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 .
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 December 04, 2025 has been entered.
Response to Amendment
The Office Action is in response to the Amendment and Remarks filed on December 04, 2025. Claims 1-2, and 4-9 are pending in the application. Claim 3 was cancelled. Claims 1 and 8 were amended, wherein support for the amendments can be found in the claims and Specification as originally filed.
The previous 35 USC 112 rejections of Claims 8 and 9 are withdrawn in light of Applicant's amendment.
Priority
Acknowledgment is made of applicant's claim for foreign priority based on an application filed in China on January 22, 2022. It is noted, however, that applicant has not filed a certified copy of the Foreign Priority Application as required by 37 CFR 1.55.
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.
Claims 1-2, and 4-7 are rejected under 35 U.S.C. 103 as being unpatentable over Liu et al., (US 2014/0323610 A1; hereafter as “Liu ‘610”) in view of Hong et al., (US 2015/0302948 A1; hereafter as “Hong”) and Zhou et al., (CN105968444 (A); English translation incorporated herein; hereafter as “Zhou”) and in further view of Zhang et al. (WO 2018/166477A1; English translation incorporated herein; hereafter as “Zhang ‘477”).
Regarding Claims 1-2, and 4-7, Liu ‘610 teaches a method for preparing graphene oxide and rubber composite materials [Abstract], corresponding to the graphene masterbatch of Claim 1. Liu ‘610 further teaches:
Graphene oxide is dispersed in deionized water [Example 2; Paragraph 0036] and then a surfactant is mixed with graphene oxide [Example 2; Paragraph 0036], corresponding to the steps of (S1) mixing a surfactant with deionized water and adding graphene oxide to obtain a graphene oxide aqueous dispersion of Claim 1, (S2) mixing a surface modifier to said S1 dispersion of Claim 1;
Natural rubber latex [Paragraph 0027], corresponding to the natural rubber latex of Claim 1;
Adding hydrogen chloride to carry out flocculation [Example 2; Paragraph 0036], corresponding to the steps of mixing to obtain a mixed emulsion, adding a flocculant to the mixed emulsion and co-precipitating a crude rubber compound of Claim 1;
Washing with water and then drying the said crude rubber compound [Example 2; Paragraph 0036], corresponding to the steps of washing and drying to obtain the graphene masterbatch of Claim 1;
a graphene oxide and rubber composite formulation with 2.5% by weight of graphene oxide [Example 2; Paragraph 0036] (20g graphene oxide / (20g graphene oxide + 100g water + 380g white carbon black + 190g bis[y-(triethoxysilyl)propyl]disulfide + 125g styrene-butadiene rubber latex) ) = 20g/815g = 2.5% by weight graphene oxide), corresponding to wherein the graphene masterbatch comprises 1-20% by weight of the graphene oxide of Claim 5;
wherein the flocculent is hydrochloric acid [Claim 5], reading on wherein the flocculant is hydrochloride solution of Claim 6; and
the styrene-butadiene rubber latex having a solid content of 10-80% [Claim 4], corresponding to wherein the natural rubber latex is 10-40 wt. % of Claim 7.
Liu ‘610 further teaches surfactant [Paragraph 0028], corresponding to the surface modifier of Claim 1.
However, Liu ‘610 is silent to adjusting the pH to 10 of Claim 1 and the anionic surfactants of Claims 1 and 2.
Nevertheless, Hong teaches graphene oxide and nanoparticle composite materials [Paragraph 0004]. Hong further teaches anionic surfactants [Paragraph 0076], corresponding to the anionic surfactants of Claim 1, including alkyl benzene sulfonates [Paragraph 0076], reading on the alkyl benzene sulfonates of Claim 2. Hong also teaches that surfactants with a net negative charge require a solvent pH greater than 5 [Paragraph 0055]. Hong also teaches that anionic surfactants can aid in attaching said surfactant to magnetically sensitive nanoparticles [Paragraph 0070].
Liu ‘610 and Hong are considered to be analogous art as the claimed invention, as all are in the same field of graphene oxide composites for vehicle tires.
Therefore, it would be obvious to adjust the pH as taught by Hong. This modification would optimize the environment for anionic surfactant functionality, which Hong also teaches, since such surfactants prefer solvents with a pH greater than about 5. It would also be obvious that the pH range taught by Hong encompasses the pH of 10.
Liu ‘610 is silent to the activator of Claim 1 and the catalyst of Claims 1 and 4.
Nevertheless, Zhou teaches tough rubber compositions [Abstract]. Zhou further teaches 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride [Abstract], which the instant Specification discloses is an activator [Page 4, Paragraph 2]. Zhou also teaches N-hydroxysuccinimide [Abstract], which the instant Specification discloses is a catalyst [Page 4, Paragraph 2]. Zhou also teaches their rubber material composition is tough, has good wear resistance and a long service life [Abstract].
Liu ‘610 and Zhou are considered to be analogous art as the claimed invention, as all are in the same field of tough rubber composites.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to add the 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide as taught by Zhou. This modification would expectedly toughen the tire composition and provide good wear resistance and a long service life.
Liu ‘610 is silent to the graphene sheets of Claim 1, and wherein the surface modifier is L-cysteine and is adopted to perform secondary modification on the graphene oxide of Claim 1.
Nevertheless, Zhang ‘477 teaches a modified fiber product comprising graphene oxide, wherein said product may comprise L-cysteine [Claim 24; Paragraph 0074], corresponding to the L-cysteine of Claim 1. Zhang ‘477 further teaches L-cysteine may be used as a reducing agent [¶ 0071-0074], corresponding to performing secondary modification on the graphene oxide of Claim 1.
Zhang ‘477 teaches a modified fiber product comprising graphene oxide and L-cysteine [Claim 24; Paragraph 0074], wherein graphene may be in the form of graphene sheets [Paragraph 0080], corresponding to the graphene sheets of Claim 1. Zhang ‘477 further teaches graphene sheets increase the amount of graphene-like substances attached to the fiber [Paragraph 0080].
Liu ‘610 and Zhang ‘477 are considered to be analogous art as the claimed invention, as all are in the same field of graphene oxide dispersions.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to graphene sheets and L-cysteine of Zhang ‘477 to the graphene oxide composite material of Liu ‘610.
Liu ‘610 is silent on the limitations “such that the anionic surfactant is employed to perform surface activation and modification on graphene components to reduce stacking of graphene sheets” of Claim 1 and “wherein modified graphene oxide particles and rubber particles in natural rubber latex form bound particles due to an electrostatic attraction of positive ions on a protein-phospholipid film on a surface of the rubber particles in natural rubber latex to keep stable” of Claim 1.
However, the ability for surfactants to perform surface activation and the formation of bound particles due to an electrostatic attraction of positive ions on a protein-phospholipid film on a surface of the rubber particles in natural rubber latex to keep stable is a function of the method of preparing the graphene by an aqueous phase and mixing this emulsion with natural rubber. Liu ‘610 teaches a substantially similar method for preparing a graphene masterbatch including the step of adding modified graphene oxide aqueous dispersion in an emulsion mixed with natural rubber as set forth above. Therefore, the surface activation and formation of bound particles due to an electrostatic attraction of positive ions on a protein-phospholipid film on a surface of the rubber particles in natural rubber latex to keep stable is expected. Case law has held that claiming of a new use, new function or unknown property which is inherently present in the prior art does not necessarily make the claim patentable. In re Best, 562 F.2d 1252, 1254, 195 USPQ 430, 433 (CCPA 1977). The courts have stated that 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. In re Spada, 911 F.2d 705, 15 USPQ2d 1655, (Fed. Cir. 1990). See also In re Best, 562 F.2d 1252, 195 USPQ 430, (CCPA 1977). "Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established." Further, if it is the applicant's position that this would not be the case, evidence would need to be provided to support the applicant's position. In the alternative that the above disclosure is insufficient to anticipate the above listed claims, it would have nonetheless been obvious to the skilled artisan to produce the claimed method, as the reference teaches each of the claimed ingredients (graphene oxide and natural rubber) in the same amounts and for the same utility (tires).
While Liu ‘610, Hong, Zhou, and Zhang ‘477 may be silent to the exact order of performing certain steps, case law has held that selection of any order of performing process steps is prima facie obvious in the absence of new or unexpected results (See MPEP 2144.04.IV.C., In re Burhans, 154 F.2d 690, 69 USPQ 330 (CCPA 1946); and In re Gibson, 39 F.2d 975, 5 USPQ 230 (CCPA 1930)).
Claims 8 and 9 are rejected under 35 U.S.C. 103 as being unpatentable over Liu et al., (US 2014/0323610 A1; hereafter as “Liu ‘610”) in view of Hong et al., (US 2015/0302948 A1; hereafter as “Hong”) and Zhou et al., (CN105968444 (A); English translation incorporated herein; hereafter as “Zhou”) and in further view of Zhang et al. (WO 2018/166477A1; English translation incorporated herein; hereafter as “Zhang ‘477”), and in further view of Liu et al., (CN104693546A; English translation incorporated herewith; hereafter as “Liu ‘546”), Chen et al., (WO2021247153A2; hereafter as “Chen”), Luan et al., (CN110358156 A; English translation incorporated herewith; hereafter as “Luan”), and Zhang et al., (CN105037830A; English translation incorporated herewith; hereafter as “Zhang ‘830”).
Regarding Claim 8, Liu ‘610, Hong, Zhou, and Zhang ‘477 teach the method for preparing the graphene masterbatch as set forth above for Claim 1 and incorporated herein by reference.
Liu ‘610 teaches a method for preparing graphene oxide and rubber composite materials into tires [Abstract, Paragraph 0007], corresponding to the claimed method for making a tire. Liu ‘610 further teaches:
Mixing the graphene oxide and rubber composite with other components in a [Paragraph 0037], corresponding to the claimed subjecting the graphene masterbatch and natural rubber block to mixing to produce a rubber mixture;
Adding accelerator TT1 [Paragraph 0037], corresponding to the claimed vulcanization accelerator;
Adding anti-ager 401 ONA [Paragraph 0037], corresponding to the claimed anti-aging agent;
Adding RD2 [Paragraph 0037], corresponding to the claimed antioxidant;
Adding zinc oxide [Paragraph 0037], corresponding to the claimed zinc oxide;
Mixing the rubber mixture in a two roll mixing mill [Paragraph 0037], corresponding to mixing the rubber mixture in an open mill; and
Adding sulfur [Paragraph 0037], corresponding to the claimed sulfur.
However, Liu ‘610 is silent to:
Plastication in an internal mixer;
Adding carbon black;
wherein the vulcanization accelerator is N-(oxydiethylene)-2-benzothiazole sulfenamide (NOBS);
wherein the anti-aging agent is N-Isopropyl-N'-phenyl-1,4-phenylenediamine;
wherein the antioxidant is poly(1,2-dihydro-2,2,4-trimethylquinoline;
cooling the rubber mixture to room temperature;
re-milling the rubber mixture on the open mill;
transferring the rubber mixture to a tire mold; and
vulcanization.
Regarding the internal mixer, carbon black, NOBS, N-Isopropyl-N'-phenyl-1,4-phenylenediamine, poly(1,2-dihydro-2,2,4-trimethylquinoline), and vulcanization of Claim 8, Liu ‘546 teaches a method for making high-performance graphene oxide rubber composites[Abstract]. Liu ‘546 further teaches:
Carbon black [Paragraph 0214 and 0217];
NOBS as an accelerator [Paragraph 0214];
p-phenylenediamine and quinoline as antioxidants in said composite [Paragraph 0031];
mixing the components of said composite in an internal mixer [Paragraph 0035];
and subjecting the mixed components to vulcanization [Paragraph 0035].
Liu ‘546 also teaches their method results in tires with high wear resistance, high strength, low heat generation, and anti-slip properties [Paragraph 0007].
Liu ‘610 and Liu ‘546 are considered to be analogous art as the claimed invention, as all are in the same field of graphene oxide rubber composites for vehicle tires.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to add the carbon black, NOBS, p-phenylenediamine and quinoline to the internal mixer and then vulcanization as taught by Liu ‘546. This modification would expectedly make tires with high wear resistance, high strength, low heat generation, and anti-slip properties, and thereby arriving at the claimed invention.
Regarding the poly(1,2-dihydro-2,2,4-trimethylquinoline) and N-Isopropyl-N'-phenyl-1,4-phenylenediamine of Claim 8, Chen teaches graphene oxide elastomer compositions for tires [Abstract; Paragraph 0002]. Chen further teaches 1,2-dihydro-2,2,4-trimethylquinoline and N-isopropyl- N'-phenyl-p-phenylenediamine as antioxidants in said compositions [Paragraph 0137]. Chen also teaches their composition allows for less fillers to be used while achieving desirable mechanical properties [Paragraph 0004].
Liu ‘610 and Chen are considered to be analogous art as the claimed invention, as all are in the same field of graphene oxide rubber composites for vehicle tires with enhanced mechanical properties.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to add the 1,2-dihydro-2,2,4-trimethylquinoline and N-isopropyl- N'-phenyl-p-phenylenediamine as taught by Chen. This modification would expectedly improve the tire composition by allowing for less fillers to be used while improving mechanical properties, and thereby arriving at the claimed invention.
Regarding cooling the rubber mixture and vulcanization of Claim 8, Luan teaches rubber tire tread compositions [Abstract]. Luan further teaches said cooling the rubber composition to 21° C to 25° C [Paragraph 0021] and vulcanization of said composition [Paragraph 0026]. Luan also teaches their rubber composition results in tires with low rolling resistance and compression heat generation while maintaining wet skid resistance and has excellent wear resistance [Paragraph 0008].
Liu ‘610 and Luan are considered to be analogous art as the claimed invention, as all are in the same field of graphene oxide polymer composites for vehicle tires.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to cool and vulcanize the rubber composition as taught by Luan. This modification would be expected to improve tire qualities like rolling, skid and wear resistance, thereby improving the final product and arriving at the claimed invention.
Regarding the open milling of Claim 8, Zhang ‘830 teaches masterbatch formulations for tires [Abstract]. Zhang ‘830 also teaches open milling of said masterbatch formulations [Paragraph 0018]. Zhang ‘830 further teaches use of carbon black [Paragraph 0008], and NOBS as an accelerator [Paragraph 0020] in said masterbatch. Zhang ‘830 also teaches their tire formulation results in tires with reduced compression fatigue heat generation and improve mechanical properties [Paragraph 0007].
Liu ‘610 and Zhang ‘830 are considered to be analogous art as the claimed invention, as all are in the same field of high-strength tires made from graphene oxide rubber masterbatches including carbon black, NOBS and open milling.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to add the carbon black and NOBS as taught by Zhang ‘830 to the tire composite material of Liu ‘610. This modification would allow the tires of Liu ‘610 to have reduced compression fatigue heat generation and improve their mechanical properties, thereby improving the final product and arriving at the claimed invention.
Regarding the tire mold of Claim 8, Hong teaches graphene oxide and nanoparticle composite materials [Paragraph 0004]. Hong further teaches said composite material can be subjected to molding process to make things such as vehicle tires [Paragraphs 0004 and 0140] and provide enhanced mechanical properties in many diverse applications [Abstract; Paragraph 0139].
Liu ‘610 and Hong are considered to be analogous art as the claimed invention, as all are in the same field of graphene oxide composites for vehicle tires.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to use molds for diverse applications such as vehicle tires as taught by Hong. This modification would enable fabricating tires with enhanced mechanical properties, improving the final product and thereby arriving at the claimed product.
While Liu ‘610, Liu ‘546, Chen, Luan, Zhang ‘830, Zhang ‘477 and Hong may be silent to the exact order of performing certain steps, case law has held that selection of any order of performing process steps is prima facie obvious in the absence of new or unexpected results (See MPEP 2144.04.IV.C., In re Burhans, 154 F.2d 690, 69 USPQ 330 (CCPA 1946); and In re Gibson, 39 F.2d 975, 5 USPQ 230 (CCPA 1930)).
Regarding Claim 9, however, Liu ‘610 is silent to the elements of Claim 9:
wherein a mass ratio of the graphene masterbatch to the natural rubber block to the vulcanization accelerator to the anti-aging agent to the antioxidant to the zinc oxide to the sulfur to the carbon black is (10-100): (50-87.5): 2: 1: 1: 5: 2: 60.
Nevertheless, Luan further teaches: (see calculations in the Table 1 below)
40-70 parts filler by weight, including carbon black and graphene oxide [Paragraph 0067], which is equivalent to 26-56 wt. %, which overlaps the claimed range of 10-100 parts of graphene oxide masterbatch (5.8-59 wt. %) and 60 parts of carbon black (23-74 wt. %);
50-95 parts natural rubber by weight [Paragraph 0067], which is equivalent to 37-68 wt. %, which overlaps the claimed range of 50-87.5 parts of natural rubber;
0.8-3 parts accelerator by weight [Paragraph 0067], which is equivalent to 0.4-3.1 wt. %, which overlaps the claimed range of 2 parts of vulcanization accelerator;
1.5-5 parts antioxidant by weight [Paragraph 0067], which is equivalent to 0.8-5 wt. %, which overlaps the claimed range of 1 part of anti-aging agent;
0-0.6 parts anti-reversion agent by weight [Paragraph 0067], which is equivalent to 0-0.6 wt. %, which overlaps the claimed range of 1 part of antioxidant;
2-6 parts zinc oxide by weight [Paragraph 0067], which is equivalent to 1-6 wt. %, which overlaps the claimed range of 5 parts of zinc oxide; and
0.6-2 parts sulfur by weight [Paragraph 0067], which is equivalent to 0.3-2.1 wt. %, which overlaps the claimed range of 2 parts of sulfur.
Luan also teaches their rubber composition results in tires with low rolling resistance and compression heat generation while maintaining wet skid resistance and has excellent wear resistance [Paragraph 0008].
Therefore, it would be obvious to one of ordinary skill in the art before the effective filing date that the filler, which includes carbon black and graphene oxide, of Luan, correspond to the claimed carbon black and graphene oxide.
Furthermore, it would be obvious the claimed minimum amount of graphene oxide and carbon black is equivalent to 41 wt. % (min. amt. = 100* (min. amt. graphene oxide + min. amt. carbon black) / (max. amt. of all other components + min. amt. graphene oxide + min. amt. carbon black) = 70/171 = 41%), and the claimed maximum amount is equivalent to 94 wt. % (max. amt. = 100* (max. amt. graphene oxide + max. amt. carbon black) / (min. amt. of all other components + max. amt. graphene oxide + max. amt. carbon black) = 160/171 = 94%). And it would be obvious that this claimed range of 41-94 wt. % graphene oxide and carbon black overlaps the range of 26-56 wt. % taught in the prior art by Luan.
Similarly, the claimed ranges of the natural rubber block to the vulcanization accelerator to the anti-aging agent to the antioxidant to the zinc oxide to the sulfur to the carbon black overlaps the respective ranges taught in Luan. By choosing the overlapping portion of the range taught in the prior art and the range claimed by the applicants, it has been held to be a prima facie case of obviousness. See MPEP section 2144.05(I). It would have also been obvious to one having ordinary skill in the art to tune the natural rubber, vulcanization accelerator, anti-aging agent, antioxidant, zinc oxide, sulfur and carbon black of Liu ‘610 with the ranges taught in Luan through routine optimization within prior art conditions or through routine experimentation.
Claims 1-2, and 4-7 are rejected under 35 U.S.C. 103 as being unpatentable over Luan et al., (CN110358156 A; English translation incorporated herewith; hereafter as “Luan”) in view of Hong et al., (US 2015/0302948 A1; hereafter as “Hong”); Liu et al., (US 2014/0323610 A1; hereafter as “Liu ‘610”), Zhou et al., (CN105968444 (A); English translation incorporated herein; hereafter as “Zhou”) and ”) and Zhang et al. (WO 2018/166477A1; English translation incorporated herein; hereafter as “Zhang ‘477”).
Luan teaches methods for preparing rubber tire tread compositions with excellent wear resistance [Abstract; Paragraph 0008]. Luan further teaches:
a graphene masterbatch [Paragraphs 0067-0094], corresponding to the graphene masterbatch of Claim 1;
filler, including graphene oxide [Paragraphs 0013 and 0072], corresponding to the graphene oxide of Claim 1;
silane coupling agent KH-5503, 3-amino propyl trimethyoxy silane, [Paragraph 0012 and 0072], corresponding to the surface modifier of Claim 1;
zinc oxide as an active agent [Paragraph 0042 and 0072], corresponding to the activator of Claim 1;
50-95 parts by weight of natural rubber [Paragraphs 0067 and 0072], which is equivalent to 26-56 wt. % of natural rubber4, corresponding to the natural rubber latex of Claim 1, and overlapping with the claimed range of 50-87.5 parts of natural rubber latex, which is equivalent to 29-51 wt. %5 of natural rubber latex of Claim 7;
mixing and blending to obtain a masterbatch [Paragraph 0072], corresponding to mixing to obtain a mixed emulsion of Claim 1.
However, Luan is silent to:
adjusting the pH to 10 of Claim 1;
anionic surfactants of Claims 1 and 2;
wherein the anionic surfactant is employed to perform surface activation and modification on graphene components to reduce stacking of graphene sheets of Claim 1;
activator of Claim 1;
catalyst of Claims 1 and 4;
wherein the surface modifier is L-cysteine and is adopted to perform secondary modification on the graphene oxide of Claim 1;
flocculant of Claim 1 and 6;
co-precipitating the crude rubber compound of Claim 1;
washing and drying to obtain the graphene masterbatch of Claim 1; and
1-20% by weight of the graphene oxide of Claim 5. Regarding adjusting the pH to 10 of Claim 1 and the anionic surfactants of Claims 1 and 2, Hong teaches graphene oxide and nanoparticle composite materials [Paragraph 0004]. Hong further teaches anionic surfactants [Paragraph 0076], corresponding to the anionic surfactants of Claim 1, including alkyl benzene sulfonates [Paragraph 0076], reading on the alkyl benzene sulfonates of Claim 2. Hong also teaches that surfactants with a net negative charge require a solvent pH greater than 5 [Paragraph 0055]. Hong also teaches that anionic surfactants can aid in attaching said surfactant to magnetically sensitive nanoparticles [Paragraph 0070].
Luan and Hong are considered to be analogous art as the claimed invention, as all are in the same field of graphene oxide composites for vehicle tires.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to add the anionic surfactant, such as alkyl benzene sulfonates, as taught by Hong. This modification would aid in attaching said surfactant to magnetically sensitive nanoparticles, and thereby arriving at the claimed invention.
Furthermore, it would also be obvious to adjust the pH as taught by Hong. This modification would optimize the environment for anionic surfactant functionality, which Hong also teaches, since such surfactants prefer solvents with a pH greater than about 5. It would also be obvious that the pH range taught by Hong corresponds with the claim pH of 10.
Regarding the graphene sheets of Claim 1, and wherein the surface modifier is L-cysteine and is adopted to perform secondary modification on the graphene oxide of Claim 1, Zhang ‘477 teaches a modified fiber product comprising graphene oxide, wherein said product may comprise L-cysteine [Claim 24; Paragraph 0074], corresponding to the L-cysteine of Claim 1. Zhang ‘477 further teaches L-cysteine may be used as a reducing agent [¶ 0071-0074], corresponding to performing secondary modification on the graphene oxide of Claim 1.
Zhang ‘477 teaches a modified fiber product comprising graphene oxide and L-cysteine [Claim 24; Paragraph 0074], wherein graphene may be in the form of graphene sheets [Paragraph 0080], corresponding to the graphene sheets of Claim 1. Zhang ‘477 further teaches graphene sheets increase the amount of graphene-like substances attached to the fiber [Paragraph 0080].
Luan and Zhang ‘477 are considered to be analogous art as the claimed invention, as all are in the same field of graphene oxide compositions.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to graphene sheets and L-cysteine of Zhang ‘477 to the graphene oxide composite material of Luan.
Regarding, the activator of Claim 1 and the catalyst of Claims 1 and 4, Zhou teaches tough rubber compositions [Abstract]. Zhou further teaches 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride [Abstract], which the instant Specification discloses is an activator [Page 4, Paragraph 2]. Zhou also teaches N-hydroxysuccinimide [Abstract], which the instant Specification discloses is a catalyst [Page 4, Paragraph 2]. Zhou also teaches their rubber material composition is tough, has good wear resistance and a long service life [Abstract].
Luan and Zhou are considered to be analogous art as the claimed invention, as all are in the same field of tough rubber composites.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to add the 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide as taught by Zhou. This modification would expectedly toughen the tire composition and provide good wear resistance and a long service life.
Regarding the flocculant of Claim 1 and 6, co-precipitating the crude rubber compound of Claim 1; and washing and drying to obtain the graphene masterbatch of Claim 1, Liu ‘610 teaches:
Adding hydrogen chloride to carry out flocculation [Example 2; Paragraph 0036], corresponding to the steps of mixing to obtain a mixed emulsion, adding a flocculant to the mixed emulsion and co-precipitating a crude rubber compound of Claim 1;
Washing with water and then drying the said crude rubber compound [Example 2; Paragraph 0036], corresponding to the steps of washing and drying to obtain the graphene masterbatch of Claim 1; and
a graphene oxide and rubber composite formulation with 2.5% by weight of graphene oxide [Example 2; Paragraph 0036] (20g graphene oxide / (20g graphene oxide + 100g water + 380g white carbon black + 190g bis[y-(triethoxysilyl)propyl]disulfide + 125g styrene-butadiene rubber latex) ) = 20g/815g = 2.5% by weight graphene oxide), which is encompassed by the claimed range of 1-20% by weight of the graphene oxide of Claim 5.
Liu ‘610 further teaches their method produces a graphene oxide rubber composite material that is well dispersed and strongly interfacially bonded [Paragraph 0008].
Luan and Liu ‘610 are considered to be analogous art as the claimed invention, as all are in the same field of graphene oxide polymer composites for vehicle tires.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to modify the rubber tire composition of Liu ‘610 by adding the graphene oxide amount, flocculant, precipitating, and washing as taught by Liu ‘610. This modification would be expected to improve dispersion and interfacial bonding, thereby improving the final product and arriving at the claimed invention.
Luan is silent on the limitations “such that the anionic surfactant is employed to perform surface activation and modification on graphene components to reduce stacking of graphene sheets” of Claim 1 and “wherein modified graphene oxide particles and rubber particles in natural rubber latex form bound particles due to an electrostatic attraction of positive ions on a protein-phospholipid film on a surface of the rubber particles in natural rubber latex to keep stable” of Claim 1. The ability for surfactants to perform surface activation and the formation of bound particles due to an electrostatic attraction of positive ions on a protein-phospholipid film on a surface of the rubber particles in natural rubber latex to keep stable is a function of the method of preparing the graphene by an aqueous phase and mixing this emulsion with natural rubber. Luan teaches a substantially similar method for preparing a graphene masterbatch including the step of adding modified graphene oxide aqueous dispersion in an emulsion mixed with natural rubber as set forth above. Therefore, the surface activation and formation of bound particles due to an electrostatic attraction of positive ions on a protein-phospholipid film on a surface of the rubber particles in natural rubber latex to keep stable is expected. Case law has held that claiming of a new use, new function or unknown property which is inherently present in the prior art does not necessarily make the claim patentable. In re Best, 562 F.2d 1252, 1254, 195 USPQ 430, 433 (CCPA 1977). The courts have stated that 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. In re Spada, 911 F.2d 705, 15 USPQ2d 1655, (Fed. Cir. 1990). See also In re Best, 562 F.2d 1252, 195 USPQ 430, (CCPA 1977). "Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established." Further, if it is the applicant's position that this would not be the case, evidence would need to be provided to support the applicant's position. In the alternative that the above disclosure is insufficient to anticipate the above listed claims, it would have nonetheless been obvious to the skilled artisan to produce the claimed method, as the reference teaches each of the claimed ingredients (graphene oxide and natural rubber) in the same amounts and for the same utility (tires).
While Luan, Hong, Zhou, Zhang ‘477, and Liu ‘610 may be silent to the exact order of performing certain steps, case law has held that selection of any order of performing process steps is prima facie obvious in the absence of new or unexpected results (See MPEP 2144.04.IV.C., In re Burhans, 154 F.2d 690, 69 USPQ 330 (CCPA 1946); and In re Gibson, 39 F.2d 975, 5 USPQ 230 (CCPA 1930)).
Claims 8-9 are rejected under 35 U.S.C. 103 as being unpatentable over Chen et al., (WO2021247153; hereafter as “Chen”) and in further view of Luan et al., (CN110358156 A; English translation incorporated herewith; hereafter as “Luan”), Hong et al., (US 2015/0302948 A1; hereafter as “Hong”); Liu et al., (US 2014/0323610 A1; hereafter as “Liu ‘610”), Zhou et al., (CN105968444 (A); English translation incorporated herein; hereafter as “Zhou”) and Zhang et al. (WO 2018/166477A1; English translation incorporated herein; hereafter as “Zhang ‘477”).
Regarding Claim 8, Luan, Hong, Liu ‘610, Zhou, and Zhang ‘477 teach the method for preparing the graphene masterbatch of Claim 1 as set forth above and incorporated herein by reference.
Luan teaches rubber tire tread compositions with improved wear resistance [Abstract; Paragraphs 0067-0094], corresponding to the claimed long-lifespan tire. Luan further teaches:
a graphene masterbatch [Paragraphs 0067-0094], corresponding to the claimed graphene masterbatch;
mixing said graphene masterbatch components, including natural rubber, and blending at 155°C [Paragraphs 0067 and 0072], corresponding to mixing and plastication of the graphene masterbatch and natural rubber block;
an internal mixer [Paragraph 0073], corresponding to the internal mixer;
adding an accelerator [Paragraph 0067and 0072], corresponding to the vulcanization accelerator;
wherein the accelerator is NOBS [Paragraph 0016], corresponding to the NOBS;
adding antioxidants [Paragraph 0067and 0072], corresponding to the antioxidant;
adding zinc oxide [Paragraph 0067and 0072], corresponding to the zinc oxide; and
adding filler, including carbon black, [Paragraph 0067and 0072], corresponding to the carbon black; and
cooling said components to 23° C [Paragraph 0075], corresponding to cooling the rubber mixture to room temperature;
adding sulfur to said components [Paragraphs 0067 and 0073], corresponding to the sulfur;
transferring said components to an open mixer [Paragraph 00074], corresponding to transferring the rubber mixture to an open mill;
open milling [Paragraph 0025], corresponding to the open milling; and
vulcanizing to obtain a tire tread rubber [Paragraph 0076], corresponding to vulcanization to obtain the tire.
Luan also teaches their rubber composition results in tires with low rolling resistance and compression heat generation while maintaining wet skid resistance and has excellent wear resistance [Paragraph 0008].
However, Luan is silent to:
Wherein the anti-aging agent is N-Isopropyl-N'-phenyl-1,4-phenylenediamine;
Wherein the antioxidant is poly(1,2-dihydro-2,2,4-trimethylquinoline); and
The tire mold.
Regarding the claimed poly(1,2-dihydro-2,2,4-trimethylquinoline) and N-Isopropyl-N'-phenyl-1,4-phenylenediamine of Claim 8, Chen teaches graphene oxide elastomer compositions for tires [Abstract; Paragraph 0002]. Chen further teaches 1,2-dihydro-2,2,4-trimethylquinoline and N-isopropyl- N'-phenyl-p-phenylenediamine as antioxidants in said compositions [Paragraph 0137]. Chen also teaches their composition allows for less fillers to be used while achieving desirable mechanical properties [Paragraph 0004].
Luan and Chen are considered to be analogous art as the claimed invention, as all are in the same field of graphene oxide rubber composites for vehicle tires with enhanced mechanical properties.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to add the 1,2-dihydro-2,2,4-trimethylquinoline and N-isopropyl- N'-phenyl-p-phenylenediamine as taught by Chen. This modification would expectedly improve the tire composition by allowing for less fillers to be used while improving mechanical properties, and thereby arriving at the claimed invention.
Regarding the claimed tire mold, Hong teaches graphene oxide and nanoparticle composite materials [Paragraph 0004]. Hong further teaches said composite material can be subjected to molding process to make things such as vehicle tires [Paragraphs 0004 and 0140] and provide enhanced mechanical properties in many diverse applications [Abstract; Paragraph 0139].
Luan and Hong are considered to be analogous art as the claimed invention, as all are in the same field of graphene oxide composites for vehicle tires.
Therefore, it would be obvious to one of ordinary skill in the field of art before the effective filing date to use molds for diverse applications such as vehicle tires as taught by Hong. This modification would enable fabricating tires with enhanced mechanical properties, improving the final product and thereby arriving at the claimed product.
While Chen, Luan, Liu ‘610, Zhou, and Zhang ‘477 may be silent to the exact order of performing certain steps, case law has held that selection of any order of performing process steps is prima facie obvious in the absence of new or unexpected results (See MPEP 2144.04.IV.C., In re Burhans, 154 F.2d 690, 69 USPQ 330 (CCPA 1946); and In re Gibson, 39 F.2d 975, 5 USPQ 230 (CCPA 1930)).
Regarding Claim 9, Luan further teaches: (see calculations in the Table 1 below)
40-70 parts filler by weight, including carbon black and graphene oxide [Paragraph 0067], which is equivalent to 26-56 wt. %, which overlaps the claimed range of 10-100 parts of graphene oxide masterbatch (5.8-59 wt. %) and 60 parts of carbon black (23-74 wt. %);
50-95 parts natural rubber by weight [Paragraph 0067], which is equivalent to 37-68 wt. %, which overlaps the claimed range of 50-87.5 parts of natural rubber;
0.8-3 parts accelerator by weight [Paragraph 0067], which is equivalent to 0.4-3.1 wt. %, which overlaps the claimed range of 2 parts of vulcanization accelerator;
1.5-5 parts antioxidant by weight [Paragraph 0067], which is equivalent to 0.8-5 wt. %, which overlaps the claimed range of 1 part of anti-aging agent;
0-0.6 parts anti-reversion agent by weight [Paragraph 0067], which is equivalent to 0-0.6 wt. %, which overlaps the claimed range of 1 part of antioxidant;
2-6 parts zinc oxide by weight [Paragraph 0067], which is equivalent to 1-6 wt. %, which overlaps the claimed range of 5 parts of zinc oxide; and
0.6-2 parts sulfur by weight [Paragraph 0067], which is equivalent to 0.3-2.1 wt. %, which overlaps the claimed range of 2 parts of sulfur.
Luan also teaches their rubber composition results in tires with low rolling resistance and compression heat generation while maintaining wet skid resistance and has excellent wear resistance [Paragraph 0008].
Therefore, it would be obvious to one of ordinary skill in the art before the effective filing date that the filler, which includes carbon black and graphene oxide, of Luan, correspond to the claimed carbon black and graphene oxide.
Furthermore, it would be obvious the claimed minimum amount of graphene oxide and carbon black is equivalent to 41 wt. % (min. amt. = 100* (min. amt. graphene oxide + min. amt. carbon black) / (max. amt. of all other components + min. amt. graphene oxide + min. amt. carbon black) = 70/171 = 41%), and the claimed maximum amount is equivalent to 94 wt. % (max. amt. = 100* (max. amt. graphene oxide + max. amt. carbon black) / (min. amt. of all other components + max. amt. graphene oxide + max. amt. carbon black) = 160/171 = 94%). And it would be obvious that this claimed range of 41-94 wt. % graphene oxide and carbon black overlaps the range of 26-56 wt. % taught in the prior art by Luan.
Similarly, the claimed ranges of the natural rubber block to the vulcanization accelerator to the anti-aging agent to the antioxidant to the zinc oxide to the sulfur to the carbon black overlaps the respective ranges taught in Luan. By choosing the overlapping portion of the range taught in the prior art and the range claimed by the applicants, it has been held to be a prima facie case of obviousness. See MPEP section 2144.05(I). It would have also been obvious to one having ordinary skill in the art to tune the natural rubber, vulcanization accelerator, anti-aging agent, antioxidant, zinc oxide, sulfur and carbon black through routine optimization within prior art conditions or through routine experimentation.
Table 1:
Calculations to convert parts by weight to percentage weight in the instant Claim 9 and the amount ranges taught in Luan et al., Paragraph 0067.
Claim 9, Element
Amt, (parts)
Minimum
Amt*, (%)
Maximum
Amt**, (%)
Luan [0067],
Element
Amt, (parts)
Minimum
Amt*, (%)
Maximum
Amt**, (%)
Graphene oxide
10-100
100*(10/171) = 5.8%
100*(100/171) = 58%
Filler (graphene oxide + C black)
40-70
100*(40/121) = 26%
100*(70/125) = 56%
Nat. rub.
50-87.5
100*(50/171) = 29 %
100*(87.5/171) = 51%
Nat. rub.
50-95
100*(50/136) = 37%
100*(95/140) = 68%
Vulc. Accel.
2
100*(2/261) = 0.8%
100*(2/ 81) = 2.5%
Accel.
0.8-3
100*(0.8/180) = 0.4%
100*(3/97) = 3.1%
Anti-aging
1
100*(1/261) = 0.4%
100*(1/171) = 1.3%
Antiox.
1.5-5
100*(1.5/178) = 0.8%
100*(5/98) = 5%
Antiox.
1
100*(1/261) = 0.4%
100*(1/81) = 1.3%
Anti-rev.
0-0.6
0%
100*(0.6/96) = 0.6%
ZnO
5
100*(5/261) = 1.9%
100*(5/81) = 6.2%
ZnO
2-6
100*(2/178) = 1%
100*(6/99) = 6%
Sulfur
2
100*(2/261) = 0.8%
100*(2/81) = 2.5%
Sulfur
0.6-2
100*(0.6/180) = 0.3%
100*(2/196) = 2.1%
C black
60
100*(60/261) = 23%
100*(60/81) = 74%
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Response to Arguments
Applicant's arguments filed December 04, 2025 have been fully considered but they are not persuasive.
Applicant argues (1) that none of the cited documents teach the claimed L-cysteine as a surface modifier. However, Applicant’s arguments with respect to Claims 1 and 8 have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument. In particular, attention is directed to the rejection above, wherein Liu ‘610 teaches graphene oxide and rubber composite [Paragraph 0037], accelerator TT [Paragraph 0037], anti-ager 401 ONA [Paragraph 0037], RD [Paragraph 0037], oxide [Paragraph 0037], mixing step in a mill[Paragraph 0037], sulfur [Paragraph 0037], Hong teaches anionic surfactants, Zhou teaches 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride [Abstract] and N-hydroxysuccinimide [Abstract], and Zhang ‘477 teaches L-cysteine [Paragraph 0071-0074]. Thus, applicant’s argument is not persuasive.
Applicant argues (2) the cited prior art documents neither teach nor suggest the two-step modification of graphene oxide involving "the anionic surfactant is employed to perform surface activation and modification on graphene components" and "the surface modifier is adopted to perform secondary modification on the graphene oxide". In response to applicant's arguments against the references individually, one cannot show nonobviousness by attacking references individually where the rejections are based on combinations of references. See In re Keller, 642 F.2d 413, 208 USPQ 871 (CCPA 1981); In re Merck & Co., 800 F.2d 1091, 231 USPQ 375 (Fed. Cir. 1986). In this case, Liu ‘610, Hong, Zhou, and Zhang ‘477 in combination teach or suggest the two-step modification of graphene oxide involving "the anionic surfactant is employed to perform surface activation and modification on graphene components" and "the surface modifier is adopted to perform secondary modification on the graphene oxide". Thus, applicant’s argument is not persuasive.
Applicant argues (3) Hong merely mentions relatively broad pH range encompassing both acidic and alkaline environments, but in the claimed invention the reaction system is adjusted to pH=10, which is a strong alkaline environment. However, Hong nevertheless teaches an overlapping pH range. By choosing the overlapping portion of the range taught in the prior art and the range claimed by the applicants, it has been held to be a prima facie case of obviousness. See MPEP section 2144.05(I). Furthermore, Hong teaches having an appropriate pH maintains, imparts or results in a desired charge effect, and the composites have specific pH ranges [0074] which further motivates modifying the pH to tailor the final product properties. Thus, applicant’s argument is not persuasive.
Applicant argues (4) since Hong does not teach pH = 10, the combined references do not teach step (S1) but step (S2) cannot be performed directly without step (S1). However, Hong does teach a pH greater than 5 which overlaps with the claimed range of pH = 10 as shown in the disclosure above. Thus, Liu ‘610, Hong, Zhou, and Zhang ‘477 in combination teach step (S1) which would be expected to allow step (S2) to be performed. Thus, applicant’s argument is not persuasive.
Applicant argues (5) none of the cited prior art documents reveal that the purpose of such a combination is to achieve the ultimate objective of first forming bound particles due to the electrostatic attraction, followed by inducing co-precipitation mediated by pi-pi interaction via flocculation. However, the prior art is not required to have the same motivation as the claimed invention. The examiner recognizes that obviousness may be established by combining or modifying the teachings of the prior art to produce the claimed invention where there is some teaching, suggestion, or motivation to do so found either in the references themselves or in the knowledge generally available to one of ordinary skill in the art. See In re Fine, 837 F.2d 1071, 5 USPQ2d 1596 (Fed. Cir. 1988), In re Jones, 958 F.2d 347, 21 USPQ2d 1941 (Fed. Cir. 1992), and KSR International Co. v. Teleflex, Inc., 550 U.S. 398, 82 USPQ2d 1385 (2007). In this case, Hong teaches that anionic surfactants aid in attaching surfactant to magnetically sensitive nanoparticles [Paragraph 0070]; Zhou teaches their rubber material composition is tough, has good wear resistance and a long service life [Abstract]; and Zhang ‘477 teaches graphene sheets increase the amount of graphene-like substances attached to the fiber [Paragraph 0080]. Thus, applicant’s argument is not persuasive.
Conclusion
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/DORIS LING/Examiner, Art Unit 1764
/ARRIE L REUTHER/Supervisory Primary Examiner, Art Unit 1764
1 According to SpecialChemical (NPL), accelerator TT is a vulcanization accelerator (see attachment).
2 According to Zhang et al. (CN105037830A), RD is an antioxidant [Paragraph 0020] (cited in IDS dated 06/02/2022).
3 According to ChemBK (NPL), KH-550 is 3-amino propyl trimethyoxy silane (see attachment).
4 See Table 1 for calculations.
5 See Table 1 for calculations.