DETAILED ACTION
In Reply filed on 12/02/2025, claims 1, 4-15, and 17-26 are pending. Claims 1 and 26 are currently amended. Claims 2-3 and 16 are canceled, and no claim is newly added. Claims 14-15 are withdrawn. Claims 1, 4-13, and 17-26 are considered in this Office 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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 12/02/2025 has been entered.
Claim Interpretation
Claim 1 recites the limitation “a viscosity from 10 mPa·s to 200 mPa·s” in lines 4-5. The viscosity would be interpreted as measured at 25 °C according to Instant Specification ([0105], as published).
Claim 1 recites the limitation “mono-functional cyanoacrylate monomers” in lines 6-7. Also, claim 26 recites the limitation “mono-functional cyanoacrylate-based monomers” in lines 3-4. The limitation(s) would be interpreted as defined in Instant Specification ([0118-0119]: having chemical formula (I), wherein R may be selected from the group consisting of an alkyl group or an alkoxyalkyl group, as published in US 20240083104 A1).
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1, 4-13 and 16-21 are rejected under 35 U.S.C. 103 as being unpatentable over DeSimone (US 20150097315 A1) in view of López Maeso (US 20180215973 A1) and Truong (US 20210354378 A1).
Regarding claim 1, DeSimone teaches a method for printing a three-dimensional (3D) article (abstract, fig. 1), comprising the steps of:
a) providing a tank comprising at least one optically transparent portion ([0127-0129]: build plate 15 is optically transparent to the radiation source; fig. 2),
b) providing a volume of liquid resin comprising having a viscosity from 10 mPa·s to 200 mPa·s ([0229]: the polymerizable liquid has a viscosity of at least 100, up to 1,000,000 cPs (i.e., mPa·s) or more at 25 degrees C; here, the disclosed range overlaps with the recited range between 100 mPa·s and 200 mPa·s; In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) (MPEP 2144.05 I); [0229]: specific end viscosity desired to be achieved will depend on factors such as the rate of fabrication desired, size and shape of the article being fabricated), wherein the volume of liquid resin comprises [cyanoacrylate-based] monomers (fig. 1, [0105, 0148]: a polymerizable liquid including monomers), [which are exclusively mono-functional cyanoacrylate monomers], a photoinitiating system ([0115, 0117]: photoinitiator) and an [acidic] inhibitor ([0123-0124]: inhibitors), held in a tank (fig. 2, [0127]: a build chamber defined by wall 14);
c) defining a polymerization zone (fig. 1, [0148]: build region);
d) emitting and controlling light and transmitting it to the liquid resin through the optically transparent portion for selectively polymerizing the liquid resin in the polymerization zone (fig. 1, [0148]; irradiating build region through build plate to produce a solid polymerized region); and
e) obtaining a three-dimensional article made of the polymerized liquid resin (fig. 1, [0148]; forming three-dimensional object);
f) [treating the obtained three-dimensional article with a non-nucleophilic rinsing solvent for removing the excess liquid resin]; and,
g) [optionally exposing the obtained three-dimensional article with an additional light source for rendering the article non tacky].
DeSimone does not specifically teach the bracketed limitations as presented above, but
López Maeso and Truong teach the limitations as follows:
Regarding the liquid resin, López Maeso teaches a volume of liquid resin ([0016, 0267-0268]) comprising cyanoacrylate-based monomers ([0078-0079]), a photoinitiator ([0027-0038]), an acidic inhibitor ([0093]; Lewis acid inhibitor), and additional monomers ([0088-0092]) for use in the production of bulk stepwise or continuous cured resins such as those used in 3DP or CLIP ([0016, 0149, 0267]: for use in 3D printing or Continuous Liquid Interface Printing (CLIP)), and the cyanoacrylate-based monomers are exclusively mono-functional cyanoacrylate monomers (López Maeso: Table II, III: e.g., Examples 1.1-1.3, 1.6-1.7).
DeSimone and López Maeso are both considered to be analogous to the claimed invention because they are in the field of layerwise 3D printing (DeSimone: abstract; López Maeso: [0016, 0149]). Therefore, it would have been obvious to one of the ordinary skill in the art at the time of filing invention to modify the liquid resin composition of DeSimone with the liquid resin comprising cyanoacrylate-based monomers, which are exclusively mono-functional cyanoacrylate monomers, a photoinitiator, an acidic inhibitor, and additional monomers as taught by López Maeso in order to obtain known results or a reasonable expectation of successful results of allowing a volume of liquid resin to be polymerized rapidly and ensuring the liquid resin to be stable in acidic conditions over prolonged time periods before polymerization for the purposes of improving the durability and robustness of the thus-formed three-dimensional article (López Maeso [0016, 0017-0018]).
Regarding the post-process of steps f) and g), Truong teaches a post-processing/apparatus that may be integrated into 3D printing system for processing 3D printed object after curing (figs. 1A-1B, [0082-0083, 0093]). Truong teaches e) treating the obtained three-dimensional article with a non-nucleophilic rinsing solvent for removing the excess liquid resin ([0045-0058]: wash liquid, e.g., hydrocarbon, ether, dipolar aprotic, ethyl acetate, hydrofluorocarbon solvents); and, f) optionally exposing the obtained three-dimensional article with an additional light source for rendering the article non tacky ([0066, 0071]: a light source, such as an ultraviolet light source, to further light cure components; here, it is implied that the article would be non-tacky after the exposure as any remaining solvent or liquid resin would be dried or cured, respectively; of note, this step is “optional,” and thus, it is not required).
Modified DeSimone and Truong are both considered to be analogous to the claimed invention because they are in the field of 3D printing (DeSimone: abstract; Truong: [0002-0004, 0093]). Therefore, it would have been obvious to one of ordinary skill in the art at the time of filing invention to modify the 3D printing process/apparatus of modified DeSimone to be integrated with the post-processing of 3D printing such as washing and further curing of an intermediate 3D printed article as taught by Truong in order to obtain known results or a reasonable expectation of successful results of removing excess resin material from the intermediate 3D article and enhancing mechanical properties so as to improve overall quality and aesthetics of a final 3D printed article.
Regarding claim 4, modified DeSimone teaches the printing method according to claim 1, in which the cyanoacrylate-based monomers are selected from 2-methoxyethyl cyanoacrylate, methyl cyanoacrylate, ethyl cyanoacrylate, n-propyl cyanoacrylate, iso-propyl cyanoacrylate or mixtures thereof (López Maeso: [0084]).
Regarding claim 5, modified DeSimone teaches the printing method according to claim 1, in which the liquid resin comprises additional photopolymerizable monomers (López Maeso: [0088-0092]: additional monomers).
Regarding claim 6, modified DeSimone teaches the printing method according to claim 1, in which the photoinitiator system is an anionic or zwitterionic photoinitiating system (López Maeso: [0027-0038]: e.g., ferrocene compound or acylgermane compound). Here, the disclosed photoinitiator system is the same as the one of Instant Specification (Instant Specification: [0171-0172, 0176-0177], as published).
Regarding claim 7, modified DeSimone teaches the printing method according to claim 6, in which the anionic or zwitterionic photoinitiating system comprises the combination of a metallocene compound and a radical photoinitiator (López Maeso: [0027-0038]: e.g., ferrocene compound, acylgermane compound, or optionally combined with a radical photoinitiator).
Regarding claim 8, modified DeSimone teaches the printing method according to claim 1, in which the non-nucleophilic solvent is selected from the group consisting of non-basic solvents, non-ionic solvents (or solutions) and mixtures thereof (Truong: [0045- 0058]: wash liquid, e.g., hydrocarbon, ether, dipolar aprotic, ethyl acetate, hydrofluorocarbon solvents).
Regarding claim 9, modified DeSimone teaches the printing method according to claim 1, in which the non-nucleophilic rinsing solvent is selected from the group consisting of hydrocarbon solvents, perfluorinated hydrocarbon solvents, ether solvents, acetate solvents, chlorohydrocarbon solvents, polar aprotic solvents, and mixtures thereof (Truong: [0045- 0058]: wash liquid, e.g., hydrocarbon, ether, dipolar aprotic, ethyl acetate, hydrofluorocarbon solvents).
Regarding claims 10 and 19, modified DeSimone teaches the printing method according to claim 1, in which the step of treating the three-dimensional article with the non-nucleophilic rinsing solvent is carried out (Truong: [0045-0048]), but does not specifically teach that the step is carried out during (1) a period of 10 minutes or less (claim 10), or (2) a period of 4 minutes or less (claim 19).
Here, although modified DeSimone does not specifically teach the specific washing time, through routine optimization and experiment, it would have been obvious to one of ordinary skill in the art that the rinsing is carried out long enough to remove all of the excess resin on a 3D printed article but not too long to destructively dissolve the 3D printed article, e.g., about 3 minutes, so as to remove the excess resin effectively without deteriorating overall quality of a final 3D article.
Regarding claim 11, modified DeSimone teaches the printing method according to claim 1, in which the step of treating the three-dimensional article with a non-nucleophilic rinsing solvent is carried out by dipping the three-dimensional article into the non-nucleophilic solvent (Truong: [0045-0048], [0060]: by spinning the objects to be cleaned in the wash liquid), but does not specifically teach that the step is carried out for a period of 15 seconds or less.
Here, although modified DeSimone does not specifically teach the specific washing time, through routine optimization and experiment, it would have been obvious to one of ordinary skill in the art that the rinsing is carried out long enough to remove the excess resin on a 3D printed article but not too long to destructively dissolve the 3D printed article, e.g., about 10 seconds, so as to remove the excess resin effectively without deteriorating overall quality of a final 3D article.
Regarding claim 12, modified DeSimone teaches the printing method according to claim 1, in which the step of exposing the three-dimensional article to the additional light source is carried out at a wavelength from 380 nm to 470 nm (Truong: [0066, 0071]: a light source, such as an ultraviolet light source, to further light cure components). Here, although the disclosed range (i.e., ultraviolet light of 10 – 400 nm)1 does not anticipate the recited range, the disclosed range overlaps with the recited range between about 380 nm to 400 nm. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) (MPEP 2144.05 I).
Regarding claims 13 and 20, modified DeSimone teaches the printing method according to claim 1, in which the step of exposing the three-dimensional article to the additional light source is carried out (Truong: [0066, 0071]), but does not specifically teach that the step is carried out for (1) a period of 60 seconds or less (claim 13), or (2) for a period from 1 to 30 seconds (claim 20).
Here, modified DeSimone teaches all the claimed limitations as claim 1 recites the step g) as an “optional” step.
Alternatively, although modified DeSimone does not specifically teach the specific exposing time by the additional light source, through routine optimization and experiment, it would have been obvious to one of ordinary skill in the art that the additional light exposure is carried out long enough to cure any remaining non-polymerized or semi-polymerized liquid on a 3D printed article but not too long to delay an overall printing process or to waste energy for unnecessary excessive curing, e.g., about 10 seconds, so as to produce a final 3D article with improved quality and aesthetics as well as in an energy-saving mode.
Regarding claim 16, modified DeSimone teaches the printing method according to claim 1, in which the cyanoacrylate-based monomers are multi-functional cyanoacrylate monomers, hybrid cyanoacrylate monomers or mixtures thereof and optionally mono-functional cyanoacrylate monomers (López Maeso: fig. 1, [0083, 0085]; Table III: e.g., Examples 2.1-2.12).
Regarding claim 17, modified DeSimone teaches the printing method according to claim 1, in which the cyanoacrylate-based monomers are selected from 2-methoxyethyl cyanoacrylate, methyl cyanoacrylate or mixtures thereof (López Maeso: Tables II, III: MECA (methoxyethyl cyanoacrylate)).
Regarding claim 18, modified DeSimone teaches the printing method according to claim 1, in which the liquid resin comprises additional photopolymerizable monomers being (meth)acrylate monomers (López Maeso: [0088-0092]: additional monomers can be methacrylate).
Regarding claim 21, modified DeSimone teaches the printing method according to claim 1, further comprising the step of using the obtained three-dimensional article for a period of 1 minutes to 5 years. Although modified DeSimone is silent about how long the obtained 3D article is used, it is implied or at least obvious that the obtained 3D article would be used as long as it is needed.
Claims 22-26 are rejected under 35 U.S.C. 103 as being unpatentable over DeSimone (US 20150097315 A1), López Maeso (US 20180215973 A1), and Truong (US 20210354378 A1) as applied to claim 1, and further in view of Uyama (JP 2009030017 A)
Regarding claim 22, modified DeSimone teaches the printing method according to claim 1, but does not specifically teach that the method further comprises the step of treating the 3D article with a dissolving solvent for a time sufficient for dissolving it ranging from 1 to 72 h.
Uyama teaches a method for dissolving a (meth)acrylic acid ester-based polymer comprising a cyano group in a liquid for recycling ([0001, 0003-005, 0016]). Uyama teaches a polymer recycling method, wherein the method comprises dissolving a recovered polymer containing the polymer in a liquid to prepare a polymer solution, and separating the polymer precipitate deposited from the polymer solution ([0006, 0045]), and according to the method, the polymer itself can be recovered to be used as a raw material for processing ([0045]).
In the same field of endeavor of using a cyanoacrylate based material (modified DeSimone: López Maeso: Table II, III: e.g., Examples 1.1-1.3, 1.6-1.7; Uyama: [0016]), it would have been obvious to one of ordinary skill in the art at the time of invention to modify the method for printing 3D object of modified DeSimone to further include a step of dissolving the polymer article into a liquid as taught by Uyama in order to obtain known results or a reasonable expectation of successful results of recycling the 3D printed article when it is broken, no longer wanted, or needed for new use to save energy and reduce waste (Uyama: derived from [0003-0006]). Here, although modified DeSimone is silent about how long it takes to dissolve the obtained 3D article with a dissolving solvent, it would be obvious that the obtained 3D article would be dissolved as long as it is dissolved up to a desired level, for example, for a sufficient time to completely dissolve it in the dissolving solvent.
Regarding claim 23, modified DeSimone teaches the printing method according to claim 22, wherein the cyanoacrylate-based monomer is 2-methoxyethyl cyanoacrylate and the dissolving solvent is chosen from the group consisting of acetone, propylene carbonate, acetonitrile, isopropanol, toluene, ethyl acetate, tritolyl phosphate, glycerol triacetate, and 2-methoxyethyl cyanoacetate (López Maeso: [0223, 0231]: methoxyethyl 2-cyanoacrylate MECA, Example 1.1; [0242]: when monofunctional CAs were used alone, acetone soluble films resulted and no (0%) insoluble material was observed).
Regarding claim 24, modified DeSimone teaches the printing method according to claim 22, wherein the cyanoacrylate-based monomer is ethyl cyanoacrylate and the dissolving solvent is chosen from the group consisting of acetone, propylene carbonate, acetonitrile, isopropanol, toluene, ethyl acetate, tritolyl phosphate, glycerol triacetate, and ethyl cyanoacetate (López Maeso: [0223, 0230-0231]: ethyl 2-cyanoacrylate ECA, Example 1.2; [0242]: when monofunctional CAs were used alone, acetone soluble films resulted and no (0%) insoluble material was observed).
Regarding claim 25, modified DeSimone teaches the printing method according to claim 22, wherein the cyanoacrylate-based monomer is methyl cyanoacrylate and the dissolving solvent is chosen from the group consisting of acetone, propylene carbonate, acetonitrile, isopropanol, toluene, ethyl acetate, tritolyl phosphate, glycerol triacetate, ethyl cyanoacetate, and methyl cyanoacetate (López Maeso: [0002]: methyl 2-cyanoacrylate; [0223, 0230-0231]: ethyl 2-cyanoacrylate ECA (Example 1.2), butyl cyanoacrylate; [0242]: when monofunctional CAs were used alone, acetone soluble films resulted and no (0%) insoluble material was observed). Here, although methyl cyanoacrylate is not tested as an exemplary monomers in López Maeso, it would have been obvious to one of ordinary skill in the art that methyl cyanoacrylate is another known and commercially available cyanoacrylate monomers (López Maeso: [0002]), and the polymer made from a resin composition comprising methyl cyanoacrylate monomers would dissolve in acetone similar to the polymer made from a resin composition comprising ethyl cyanoacrylate or butyl cyanoacrylate (López Maeso: [0242]).
Regarding claim 26, modified DeSimone teaches a method for printing a 3D article the step of:
a) providing a volume of liquid resin comprising mono-functional cyanoacrylate- based monomers, a photoinitiator system and an acidic inhibitor, held in a tank, said tank comprising at least one optically transparent portion (see above, the 103 rejection of claim 1);
b) defining a polymerization zone (id.);
c) emitting and controlling light and transmitting it to the liquid resin through the optically transparent portion for selectively polymerizing the liquid resin in the polymerization zone (id.);
d) obtaining a three-dimensional article made of the polymerized liquid resin (id.);
e) treating the obtained three-dimensional article with a non-nucleophilic rinsing solvent for removing the excess liquid resin (id.);
f) exposing the obtained three-dimensional article with an additional light source for rendering the article non-tacky (id.);
g) using the obtained three-dimensional article for a period of time (see above, the 103 rejection of claim 21); and
h) treating the 3D article with a dissolving solvent for a time sufficient for dissolving it (see above, the 103 rejection of claim 22).
Thus, modified DeSimone teaches all the claimed limitations, and the motivation to combine applied to claims 1, 21, and 22 equally applies here.
Claims 1, 4-13 and 16-21 are rejected under 35 U.S.C. 103 as being unpatentable over DeSimone (US 20150097315 A1) in view of Delrot (WO 2020094593 A1) and Truong (US 20210354378 A1).
Regarding claim 1, DeSimone teaches a method for printing a three-dimensional (3D) article (abstract, fig. 1), comprising the steps of:
a) providing a tank comprising at least one optically transparent portion ([0127-0129]: build plate 15 is optically transparent to the radiation source; fig. 2),
b) providing a volume of liquid resin comprising having a viscosity from 10 mPa·s to 200 mPa·s ([0229]: the polymerizable liquid has a viscosity of at least 100, up to 1,000,000 cPs (i.e., mPa·s) or more at 25 degrees C; here, the disclosed range overlaps with the recited range between 100 mPa·s and 200 mPa·s; In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) (MPEP 2144.05 I); [0229]: specific end viscosity desired to be achieved will depend on factors such as the rate of fabrication desired, size and shape of the article being fabricated), wherein the volume of liquid resin comprises [cyanoacrylate-based] monomers (fig. 1, [0105, 0148]: a polymerizable liquid including monomers), [which are exclusively mono-functional cyanoacrylate monomers], a photoinitiating system ([0115, 0117]: photoinitiator) and an [acidic] inhibitor ([0123-0124]: inhibitors), held in a tank (fig. 2, [0127]: a build chamber defined by wall 14);
c) defining a polymerization zone (fig. 1, [0148]: build region);
d) emitting and controlling light and transmitting it to the liquid resin through the optically transparent portion for selectively polymerizing the liquid resin in the polymerization zone (fig. 1, [0148]; irradiating build region through build plate to produce a solid polymerized region); and
e) obtaining a three-dimensional article made of the polymerized liquid resin (fig. 1, [0148]; forming three-dimensional object);
f) [treating the obtained three-dimensional article with a non-nucleophilic rinsing solvent for removing the excess liquid resin]; and,
g) [optionally exposing the obtained three-dimensional article with an additional light source for rendering the article non tacky].
DeSimone does not specifically teach the bracketed limitations as presented above, but
Delrot and Truong teach the limitations as follows:
Regarding the liquid resin, Delrot teaches a method for printing a three-dimensional (3D) article (figs. 1A, 1B; page 5 line 14 – page 6 line 22), comprising the steps of: b) providing a volume of liquid resin comprising cyanoacrylate-based monomers, a photoinitiating system, and an acidic inhibitor, wherein the volume of liquid resin is held in a tank (figs 1A, 1B, page 25 lines 6-23: the liquid photoresponsive material 12 is held inside a container 13 that is optically transparent to the wavelength of the light; page 5 line 14 – page 6 line 22: a cyanoacrylate-based formulation comprising a cyanoacrylate prepolymer, an acid stabilizer, a photo-initiator and a synergist, a polymerization inhibitor; page 17 lines 15-19; page 33 line 11-page 34 line 3: e.g., Formulations 1, 2, and 4).
DeSimone and Delrot are both considered to be analogous to the claimed invention because they are in the field of 3D printing using a photoresponsive liquid resin (DeSimone: abstract, [0003]; Delrot: abstract, page 5 lines 27-30). Therefore, it would have been obvious to one of the ordinary skill in the art at the time of filing invention to modify the liquid resin composition comprising a photocurable material of DeSimone with another liquid resin composition comprising cyanoacrylate-based monomers, which are exclusively mono-functional cyanoacrylate monomers, as taught by Delrot in order to obtain known results or a reasonable expectation of successful results of obtaining an additively-manufactured 3D printed article having a reduced tackiness and demanding fewer post-processing step (Delrot: page 5 lines 27-30).
Regarding the post-process of steps e) and f), Truong teaches a post-processing/apparatus that may be integrated into 3D printing system for processing 3D printed object after curing (figs. 1A-1B, [0082-0083, 0093]). Truong teaches e) treating the obtained three-dimensional article with a non-nucleophilic rinsing solvent for removing the excess liquid resin ([0045-0058]: wash liquid, e.g., hydrocarbon, ether, dipolar aprotic, ethyl acetate, hydrofluorocarbon solvents); and, f) optionally exposing the obtained three-dimensional article with an additional light source for rendering the article non tacky ([0066, 0071]: a light source, such as an ultraviolet light source, to further light cure components; here, it is implied that the article would be non-tacky after the exposure as any remaining solvent or liquid resin would be dried or cured, respectively; of note, this step is “optional,” and thus, it is not required).
DeSimone and Truong are both considered to be analogous to the claimed invention because they are in the field of 3D printing (DeSimone: abstract; Truong: [0002-0004, 0093]). Therefore, it would have been obvious to one of ordinary skill in the art at the time of filing invention to modify the 3D printing process/apparatus of DeSimone to be integrated with the post-processing of 3D printing such as washing and further curing an intermediate 3D printed article as taught by Truong in order to obtain known results or a reasonable expectation of successful results of removing excess resin material from the intermediate 3D article and enhancing mechanical properties so as to improve overall quality and aesthetics of a final 3D printed article.
Regarding claim 4, modified DeSimone teaches the printing method according to claim 1, in which the cyanoacrylate-based monomers are selected from 2-methoxyethyl cyanoacrylate, methyl cyanoacrylate, ethyl cyanoacrylate, n-propyl cyanoacrylate, iso-propyl cyanoacrylate or mixtures thereof (Delrot: page 17 lines 15-19; page 33 line 11-page 34 line 3: e.g., Formulation 1).
Regarding claim 5, modified DeSimone teaches the printing method according to claim 1, in which the liquid resin comprises additional photopolymerizable monomers (Delrot: page 15 line 5 – page 16 line 13: such as acrylate, methacrylate, or vinyl-terminated siloxane monomers).
Regarding claim 6, modified DeSimone teaches the printing method according to claim 1, in which the photoinitiator system is an anionic or zwitterionic photoinitiating system (Delrot: page 19 lines 15-24: e.g., acylgermane-based photoinitiator (Ivocerin); page 18 lines 22-27: ferrocene as a synergist that interacts with said photoinitiator; page 33 line 11-page 34 line 3: e.g., Formulations 1-4). Here, the disclosed photoinitiator system is the same as the one of Instant Specification (Instant Specification: [0171-0172, 0176-0177], as published).
Regarding claim 7, modified DeSimone teaches the printing method according to claim 6, in which the anionic or zwitterionic photoinitiating system comprises the combination of a metallocene compound and a radical photoinitiator (Delrot: page 19 lines 15-24: e.g., acylgermane-based photoinitiator (Ivocerin), TPO, Irgacure, DEAP; page 18 lines 22-27: ferrocene as a synergist that interacts with said photoinitiator).
Regarding claim 8, modified DeSimone teaches the printing method according to claim 1, in which the non-nucleophilic solvent is selected from the group consisting of non-basic solvents, non-ionic solvents (or solutions) and mixtures thereof (Truong: [0045- 0058]: wash liquid, e.g., hydrocarbon, ether, dipolar aprotic, ethyl acetate, hydrofluorocarbon solvents).
Regarding claim 9, modified DeSimone teaches the printing method according to claim 1, in which the non-nucleophilic rinsing solvent is selected from the group consisting of hydrocarbon solvents, perfluorinated hydrocarbon solvents, ether solvents, acetate solvents, chlorohydrocarbon solvents, polar aprotic solvents, and mixtures thereof (Truong: [0045- 0058]: wash liquid, e.g., hydrocarbon, ether, dipolar aprotic, ethyl acetate, hydrofluorocarbon solvents).
Regarding claims 10 and 19, modified DeSimone teaches the printing method according to claim 1, in which the step of treating the three-dimensional article with the non-nucleophilic rinsing solvent is carried out (Truong: [0045-0048]), but does not specifically teach that the step is carried out during (1) a period of 10 minutes or less (claim 10), or (2) a period of 4 minutes or less (claim 19).
Here, although modified DeSimone does not specifically teach the specific washing time, through routine optimization and experiment, it would have been obvious to one of ordinary skill in the art that the rinsing is carried out long enough to remove all of the excess resin on a 3D printed article but not too long to destructively dissolve the 3D printed article, e.g., about 3 minutes, so as to remove the excess resin effectively without deteriorating overall quality of a final 3D article.
Regarding claim 11, modified DeSimone teaches the printing method according to claim 1, in which the step of treating the three-dimensional article with the non-nucleophilic rinsing solvent is carried out by dipping the three-dimensional article into the non-nucleophilic solvent (Truong: [0045-0048], [0060]: by spinning the objects to be cleaned in the wash liquid), but does not specifically teach that the step is carried out for a period of 15 seconds or less.
Here, although modified DeSimone does not specifically teach the specific washing time, through routine optimization and experiment, it would have been obvious to one of ordinary skill in the art that the rinsing is carried out long enough to remove the excess resin on a 3D printed article but not too long to destructively dissolve the 3D printed article, e.g., about 10 seconds, so as to remove the excess resin effectively without deteriorating overall quality of a final 3D article.
Regarding claim 12, modified DeSimone teaches the printing method according to claim 1, in which the step of exposing the three-dimensional article to the additional light source is carried out at a wavelength from 380 nm to 470 nm (Truong: [0066, 0071]: a light source, such as an ultraviolet light source, to further light cure components). Here, although the disclosed range (i.e., ultraviolet light of 10 – 400 nm)2 does not anticipate the recited range, the disclosed range overlaps with the recited range between about 380 nm to 400 nm. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) (MPEP 2144.05 I).
Regarding claims 13 and 20, modified DeSimone teaches the printing method according to claim 1, in which the step of exposing the three-dimensional article to the additional light source is carried out (Truong: [0066, 0071]), but does not specifically teach that the step is carried out for (1) a period of 60 seconds or less (claim 13), or (2) for a period from 1 to 30 seconds (claim 20).
Here, modified DeSimone teaches all the claimed limitations as claim 1 recites the step g) as an “optional” step.
Alternatively, although modified DeSimone does not specifically teach the specific exposing time by the additional light source, through routine optimization and experiment, it would have been obvious to one of ordinary skill in the art that the additional light exposure is carried out long enough to cure any remaining non-polymerized or semi-polymerized liquid on a 3D printed article but not too long to delay an overall printing process or to waste energy for unnecessary excessive curing, e.g., about 10 seconds, so as to produce a final 3D article with improved quality and aesthetics as well as in an energy-saving mode.
Regarding claim 16, modified DeSimone teaches the printing method according to claim 1, in which the cyanoacrylate-based monomers are multi-functional cyanoacrylate monomers, hybrid cyanoacrylate monomers or mixtures thereof and optionally mono-functional cyanoacrylate monomers (Delrot: page 17 lines 15-19; page 33 line 11-page 34 line 3: e.g., Formulation 3).
Regarding claim 17, modified DeSimone teaches the printing method according to claim 1, in which the cyanoacrylate-based monomers are selected from 2-methoxyethyl cyanoacrylate, methyl cyanoacrylate or mixtures thereof (Delrot: page 17 lines 15-19; page 33 line 11-page 34 line 3: e.g., Formulation 1).
Regarding claim 18, modified DeSimone teaches the printing method according to claim 1, in which the liquid resin comprises additional photopolymerizable monomers being (meth)acrylate monomers (Delrot: page 15 line 5 – page 16 line 13: such as methacrylate).
Regarding claim 21, modified DeSimone teaches the printing method according to claim 1, further comprising the step of using the obtained three-dimensional article for a period of 1 minutes to 5 years. Although modified DeSimone is silent about how long the obtained 3D article is used, it is implied or at least obvious that the obtained 3D article would be used as long as it is needed.
Claims 22 and 26 are rejected under 35 U.S.C. 103 as being unpatentable over DeSimone (US 20150097315 A1), Delrot (WO 2020094593 A1), and Truong (US 20210354378 A1) as applied to claim 1, and further in view of Uyama (JP 2009030017 A)
Regarding claim 22, modified DeSimone teaches the printing method according to claim 1, but does not specifically teach that the method further comprises the step of treating the 3D article with a dissolving solvent for a time sufficient for dissolving it ranging from 1 to 72 h.
Uyama teaches a method for dissolving a (meth)acrylic acid ester-based polymer comprising a cyano group in a liquid for recycling ([0001, 0003-005, 0016]). Uyama teaches a polymer recycling method, wherein the method comprises dissolving a recovered polymer containing the polymer in a liquid to prepare a polymer solution, and separating the polymer precipitate deposited from the polymer solution ([0006, 0045]), and according to the method, the polymer itself can be recovered to be used as a raw material for processing ([0045]).
In the same field of endeavor of using a cyanoacrylate based material (modified DeSimone: Delrot: page 5 line 14 – page 6 line 22: a cyanoacrylate-based formulation comprising a cyanoacrylate prepolymer; page 17 lines 15-19; page 33 line 11-page 34 line 3: e.g., Formulations 1, 2, and 4; Uyama: [0016]), it would have been obvious to one of ordinary skill in the art at the time of invention to modify the method for printing 3D object of modified DeSimone to further include a step of dissolving the polymer article into a liquid as taught by Uyama in order to obtain known results or a reasonable expectation of successful results of recycling the 3D printed article when it is broken, no longer wanted, or needed for new use to save energy and reduce waste (Uyama: derived from [0003-0006]). Here, although modified DeSimone is silent about how long it takes to dissolve the obtained 3D article with a dissolving solvent, it would be obvious that the obtained 3D article would be dissolved as long as it is dissolved up to a desired level, for example, for a sufficient time to completely dissolve it in the dissolving solvent.
Regarding claim 26, modified DeSimone teaches a method for printing a 3D article the step of:
a) providing a volume of liquid resin comprising mono-functional cyanoacrylate- based monomers, a photoinitiator system and an acidic inhibitor, held in a tank, said tank comprising at least one optically transparent portion (see above, the 103 rejection of claim 1);
b) defining a polymerization zone (id.);
c) emitting and controlling light and transmitting it to the liquid resin through the optically transparent portion for selectively polymerizing the liquid resin in the polymerization zone (id.);
d) obtaining a three-dimensional article made of the polymerized liquid resin (id.);
e) treating the obtained three-dimensional article with a non-nucleophilic rinsing solvent for removing the excess liquid resin (id.);
f) exposing the obtained three-dimensional article with an additional light source for rendering the article non-tacky (id.);
g) using the obtained three-dimensional article for a period of time (see above, the 103 rejection of claim 21); and
h) treating the 3D article with a dissolving solvent for a time sufficient for dissolving it (see above, the 103 rejection of claim 22).
Thus, modified DeSimone teaches all the claimed limitations, and the motivation to combine applied to claims 1, 21, and 22 equally applies here.
Response to Arguments
RE: The 103 rejection based on DeSimone in view of López Maeso and Truong
Applicant's arguments filed on 12/02/2025 have been fully considered but they are not persuasive. It is noted that the applicants have modified the claims with the latest amendment dated 12/02/2025, and wherein the arguments are based on these changes.
The Applicant argues (see pages 7-8 of Remark) that DeSimone in view of López Maeso and Truong does not teach the limitation “providing a volume of liquid resin comprising having a viscosity from 10 mPa·s to 200 mPa·s” as recited in claim 1 because (1) the disclosed viscosity range of DeSimone, ranging from at least 100 cPs, up to 1,000,000 cPs (i.e., mPa·s) or more at 25 degrees C (DeSimone: [0229]), is too broad to teach any valuable range, (2) the disclosed viscosity example of López Maeso, i.e., Example 7: 254 cP or 461 cP (López Maeso: [0269]), is beyond the recited scope.
The Examiner respectfully disagrees with this argument.
DeSimone teaches the limitation “providing a volume of liquid resin comprising having a viscosity from 10 mPa·s to 200 mPa·s” (DeSimone: [0229]: having a viscosity at least 100 cPs, up to 1,000,000 cPs (i.e., mPa·s) or more at 25 degrees C) by having an overlapping range with the recited range between 100 cP and 200 cP. See MPEP 2144.05 I. Although the disclose range is broader than the recited range, it does teach or suggest the minimum viscosity that is required for 3D printing system as disclosed in DeSimone, which is close to the recited viscosity range.
López Maeso does not teach away the photocurable liquid resin comprising mono-functional cyanoacrylate monomers (exclusively for cyanoacrylate monomers) to have the viscosity as recited. The viscosity of a specific example (López Maeso: [0269]: Example 7: 254 cP or 461 cP) does not necessarily mean that the viscosity should be always higher than 254 cP. Rather, López Maeso teaches that the viscosity of a liquid composition can be adjusted to a desired level by using a thickener from an un-thickened cyanoacrylate monomer resin having a viscosity 10 cP (López Maeso: [0105, 0269]), and thus, the liquid composition can have a viscosity at least more than 10 cP.
Moreover, DeSimone discloses that specific end viscosity desired to be achieved will depend on factors such as the rate of fabrication desired, size and shape of the article being fabricated, the presence or absence of increased pressure, etc. (DeSimone: [0229]). Therefore, a viscosity of a liquid resin for 3D printing is a result-effective variable (i.e., a variable which achieves a recognized result, before the determination of the optimum or workable ranges of said variable might be characterized as routine experimentation (MPEP 2144.05 (II)(B)). Moreover, through routine optimization and experiment, it would have been obvious to one of ordinary skill in the art to optimize the viscosity of the liquid resin to be appropriate to 3D printing condition using a thickener or a viscosity modifier, for example, in consideration of fabrication speed.
At last, the instant disclosure does not establish unexpected results over a claimed rage of the viscosity from 10 mPa·s to 200 mPa·s (Instant Specification: Examples 1-5, and Example 7 in part). It simply lists a viscosity of a mono-functional cyanoacrylate monomer resin, which is from 6 to 200 cP in use of a thixotropic agent.
Thereby, after reconsideration, claim 1 remains rejected.
RE: The 103 rejection based on Delrot in view of Truong
Applicant's arguments filed on 12/02/2025 have been fully considered but they are moot. It is noted that the applicants have modified the claims with the latest amendment dated 12/02/2025, and wherein the arguments are based on these changes.
The basis of the applicant’s argument is based upon the changes regarding the limitation “providing a volume of liquid resin comprising having a viscosity from 10 mPa·s to 200 mPa·s”. After further search and reconsideration, the DeSimone reference is applied to the rejection as a primary reference. Thus, when DeSimone’s teaching is modified in view of Delrot and Truong, modified DeSimone does teach/suggest all the claimed limitations and the motivation to combine.
Of note, the disclosed viscosity of Delrot (Delrot: page 14 lines 27-30: between 2,000 and 50,000 cP) does not teach away the liquid resin for a layerwise additive manufacturing to have a desired viscosity range as disclosed by the primary reference DeSimone (DeSimone: [0229]: having a viscosity at least 100 cPs, up to 1,000,000 cPs or more) as a 3D object manufactured by a layerwise manner is held in a build platform rather than being required to float in the liquid resin. Moreover, using the liquid resin comprising mono-functional cyanoacrylate monomers does not necessarily mean that the liquid resin can only have the viscosity as disclosed in Delrot as a viscosity of the liquid resin can be adjusted by adding a viscosity modifier.
Thereby, after reconsideration, claim 1 remains rejected.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Wiese (US 20050215744 A1) teaches a building material and a bath fluid comprising cyanoacrylates for rapid prototyping method (abstract, [0035, 0090]).
Hagiwara (US 5,849,459) teaches a resin composition for stereolithography and a process for producing a three-dimensional object, comprising cyanoacrylate as an energy absorber (abstract, col. 6 lines 21-37).
Robeson (US 20170028618 A1) teaches a method of forming a 3D object in a pool of immiscible liquid (abstract, fig. 1).
Any inquiry concerning this communication or earlier communications from the examiner should be directed to INJA SONG whose telephone number is (571)270-1605. The examiner can normally be reached Mon. - Fri. 8 AM - 5 PM.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Xiao (Sam) Zhao can be reached on (571)270-5343. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/INJA SONG/Examiner, Art Unit 1744
1 Ultraviolet radiation is electromagnetic radiation of wavelengths of 10-400 nm (see https://en.wikipedia.org/wiki/Ultraviolet).
2 Ultraviolet radiation is electromagnetic radiation of wavelengths of 10-400 nm (see https://en.wikipedia.org/wiki/Ultraviolet).