DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim 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 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.
Claims 1-8 are rejected under 35 U.S.C. 103 as obvious over Klaerner et al. (US Pub 2003/0108879) evidenced by Matyjaszewski et al. (US Pub 2004/0204556) in view of Tanaka et al. (U.S. 2011/0000658).
Regarding claims 1, 3-5, and 7, Klaerner discloses in the entire document, particularly in the abstract and at Figs 1-5 and ¶s 0002, 0007, 0014, 0028, 0122, 0126, 0213, examples 18 and 20, polymer brushes, which comprise a substrate having a surface modified with a hydrophobic polymer segment, attached to which is a water-dispersible or water-soluble polymer segment having functional groups that bind probes and extend from the surface. The substrate having a first layer composed of a number of hydrophobic polymer chains attached to the substrate surface, and a second layer composed of a number of polymer chains, each of which include a water-soluble or water-dispersible segment having two termini, one terminus being free and the other being bound to a hydrophobic polymer chain. From Figs 2 and 5 and ¶s 0007, 0012, 0014, 0016-0017, 0028, the polymer brush has improved stability in aqueous environments achieved by the presence of hydrophobic polymer chains on the substrate surface of the brush, forming a hydrophobic layer of a controlled thickness; the provision of such a brush wherein polymer chains having a water-soluble or water-dispersible segment having functional groups capable of bonding to a probe are attached to the hydrophobic polymer chains; the provision of such a brush wherein the molecular weight and/or density of the hydrophobic polymer chains is controlled to optimize bond stability to the substrate surface. The substrate surface has a layer on the substrate surface comprising polymer chains having two termini and a water-soluble or water-dispersible intermediate segment between the termini. The brush comprising a substrate surface, a hydrophobic layer comprising hydrophobic polymer chain segments attached to the substrate surface having a dry thickness of at least about 50 angstroms, and a hydrophilic layer attached to the hydrophobic layer containing functional groups for the attachment of a probe for binding the molecule. The polymer layer comprises a first hydrophobic layer attached to the substrate surface, and a second hydrophilic layer attached to the hydrophobic layer containing sites for the attachment of a probe for binding the molecule. The hydrophobic layer on a substrate surface having a dry thickness of at least about 50 angstroms, has the hydrophilic layer formed on said hydrophobic layer. An improved polymer brush can be prepared by growing polymer chains from the substrate surface wherein at least a portion of the chains comprise a first segment or block which is hydrophobic, in order to form a hydrophobic layer of some minimum thickness on the substrate surface (e.g., about 50 angstroms, 75 angstroms, 100 angstroms or more), a second water-soluble or water-dispersible segment or block then being grown from at least a portion of hydrophobic segment ends. This hydrophobic layer renders the polymer chains more stable to aqueous environments, the layer acting as a barrier to reduce, and possibly prevent, hydrolysis of the covalent bonds linking the chains to the substrate surface. As a result, the polymer brushes of the present invention can be used under more extreme conditions (e.g., higher temperatures, pressures, pH), and can additionally be reused for some applications (the brushes now being able to undergo washing to remove bound molecules and/or probes).
From Fig. 5 and ¶s 0120-0122, 0126, 0213 and 0216 when quenching is used some means is employed like a chemical means of RTP initiator for the initiator layer can be controlled to space or dummy molecules initially placed on the substrate surface for growth of the first polymeric, e.g. hydrophobic, layer. The termini of the polymer chain segments or blocks which have been formed remain active once all of the monomer present has been consumed or reacted. As a result, additional chain block or segment growth will occur if more monomer is added to the surface. In such instances, the surface density of these subsequent segments will be dependent upon the density of the reactive or living segment ends. Accordingly, the density of these subsequent segments can be reduced, relative to the number of living segments ends, by first rendering a portion of these ends inactive (i.e., terminating or quenching the "living" ends, such that they are incapable of re-initiating polymer chain growth). Chemical treatment, typically employed with ATRP (atom transfer radical polymerization) systems, wherein for example the active alkyl halide group is subjected to nucleophilic displacement of the halide.
From Id the polymer-modified surface may be referred to as having a "polymer layer" on top of the surface. The depiction in FIG. 5 actually shows the substrate (e.g., a wafer), an initiator layer (e.g., bound initiator or initiator-control adduct), a "polymer layer" and then some polymer chains on top of the polymer layer {reading on polymerization initiator layer coated on a surface of the substrate }. The polymer chains on top of the polymer layer are part of the polymer layer and are shown for illustration purposes to show what the polymer layer comprises in the embodiment shown in FIG. 5. Generally, the polymer-modified surface will have a determinable thickness. The thickness of the polymer layer, measured from the substrate surface, is selected based upon the particular application. In general, however, dry thickness of the polymer layer (either the hydrophobic layer, the hydrophilic layer, or the two layers combined, as further described herein) may in some instances ranges from about 20 to about 2000 angstroms (2 to 200 nm), which overlaps with the thickness range of claim 5.
From examples 18 and 20 the initiator for the initiator layer is synthesized from p-(Chloromethyl)phenyltrimethoxysilane (0.4 g, 1.62 mmol) and N,N-diethyl dithiocarbamate sodium salt (0.370 mg, 2.17 mmol) were each dissolved separately in 3 mL of dry THF. The N,N-diethyl dithiocarbamate solution was added slowly to the p-(Chloromethyl)-phenyltrimethoxysilane solution via a syringe. Matyjaszewski evidences at examples 263 and 266 and ¶s 0572-0573, and 0578-0579 that ((chloromethyl)-phenylethyl)-trimethoxysilane or ((chloromethyl)phenylethyl)dimethylchlorosilane is a macroinitiator or an initiator for the modification of surfaces like silica particles. The (Chloromethyl)-phenyltrimethoxysilane ((chloromethyl)-phenylethyl)-trimethoxysilane or (chloromethyl)phenylethyl)dimethylchlorosilane read on Formula (I), where for the former reading on (I) with X as chloro, R1 is methylene, n = 1, m = 0, R3 is methoxy.
From ¶ 0367 when using a dummy or spacer molecule, p-(chloromethyl)phenyltrimethoxysilane and phenyltrimethoxysilane {i.e. a second organosilane} are mixed together at the beginning of the process. The sodium salt is then introduced in a slight excess compared to the p-(chloromethyl) derivative.
From ¶s 0230-0232 the substrate is generally a material having a defined surface (e.g., rigid or semi-rigid surface). In many embodiments, at least one surface of the substrate will be substantially flat, although in other embodiments small beads, pellets, porous, etched substrates or irregular objects may provide the surface. The substrate may be organic or inorganic. Examples of suitable substrates include, in addition to those previously referenced herein, glass (e.g., silica glass), quartz, fiber optic threads, silicon (including silicon dioxide), inorganic and organic microspheres, plastic and polymer-coated substrates. Polymer substrates {reading on “resin” of pending Claim 7} may have functional groups intrinsic to the polymer or may have surface functional groups introduced by chemical treatment, corona discharge, plasma treatment, etc.
Regarding claims 3 and 4, Klaerner discloses that monomers can be polymerizable vinyl monomers, including those claimed in the Markush group of claim 4. See paragraph [0047].
However Klaerner does not expressly disclose that the (Chloromethyl)-phenyltrimethoxysilane is with a hydrolysis and condensation polymerization polymer with metal alkoxide like Si(OR)4, like tetraalkoxysilane or a thickness of 250 to 700 nm (claim 6) or that the second organosilane is that of formula II (claim 2) or that the plastic substrate is of a particular resin (claim 8).
Tanaka is directed to an underlying layer of a hydrophilic layer with the former having (chloromethyl)-phenyltrimethoxysilane as in Klaerner of the initiation layer under the polymer layer as in Fig. 5 as disclosed in the abstract and at ¶s 0100, 0195, 0130, 0249. From the abstract a hydrophilic member is provided which comprises a substrate of every kind having formed thereon a surface having excellent antifouling properties, quick-drying properties of water or the like, and wear resistance and being flexible. The hydrophilic member is characterized by having an overcoat layer formed from a hydrophilic composition containing at least one of a hydrophilic polymer (A) containing a specific structure and a hydrophilic polymer (B) containing a specific structure; and an undercoat layer formed from a composition for forming the undercoat layer containing an alkoxide (C) represented by the general formula (III) of M(OR14)4 wherein M represents an element selected from among Si, Ti, and Zr {reading on metal alkoxide with Si as Si(OR14)} and an alkoxysilane (D) represented by the general formula (IV) of Si(OR15)aR164-a wherein R14 to R16 each independently represents a hydrogen atom or a hydrocarbon group, like and “a” represents 2 or 3. From ¶s 0100-0101 and 0194 an example of alkoxysilane (D) where “a” is 3, namely trifunctional alkoxysilanes, that can be hydrophobic is for the undercoat layer (p-chloromethyl)phenyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, which can be used alone or in combination with other alkoxysilanes of (D) {the latter six meeting formula II of pending claim 2 where p and q each equal zero and r=3 so R8 is not present and R7 is an alkoxy group of 3 carbons. From ¶ 0032 a hydrocarbon group is an alkyl group containing 1 to 8 carbon atoms, such as methyl group, an ethyl group, a propyl, or butyl group for R14 {overlapping as OR14 with alkoxy group having 1 to 4 carbon atoms of R9 of (SiOR9)4}.
From ¶s 0105-0106 and 0013 a catalyst (E) is preferably contained in the hydrophilic composition and the composition for forming an undercoat layer. The contained catalyst (E) can accelerate the reaction of the specific hydrophilic polymer (A) and the specific hydrophilic polymer (B), or can accelerate reaction of the specific alkoxide (C) and the specific alkoxysilane (D). As the catalyst (E), an acid or a basic compound is used as it is or in a state of being dissolved in water or in an alcohol (hereinafter, these are also inclusively referred to as "acidic catalysts and basic catalysts", respectively). The concentration of the acid or the basic compound which constitutes the catalyst is high, hydrolysis rate and polycondensation rate tend to become large {reading on polymerization initiator layer of formula 1 as chloromethylphenyltrimethoxysilane and metal alkoxide of tetraalkoxysilane as tetra-functional alkoxide has hydrolysis and condensation polymerization polymer for pending Claims 1 and 15}. From ¶ 0013 in mixing a hydrophilic polymer having a reactive group at the end of the polymer chain into the hydrophilic layer, the hydrophilic polymer chains are oriented in a graft pattern in the outermost surface of the hydrophilic layer to realize more excellent antifouling properties. Further, by combining a trifunctional alkoxysilane and a tetra-functional alkoxide as an undercoat layer, enough flexibility can be imparted to the film formed on the substrate, thus a hydrophilic member having excellent antifouling properties, excellent quick-drying properties of water or the like, and excellent wear resistance, and having enough flexibility being completed.
From ¶ 0249 the thickness of the undercoat layer still more preferably from 0.05 µm to 50 µm., i.e., 50 to 50000 nm overlapping the range of pending Claim 6. From ¶s 0193-0198 the substrate can be any of glass, plastics, metals, ceramics, wood, stones, cement, concrete, fibers, fabrics, paper, leathers, tiles, rubbers, latexes, and their combinations and laminates. Plastic substrates include polyester, like polyethylene terephthalate, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene-vinyl alcohol, polystyrene, polycarbonate, and acrylic resin others {reading on pending Claims 8}.
In accordance with MPEP § 2144.06 “Art Recognized Equivalence for the Same Purpose” "It is prima facie obvious to substitute equivalents, motivated by the reasonable expectation that the respective species will behave in a comparable manner or give comparable results in comparable circumstances." In re Ruff 118 USPQ 343; In re Jeze/158 USPQ 99; "the express suggestion to substitute one equivalent for another need not be present to render the substitution obvious." In re Font, 213 USPQ 532. In the alternative in accordance with MPEP § 2144.06 “ “It is prima facie obvious to combine two compositions each of which is taught by the prior art to be useful for the same purpose, in order to form a third composition to be used for the very same purpose.... [T]he idea of combining them flows logically from their having been individually taught in the prior art.” In re Kerkhoven, 626 F.2d 846, 850, 205 USPQ 1069, 1072 (CCPA 1980) (citations omitted) (Claims to a process of preparing a spray-dried detergent by mixing together two conventional spray-dried detergents were held to be prima facie obvious.). See also In re Crockett, 279 F.2d 274, 126 USPQ 186 (CCPA 1960) (Claims directed to a method and material for treating cast iron using a mixture comprising calcium carbide and magnesium oxide were held unpatentable over prior art disclosures that the aforementioned components individually promote the formation of a nodular structure in cast iron.); and Ex parte Quadranti, 25 USPQ2d 1071 (Bd. Pat. App. & Inter. 1992) (mixture of two known herbicides held prima facie obvious).
Here Klaerner has on a substrate a layer with chloromethylphenyltrimethoxysilane as an initiator layer for the purpose of an underlayer along with phenyltrimethoxysilane as a second organosilane for an oriented i.e. brush hydrophilic layer and over the substrate. Tanaka has an underlayer with hydrolyzed and condensed polymerized polymer of chloromethylphenyltrimethoxysilane along with tetraalkoxysilane of Si(OR)4 for the purpose of an underlayer on a substrate for an oriented hydrophilic layer over the underlayer. Given this similarity of purpose the underlayer of hydrolyzed and condensed polymerized polymer of chloromethyphenyltrimethoxysilane along with tetraalkoxysilane as an undercoat layer of Tanaka in a thickness from 50 to 50000 nm and with the second organosilane as methyl, ethyl, propyl or butyl tri(m)ethoxysilane are combined with the initiator layer of chloromethyphenyltrimethoxysilane of Klaerner. Also the plastic substate of Klaerner can be a polyethylene terephthalate resin, polycarbonate resin or acrylic resin.
One of ordinary skill in the art before the effective filing of the pending patent application would have considered it prima facie obvious as for example at least under rationale G of MPEP § 2141 III and 2143 I G to have from Klaerner a substrate for formation of a polymer brush having of the substrate surface a polymerization initiator layer on the substrate an initiator layer with a thickness of 5 to 200 nm with chloromethylphenyltrimethoxysilane meeting formula I with a second organosilane of phenyltrimethoxysilane under a hydrophilic layer for a polymer brush, where from Tanaka having an undercoat layer with a thickness of 50 to 50000 nm of a hydrolyzed and condensed polymer of chloromethylphenyltrimethoxysilane and metal alkoxide of tetraalkoxysilane and also has a second organosilane of methyl, ethyl, propyl or butyl tri(m)ethoxysilane with an oriented hydrophilic overcoat such hydrolyzed and condensed polymer of chloromethylphenyltrimethoxysilane and metal alkoxide of tetraalkoxysilane and also a second organosilane of methyl, ethyl, propyl or butyl tri(m)ethoxysilane are combined in the initiator layer as an undercoat of Klaerner with the chloromethylphenyltrimethoxysilane, and phenyltrimethoxysilane for an initiator layer thickness of 50 to 50000 nm motivated to have enough flexibility imparted to the film formed on the substrate for an overcoat of oriented hydrophilic member having excellent antifouling properties, excellent quick-drying properties of water or the like, and excellent wear resistance, and having enough flexibility. The combination of Tanaka with Klaerner has a reasonable expectation of success for one skilled in the art because both Tanaka and Klaerner have a chloromethylphenyltrimethoxysilane containing layer as an undercoat, the latter as an initiator layer, for an overlying oriented hydrophilic layer.
Claim 9 is rejected under 35 U.S.C. 103 as obvious over Klaerner et al. (US Pub 2003/0108879) evidenced by Matyjaszewski et al. (US Pub 2004/0204556) in view of Tanaka et al. (U.S. 2011/0000658) and further in view of Holzl et al. (US Pub 2012/0121861).
Modified Klaerner does not expressly disclose a plating layer. Holzl directed as is Klaerner as modified to brush polymers as disclosed in the abstract and at ¶s 0053, 0085-0094 and 0113-0114 for a modified halogenated polymer surface with a brush polymer from grafting from immobilized initiators on a substrate surface. Such modified halogenated polymer substrate can be used with generating structured metallic thin films on the surface by chemical plating.
One of ordinary skill in the art before the effective filing of the pending patent application would have considered it prima facie obvious as for example at least under rationale G of MPEP § 2141 III and 2143 I G to have from Klaerner as modified a substrate for formation of a polymer brush having of the substrate surface a polymerization initiator layer on the substrate an initiator layer with chloromethylphenyltrimethoxysilane meeting formula I with a second organosilane of phenyltrimethoxysilane under a hydrophilic layer for a polymer brush, where the polymerization initiator layer as an undercoat layer of a hydrolyzed and condensed polymer of chloromethylphenyltrimethoxysilane and metal alkoxide of tetraalkoxysilane with an oriented hydrophilic overcoat such hydrolyzed and condensed polymer of chloromethylphenyltrimethoxysilane and metal alkoxide of tetraalkoxysilane, where from Holzl the brush polymers of the modified halogenated surface has structured metallic thin films plated on the surface motivated to have additional applications for such brush polymers as for the surface material of Claim 9. Furthermore the combination of Holzl with modified Klaerner has reasonable expectation of success to one skilled in the art because both have initiators on substrates with subsequent polymerization from those initiators into brush polymers and their applications.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Blaine Copenheaver whose telephone number is (571)272-1156. The examiner can normally be reached M-F 8-5.
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/BLAINE COPENHEAVER/Primary Examiner, Art Unit 1781
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