilled artisan, concerned with depth cure, to add up conversion particles, such one or more of NaYF4, BaYF5, NaGdF4, LiYF4, NaYbF4, Na3ScF6, YF3, and GdOF, as taught by Liu, to the compositions set forth by Schaedler, as discussed above, with a reasonable expectation of successfully achieving a deep through cure (full depth cure) of the 3D printed articles in absence of evidence to the contrary and/or unexpected results.
Regarding claims 5-7: Schaedler sets forth using photoinitiators, such as peroxides; thioxanthones; 2,2-dimethoxy-2-phenylacetophenone; 2-hydroxy-2-methylpropiophenone; camphorquinone; bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide; diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide; benzophenone; azobisisobutyronitrile; benzoyl peroxide; or combinations thereof—see col. 15, lines 40-45. Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide; diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide are acylphosphine oxide cleavage (cracking) free radical photoinitiators, while thioxanthones are sulfur containing hydrogen abstraction type photoinitiators.
Regarding claims 8: Schaedler sets forth using thermal initiators, such as benzophenone, azobisisobutyronitrile, peroxides, benzoyl peroxide, dicumyl peroxide, or combinations thereof—see col. 15, lines 59-60.
Regarding claim 9: Schaedler sets forth optional additives, such as surfactants which reduce surface tension between two phase which decreases surface tension and thereby preventing particles from aggregating and settling.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure, as well as, the progression and/or state of the art.
Morin et al (US10,174,146) sets forth a dual cure acrylic formulation (a photo-thermal formulation) comprising polymerizable acrylic oligomers and monomers; a thermal initiator, a photoinitiator, and a peroxide compound. Morin sets forth, by example, the compositions can comprise up to 60 parts by weight of filler—see example 1 and abstract. Morin teaches the combination of the photoinitiator, the thermal initiator, in combination with the peroxide generates free radicals under UV radiation or heat or both, wherein a fraction of the mixture may be cured by exposing the formulation to light and the remainder of the formulation is cured exposing said formulation to a temperature below the decomposition temperature of the peroxide—see col. 4. Morin does not explicitly teach or fairly suggest the filler is a metal powder being one or more of iron, copper, aluminum, silver, tin, magnesium, nickel, titanium, vanadium, chromium, manganese, cobalt, nickel, zinc, gallium, germanium, aluminum alloy, copper alloy, stainless steel alloy, and nickel alloy. Nor does Morin explicitly teach and/fairly suggest adding up-conversion materials, such as one or more of NaYF4, BaYF5, NaGdF4, LiYF4. NaYbF4, Na3SeF6, YF3 and GdOF, to the formulations. Morin does not explicitly teach said obtaining a green body from said formulations. Nor does Morin set forth methods of using said formulation in additive manufacturing methods as found in the instant claims.
Chaput et al (US 2021/0024422) sets forth methods for manufacturing green ceramic or metal parts using additive manufacturing methods. Said method comprises the use of a photo-thermal curable formulation comprising 25 to 65 parts by weight of a ceramic powder and/or metal powder, an acrylic oligomer monomers (photosensitive resin and monomer); and a thermal polymerization initiator. Chaput teaches away from the use of a photoinitiator and instead relies on the properties of the ceramics or metal powders to absorb the light energy from a radiation source/exposure and emit heat into the formulation to generate free radicals from the thermal polymerization initiator to cure said formulation for obtaining the green body. Chaput does not teach or fairly suggest the addition up-conversion materials, such as one or more of NaYF4, BaYF5, NaGdF4, LiYF4. NaYbF4, Na3SeF6, YF3 and GdOF.
Oprych et al (chemphotochem, 2019) teaches adding up-conversion particles to multi-functional methacrylate formulation comprising blue- and UV-sensitive photoinitiators. Oprych does not expressly teach or suggest the formulation comprise photosensitive monomers, thermal initiator, additives, or metal powders, such as one or more of iron, copper, aluminum, silver, tin, magnesium, nickel, titanium, vanadium, chromium, manganese, cobalt, nickel, zinc, gallium, germanium, aluminum alloy, copper alloy, stainless steel alloy, and nickel alloy. Nor does Oprych set forth methods of using said formulation in additive manufacturing methods as found in the instant claims.
Polidore et al (US 11,787,878) sets forth photocurable composition for stereolithographic three-dimensional printing, wherein the photocurable composition comprises a photoreactive oligomer component comprising a hydrophobic oligomer comprising a photoreactive end group, a photoreactive monomer component comprising a photoreactive monomer having a photoreactive end group, and a photoinitiation composition comprising a photoinitiator. Polidore teaches the composition can additionally comprise a scintillating agent that can absorb high-energy invisible radiant energy and emit, in response to excitation by the absorbed energy, radiant energy of a lower level and longer wavelength than the exciting energy but still of a shorter wavelength and higher energy level than visible light—col. 10. Polidore additionally suggest said composition can comprise a laser-direct structuring additive, such as a metal powder for obtain a conductive layer or portion in the cured article. Said metal powder is suggested to be added in amounts of 2 to 20 parts per 100 parts of the composition—see col. 13-14. Polidore does not teach or fairly suggest to a skilled artisan the addition up-conversion materials, such as one or more of NaYF4, BaYF5, NaGdF4, LiYF4. NaYbF4, Na3SeF6, YF3 and GdOF.
Liu et al (US12,184,672 and Nat. Comm.,2020) teaches near-infrared photopolymerization of acrylic ink formulations comprising a photosensitive oligomer, a photosensitive monomer, a photoinitiator, a filler (silicon dioxide) in an amount of 13. wt. %, a pigment, and up-conversion particles. Liu does not expressly teach and/or fairly suggest the addition of 50-90 parts by of a metal powder or a thermal polymerization initiator. Additionally, Liu et al sets forth a near infrared adhesive composition comprising an acrylic resin, acrylic monomers, a photoinitiator, a thermal initiator, and up conversion particles. Lui does not expressly set forth the addition of metal powders in amounts from 50 to 95% nor does Liu set forth a method of additive manufacture to obtain a green body. Liu sets forth bonding substrates, such as glass, wood, plastic and other substrates to form bonded laminates.
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/SANZA L. McCLENDON/Primary Examiner, Art Unit 1765
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