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 .
Response to Arguments
In their response dated 10/24/2025 applicants amended claim 13 to include aspect ratio of the particles and mean particle size. Applicants also added new claims 18 and 19. Claim 17 was canceled.
The applicants requested reconsideration of the rejection arguing following:
With respect to claim 13, applicants stated that Unal does not teach the aspect ratio of the particles.
Applicant’s amendment includes aspect ratio of the polyurethane particles to be between 1:0.5 and 1:0.5 inclusive of end ranges. This would render the particulates having “rod-like” structure. Unal teaches polyurethane dispersion mixed with alumina suspension (see for example example 3 [0077]. Unal teaches in [0062] that the particles have mean particles size of 20-2000 nm [0063] and addition of inorganic particles which are rod-like or platelet shaped will affect the final shape of the polymeric composite particle [0054]. While Unal discloses the aspect ratio of 3:1, normalizing it to 1 the aspect ratio is 1:0.33. As such Unal does disclose the aspect ratio. Having said that applicants utilize the process of claim 1, to create polyurethane particles, and specification while supports the amendment does not provide adequate disclosure of how exactly the applicants control the aspect ratio of the precipitate in order. The statement in the specification is the same as the statement in the claim as amended.
With respect to claim 1, applicants stated that Monteil does not identify that the polyurethane is a crystallizing polyurethane. Applicants further indicated that instant specification [0049] defines a crystallizing polyurethane as one having a melting peak using DSV at a temperature of 20oC or greater.
With respect to crystallization of polyurethanes, it is well established fact in the art that melting point does not dictate the crystallizability of the polyurethane. Crystallizability of polyurethane depends molecular structure, processing conditions and temperature. Some polyurethanes have melting range rather than single point and their crystallization behavior depends on cooling rate and other factors (cold temperatures and temperature fluctuations not water itself). While applicant’s specification defines polyurethane having melting point using DSC, instant independent claims are much broader in scope. Under broadest reasonable interpretation, the polyurethane can be prepolymer, the rate at which polyurethane crystallizes is an open to interpretation and therefore includes those polyurethanes that crystallize very slowly.
The primary reference of Johansen teaches process while Monteil discloses polyurethanes can be also places in freezing temperatures to form particulates. Monteil further states that the size of the particles depends to some degree upon the manner of stirring or mixing. It is also well established that the precipitation and crystallization can occur simultaneously, because by precipitation, polyurethan does have crystalline character from either soft block, hard block or both. Again, the claims do not contain any information as to how crystalline the polyurethane has to be, if it is polymer or prepolymer or oligomer, and how fast it has to crystallize. Current claims state that the dispersion is stored until a precipitate is formed which really does not set any limits with respect to time. Lastly the polyurethanes of Monteil include diisocyanate of a polyether of propylene glycol is dispersible in water due to presence of glycol.
Having said that, applicant’s newly added claim requiring melting peak at 20oC, is new issue and consideration as such new rejection will be applied. Since claim 18 has to meet all the limitations of instant claim 1 on which it depends, the new reference will have to include both claim 1 and claim 18 and it will still be final as necessitated by amendment.
Claim Objections
Claim 13 as amended is objected to because of the following informalities: Newly added limitation of “wherein the number-based mean particle size, as determined by optical microscopy is equal to or less than 10 mmm” is already present in lines 4 and 5 of the claim. The limitation is redundant as it is repeated twice. One occurrence should be deleted. Appropriate correction is required.
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.
Claim Rejections - 35 USC § 102
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claim 13-16 are rejected under 35 U.S.C. 102(a)(2) as being anticipated by Unal (US 2013/0101540).
With respect to claim 13, Unal discloses polyurethane dispersion comprising inorganic nanoparticles. Wherein the inorganic particles are incorporated (embedded) into polymeric matrix (Abstract). Specifically, in Example 3 [0077] polyurethane dispersion was mixed with colloidal alumina suspension. There are two types of nanoparticles taught in example 3. First type is a rod-shaped particle and the second type is platelet shaped particle. Resulting particle diameter is reported in Table 2 [0078], for example 3a, the mean diameter is 0.103 which is less than 1000 nm.
With respect to the aspect ratio of longer axis to shorter axis is 3:1, which falls within claimed range of 1:0.1 to ≤ 1:1 since long axis is 3 times the short axis, while instant invention allows longer axis to be 10 times the short axis. More preferred embodiment has a ratio of 6:1, the longest dimension being 20-2000 nm, which is less than 10 mm. As it was mentioned in the response to arguments, the 3:1 ratio is equivalent to 1:0.333 when normalized to 1. AS such Unal still meets the particle size as required by instant claim 13.
With respect to the particle size being less than or equal to 10 mm please see rejection of claim 16 below.
With respect to claim 15, claim 32 of Unal discloses composition that can be used as a coating or a film. In [0002] Unal further discloses adhesives and sealants.
With respect to claim 16, final polyurethane composite has particle size of 11.6 microns and 33.868 microns (Table 3). The prior art has particle size within claimed range, although determined by different testing method, this is a physical characteristic of the material and will necessarily be present regardless of the method by which it is measured. As such particle sizes like these even if measured by optical microscope will still have diameter that lies within claimed invention. While Unal does not disclose how the inorganic particle size is determined, due to shape such as rod or platelet, such measurement has to be done by equipment capable of measuring particulates other than spherical. As such particle size is viewed as inherent property.
Claim Rejections - 35 USC § 103
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claims 1-5, 9, 11, 12 are rejected under 35 U.S.C. 103 as being unpatentable over Smith-Johannsen (US 3,236,788 from now on Smith) in view of Monteil (US 3,171,870).
With respect to claims 1 and 2, Smith teaches combining polymers with inorganic filler (titanium dioxide and calcium carbonate, see example 4). Used in example 5 is Hycar 1577 which is a latex of acrylonitrile and butadiene. The two fillers were combined with latex and frozen according to example 1 (col. 10). The dispersion is poured into a plate (or container) and placed in freezer at a temperature of 0oF which is equivalent to approximately -17oC. The Hycar 1577 had particle size of 400 angstrom which is equivalent to 40 nm.
The prior art has particle size within claimed range, although determined by different testing method, this is a physical characteristic of the material and will necessarily be present regardless of the method by which it is measured.
Smith further teaches in col. 7 that frozen dispersions can be thawed such that resulting water can be removed such that the structure of the resin formed during freeze coagulation is maintained.
Smith states that to freeze, the dispersion can be poured into molds of suitable sizes in lieu of exemplified plate (col. 5).
Regardless of the container in which the dispersions are cooled. Removing water isolates precipitate. Per disclosure in col. 9, the particulates can also be heated to removed water to a temperature that is lower than polymer fusion temperature to ensure the shape of the polymeric precipitate is maintained.
Smith discloses many polymers but fails to show that polyurethane can be utilized to produce composites via freeze coagulation.
Monteil discloses method for processing polymers which involves freeze coagulation. The polymers of Monteil include acrylonitrile rubber (col. 3, lines 63-67), acrylonitrile resins and vinyl resins which are also disclosed in Smith. Monteil also discloses that polyurethane can be used as well (col. 4, lines 5-10) which sets for functional equivalency between polyurethane and polymers of Smith. Any polymer used in the freeze coagulation or freeze precipitation has to be crystallizing polymer in order to precipitate or coagulate. This is explicitly taught in Monteil who says that polymer is placed in freezing (refrigerating) condition for the particulates to form and that the size of the particulates depends on the extent of mixing (col. 3, lines 45-50, col. 4, l. 30-46), wherein one example of polyurethane is a pre-polymer of toluenediisocyanate and propyleneglycol ether which dispersible and will precipitate (crystallize).
It would have been obvious to one having skill in the art to utilize polyurethane in process of Smith. One of ordinary skill in the art would understand that polyurethane can coagulate or form precipitate as shown in Monteil. Utilizing polyurethane would be an obvious choice, because polyurethanes cure at low temperature and freezing the dispersion would prevent premature curing.
With respect to claim 3, Smith teaches in col. 1 that his invention is directed to freezing aqueous dispersion or latex in controlled manner to form frozen mass. The thawed mass (once water is removed) is broken down by suitable means such as grinding (lines 42-43)
With respect to claim 4, Hycar 1577 has solids content of 38% (col. 10, lines 44-46).
With respect to claim 5, freezing temperature is -17oC (col. 9, lines 1-2).
With respect to claim 9, the content of inorganic particles in example 5 is 20% by weight.
With respect to claim 11, inorganic particle includes titanium dioxide (see example 5).
With respect to claim 12, composition of Smith is free of solid isocyanates (see examples)
Claims 6, 7 are rejected under 35 U.S.C. 103 as being unpatentable over Smith-Johannsen (US 3,236,788 from now on Smith) and Monteil further in view of Thomas (US 2,426,127).
Discussion of Smith from paragraph 2 of this office action is incorporated here by reference. While Smith teaches the basic freeze coagulation, the reference is silent on several details which are otherwise known in the art.
With respect to claim 7, Smith in one of the methods places the coagulates on absorbent toweling and in order to remove water the temperature has to rise to at least 0oC (col. 9, lines 3-5). Consequently the coagulates of Smith will reach the claimed temperature. However since the applicants did not identify how long the coagulates are subject to the claimed temperature, Smith meets the claims.
Smith teaches that the size of the coagulates obtained in the process vary on several factors. These include extent of mixing and the speed with which the dispersions are frozen. The formed particulates can be used in molding or as coatings. Smith is silent with respect to various alternative methods of separating the particulates from water.
Thomas teaches forming suspended particulates in a coagulation vessel. The temperature is lowered to less than zero (col. 4 lines 15-20).
With respect to claim 6, The coagulates suspended in the liquid are washed filtered and dried (col. 4, lines 60-63).
In the light of the above disclosure, one of ordinary skill in the art would readily know various methods of separating solids from liquids. As such it would have been obvious to one having ordinary skill in the art to utilize filtration in the teachings of Smith. Filtration would still provide separated coagulants suitable for making molded articles.
Claims 8 and 10 are rejected under 35 U.S.C. 103 as being unpatentable over Smith-Johannsen (US 3,236,788 from now on Smith) in view of Monteil (US 3,171,870) as applied to claims 1-5, 9, 11, 12, 17 above, and further in view of Unal (US 2013/0101540).
Discussion of Smith and Monteil from paragraph 2 of this office action is incorporated here by reference.
Difference between instant invention and Smith is better explanation as to what type of polyurethanes can be utilized to make the composites and water content.
The discussion of Unal from paragraph 1 of this office action is incorporated here by reference. Unal further teaches that polyurethanes utilized to make composites using polyurethane latex and dispersion of inorganic fillers.
With respect to claim 8, the composite of Unal in various examples disclose water content of 0 (Example 5a), 4.30 % (example 5b), 4.91% (Example 5d), 1.82% (example 3b)
With respect to claim 10, Unal teaches polyurethanes having number average molecular weight of 10,000-100,000 [0061] are good for making latex dispersions via coagulation. The same is expected in Smith, because Smith teaches one method of applying heat at slightly elevated temperatures but below melt/fusion temperature of the composite particulate. Trace amounts of water are always expected.
Polyurethanes having number average molecular weight as that of Unal allow formation of nanocomposites particulates that are stable and result in composite particles having relatively large mean particle size values [0084] completely encapsulating the inorganic filler [0096] which contributes to stability.
In the light of the above disclosure it would have been obvious to one having ordinary skill in the art to utilized polyurethane of Smith that has molecular weight as disclosed in Unal because the polyurethane not only has to be able to form latex and coagulates but also have to be able to form coating on a substrate (both references teach coatings). It would be obvious to also minimize content of water, because water can negatively affect the composite. For example, water in polyurethane can lead to softening or hardening, as well as changes in structure which further lead to reduced lifespan. One of ordinary skill in the art would readily understood the effects of water on a composite.
New grounds of rejection for new claims 18 and 19:
Claims 1-5, 9, 11, 12, 18 and 19 are rejected under 35 U.S.C. 103 as being unpatentable over Smith-Johannsen (US 3,236,788 from now on Smith) in view of Achten (WO 2018/046739, wherein US 2019/0184632 is used as translation).
Note, rejection of claims 2-5, 11, 12 are attributed to the teaching of Smith not Achten already rejected in paragraph 2 and will be repeated here. Rejection of claims 2-5, 11 and 12 does not constitute new grounds of rejection.
With respect to claims 1, 2, 18 and 19, Smith teaches combining polymers with inorganic filler (titanium dioxide and calcium carbonate, see example 4). Used in example 5 is Hycar 1577 which is a latex of acrylonitrile and butadiene. The two fillers were combined with latex and frozen according to example 1 (col. 10). The dispersion is poured into a plate (or container) and placed in freezer at a temperature of 0oF which is equivalent to approximately -17oC. The Hycar 1577 had particle size of 400 angstrom which is equivalent to 40 nm.
The prior art has particle size within claimed range, although determined by different testing method, this is a physical characteristic of the material and will necessarily be present regardless of the method by which it is measured.
Smith further teaches in col. 7 that frozen dispersions can be thawed such that resulting water can be removed such that the structure of the resin formed during freeze coagulation is maintained.
Smith states that to freeze, the dispersion can be poured into molds of suitable sizes in lieu of exemplified plate (col. 5).
Regardless of the container in which the dispersions are cooled. Removing water isolates precipitate. Per disclosure in col. 9, the particulates can also be heated to removed water to a temperature that is lower than polymer fusion temperature to ensure the shape of the polymeric precipitate is maintained.
Smith discloses many polymers but fails to show that polyurethane can be utilized to produce composites via freeze coagulation.
Achten discloses a dispersion of polyurethane which includes tradenames such as Dispercoll U XP 2682 which are anionic polyurethane waterborne polymer, which also means that is it both crystallizable and will precipitate when subject to the cooling temperatures below 0 degrees [0085]. Other polymers include polyamides, polyesters, polyaclkylene oxide, plasticized PVC. The two polyurethanes that are exemplified include anionic polyurethane Dispercoll and elastomeric polyurethane Dismomelt [0053].
The polymers of Achten are reported to have a melting has a melting range at 20oC or higher, wherein the melting peak will implicitly be within the melting range (See Achten’s claim 16).
In the light of the above disclosure it would have been obvious to one having ordinary skill in the art to utilize the polymers of Achten in the disclosure of Smith and thereby obtain the claimed invention. This is because Smith already discloses the same type of polymers, but it is silent with respect to their melting range as measured by DSC. In Summary, the polymers of Achten having defined melting point as measured by DSC will not adversely affect the process of Smith, because the polymers of Achten are shown to also crystallize at the same temperatures.
With respect to claim 3, Smith teaches in col. 1 that his invention is directed to freezing aqueous dispersion or latex in controlled manner to form frozen mass. The thawed mass (once water is removed) is broken down by suitable means such as grinding (lines 42-43)
With respect to claim 4, Hycar 1577 has solids content of 38% (col. 10, lines 44-46).
With respect to claim 5, freezing temperature is -17oC (col. 9, lines 1-2).
With respect to claim 9, the content of inorganic particles in example 5 is 20% by weight.
With respect to claim 11, inorganic particle includes titanium dioxide (see example 5).
With respect to claim 12, composition of Smith is free of solid isocyanates (see examples)
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, 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 nonprovisional extension fee (37 CFR 1.17(a)) 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 mailing date of this final action.
Correspondence
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/KATARZYNA I KOLB/Primary Examiner, Art Unit 1767 November 20, 2025
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