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 .
Election/Restrictions
Claims 11-15 and 21-24 are withdrawn from further consideration pursuant to 37 CFR 1.142(b), as being drawn to a nonelected inventions, there being no allowable generic or linking claim. Applicant timely traversed the restriction (election) requirement in the reply filed on 5/20/2025.
Response to Amendment
The amendment filed on 12/1/2025 has been entered. Claim(s) 1, 6-7 and 21 is/are currently amended. Claim(s) 16-20 has/have been cancelled. Claim(s) 1-15 and 21-24 is/are pending with claim(s) 11-15 and 21-24 withdrawn from consideration. Claim(s) 1-10 is/are under examination in this office action.
Response to Arguments
Applicant's argument filed on 12/1/2025, with respect to 112(b) rejection has been fully considered and is persuasive. The 112(b) rejection is withdrawn.
Applicant's argument filed on 12/1/2025, with respect to 103 rejection has been fully considered but is not persuasive.
Applicant argued that a ratio of a first complex (formed by the transition metal ion and the at least one transition metal ion coordination site on the ligand (e.g., Zn-PVA)) to a second complex (formed by the transition metal ion and water (e.g., Zn-H2O)) in the claimed range facilitates fast self-healing of the hydrogel polymer. Neither Hassan nor Mitsuo forms a self-healing hydrogel polymer network - therefore nothing in the cited art recognizes any self-healing ability.
In response, as stated in the 103 rejection, the recited self-healing is a property of the PVA/metal ion hydrogel product. Since the prior art teaches the same product as the current invention, the recited property is expected to be present. See MPEP 2112.01. In addition, according to the applicant, such ultra-fast self-healing polymers based on Zn-PVA complexes are created by using a freezing-thawing method described in C. Hassan et al., "Structure and Applications of poly(vinyl alcohol) hydrogels produced by conventional crosslinking or by freezing/thawing methods," Adv. Polym. Sci. 153, 37 (2000)). Since the applicant uses the same method for preparing the hydrogel as the prior art, the resulting product is expected to have the same properties.
Applicant argued that the fact that a certain result or characteristic may occur or be present in the prior art is not sufficient to establish the inherency of that result or characteristic. Here there is no disclosure of the relationship between the variable (a ratio of a first complex of the transition metal ion and the transition metal ion coordination site and a second complex of the transition metal ion and water that is greater than or equal to about 1:1 and less than or equal to about 5:1) and the result (self- healing properties and more specifically rates of self-healing) in the prior art. Because the cited art does not recognize that the variable affects the relevant property or result, then the variable is not result-effective and the claims are non-obvious. For all these reasons, the Examiner's reconsideration and allowance of amended independent claim 1 and its dependent claims is earnestly solicited.
In response, applicant seems to argue that the claimed ratio is critical and gives unexpected result. According to the applicant, this ratio is based on the assumption that Zn ion has a coordination number of 4, Zn-PVA complex, that is, [Zn2+(CH2CHO−)4]2− has a molar ratio of 10:2.5. In other words, one mole of zinc ion could form a complex with 4 moles of hydroxyl group in PVA [0086 spec.]. Since the prior art teaches the same Zn-PVA complex as stated in the 103 rejection, this ratio is expected to be present. Whether unexpected results are the result of unexpectedly improved results or a property not taught by the prior art, the “objective evidence of nonobviousness must be commensurate in scope with the claims which the evidence is offered to support." In re Clemens, 622 F.2d 1029, 1036, 206 USPQ 289, 296 (CCPA 1980); MPEP 716.02(d). In the instant case, the examples are not commensurate in scope with the claims. For instance, claim 1 recites a PVA and a transitional metal ion, which covers unlimited variety of PVA polymers and wide variety of transitional metal ions. However, the specification only employs one PVA-Zn combination [0133 spec.]. It is not known if other PVA-transitional metal ions combination will give the same result. The claim does not limit any concentrations of the PVA, Zn, and water. Therefore, criticality cannot be based on the concentrations of the PVA, Zn, and water. Since the examples are not reasonably commensurate with the full scope of claimed materials, and the Applicant has not provided any additional information that would allow one skilled in the art to extend the results associated with the data to the full scope of the claim, the examples cannot be relied upon to establish non-obviousness of the claimed invention.
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 text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
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.
Claim(s) 1-10 is/are rejected under 35 U.S.C. 103 as being unpatentable over Hassan et al (“Structure and Applications of Poly(vinyl alcohol) Hydrogels Produced by Conventional Crosslinking or by Freezing/Thawing Methods”, Advances in Polymer Science, Vol. 153, 2000) in view of Mitsuo et al (JP 2007031601 A, machine translation is referenced herein).
Regarding claims 1 and 2, Hassan teaches preparing polyvinyl alcohol (PVA) hydrogels by freezing/thawing method: aqueous solutions of between 2.5 and 15 wt % PVA were frozen at -20 °C and thawed back to room temperature [P45 section 4]. PVA hydrogels prepared by freezing and thawing techniques were used as adhesives [P47 last para.].
Hassan does not teach a transition metal ion distributed in the PVA network.
In the same field of endeavor, Mitsuo teaches an adhesive hydrogel comprising PVA and a metal salt such as zinc nitrate [0005, 0034]. Such metal salt helps improving water retention, flexibility, adhesiveness, and gel strength of the hydrogel [0034].
It would have been obvious to one of ordinary skill in the art at the time of filing to add a metal salt such as zinc nitrate in Hassan’s PVA hydrogel for the benefits of improving water retention, flexibility, adhesiveness, and gel strength of the hydrogel.
The PVA hydrogel reads on the claimed hydrogel polymer network. The recited “defines one or more ligands having a transition metal ion coordination site comprising hydroxy groups” is a property of the PVA hydrogel and is necessarily present.
The zinc nitrate reads on the claimed transition metal ion. The recited “capable of interacting with the transition metal ion coordination site via a reversible coordination bond” is a property of the metal ion and is necessarily present.
The recited “the polymer network is capable of self-healing a mechanical crack or cut in less than or equal to about 30 minutes at ambient conditions” is a property of the PVA/metal ion hydrogel product. “Products of identical chemical composition cannot have mutually exclusive properties." A chemical composition and its properties are inseparable. Therefore, if the prior art teaches the identical chemical structure, the properties applicant discloses and/or claims are necessarily present. “When the PTO shows a sound basis for believing that the products of the applicant and the prior art are the same, the applicant has the burden of showing that they are not.” In re Spada, 911 F.2d 705, 709, 15 USPQ2d 1655, 1658 (Fed. Cir. 1990)). See MPEP 2112.01. Since the prior art teaches the same product as the current invention, the recited property is expected to be present.
In addition, according to the applicant, such ultra-fast self-healing polymers based on Zn-PVA complexes are created by using a freezing-thawing method described in C. Hassan et al., "Structure and Applications of poly(vinyl alcohol) hydrogels produced by conventional crosslinking or by freezing/thawing methods," Adv. Polym. Sci. 153, 37 (2000)). Since the applicant uses the same method for preparing the hydrogel as the prior art, the resulting product is expected to have the same properties.
Water is necessarily present in a hydrogel. Mitsuo expressively teaches that the PVA hydrogel comprises water [0003]. A first complex of the transition metal ion (i.e., zinc nitrate) and the transition metal ion coordination site (i.e., the OH group in PVA) is necessarily present because of the presence of PVA and zinc nitrate. A second complex of the transition metal ion and water is also necessarily present because of the presence of zinc nitrate and water.
Applicant teaches 10 wt% of PVA water solution containing zinc nitrate hexahydrate with molar ratios (NPvA:Nzn) of 10:1, 10:1.5, 10:2, 10:2.5, and 10:3 [0133 spec.]. Mitsuo teaches the concentration of the solution containing the PVA-based resin (A) and the metal salt (B) is preferably 10 to 80% (by weight) [0036]; the water content is 20-90 wt% in the hydrogel [P22, first para.]. Mitsuo teaches similar ratio of OH groups in PVA to metal salts as stated above. Thus, the prior art teaches substantially identical hydrogel composition. Therefore, the recited “a ratio of the first complex to the second complex is greater than or equal to about 1:1 and less than or equal to about 5:1” is expected to be present.
Regarding claim 3, the recited “the polymer network is capable of self-healing a mechanical crack or cut in less than or equal to about 1 minute at ambient conditions” is a property of the product and is expected to be present in the prior art product as stated above.
Regarding claim 4, Hassan teaches that crosslinking agents can be used for PVA hydrogel [P39 section 2]. Mitsuo also teaches using crosslinking agents in PVA based hydrogels [0002].
Regarding claim 5, the recited “the hydrogel polymer network has a Young's modulus (E) of greater than or equal to about 0.01 kPa to less than or equal to 100 kPa” is a property of the product and is expected to be present in the prior art product as stated above.
Regarding claim 6, Mitsuo teaches that the content (by weight) of the metal salt (B) relative to the PVA-based resin (A) is not particularly limited, but is 1 to 250% [0035]. Hassan teaches a number average molecular weight of PVA of 77,000 [P38 section 1], which should have about 1750 vinyl alcohol unit (MW=44) or 1750 OH groups. Assuming the metal salt is zinc nitrate with molecular weight of 189.38, the ratio of moles of hydroxy groups in PVA to moles of zinc ions is about 1.72:1 (or 8.6:5) to about 430:1, as calculated by the examiner, overlapping the claimed range of greater than or equal to about 10:5 to less than or equal to about 20:1. A prima facie case of obviousness exists where the claimed ranges overlap ranges disclosed by the prior art (MPEP 2144.05.I).
Regarding claim 7, water is necessarily present in a hydrogel. Mitsuo expressively teaches that the PVA hydrogel comprises water [0003]. A first complex of the transition metal ion (i.e., zinc nitrate) and the transition metal ion coordination site (i.e., the OH group in PVA) is necessarily present because of the presence of PVA and zinc nitrate. A second complex of the transition metal ion and water is also necessarily present because of the presence of zinc nitrate and water.
Applicant teaches 10 wt% of PVA water solution containing zinc nitrate hexahydrate with molar ratios (NPvA:Nzn) of 10:1, 10:1.5, 10:2, 10:2.5, and 10:3 [0133 spec.]. Mitsuo teaches the concentration of the solution containing the PVA-based resin (A) and the metal salt (B) is preferably 10 to 80% (by weight) [0036]; the water content is 20-90 wt% in the hydrogel [P22, first para.]. Mitsuo teaches similar ratio of OH groups in PVA to metal salts as stated above. Thus, the prior art teaches substantially identical hydrogel composition. Therefore, the recited “a ratio of the first complex to the second complex is greater than or equal to about 1:1 and less than or equal to about 4:1” is expected to be present.
Regarding claim 8, the recited “capable of an elongation under strain of greater than or equal to about 100% after self-healing of the mechanical crack or cut” is a property of the product and is expected to be present in the prior art product as stated above.
Regarding claim 9, the recited “having a transmissivity of greater than or equal to about 70% for electromagnetic radiation wavelengths of greater than or equal to about 380 nm to less than or equal to about 780 nm” is a property of the product and is expected to be present in the prior art product as stated above.
Regarding claim 10, the recited “having a sheet resistance of less than or equal to about 10 Ω/square” is a property of the product and is expected to be present in the prior art product as stated above.
Conclusion
THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any extension fee pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to JIANGTIAN XU whose telephone number is (571)270-1621. The examiner can normally be reached Monday-Thursday.
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/JIANGTIAN XU/Primary Examiner, Art Unit 1762