DETAILED ACTION
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 08/20/2025 has been entered.
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 .
Applicant filed an Amendment on 08/20/2025. Claims 1 and 9 have been amended. Claims 14-15 have been cancelled. Claim 18 has been added.
Claims 1-3, 5-13 and 16-18 are pending.
Claims 1-3, 5-18 and 16-18 are rejected.
Specification
The disclosure is objected to because of the following informalities:
In response to the previous objection to the specification, the specification at page 16, paragraph beginning at line 2, has been amended to read:
“HLB value = 20 x (percent mass of hydrophilic group/(sum of weight of hydrophilic group/molecular weight of surfactant) Relationship 1”.
This appears to be an incorrect formula or “relationship” for the following reasons. The Griffin formula for determining HLB is known to be:
HLB value = 20 x (molecular weight of hydrophilic group portion) / (molecular weight of a surfactant),
as is evidenced by Nakagawa, US 8733920 B2 at col. 15, lines 35-42.
Amending the term:
“HLB value = 20 x (percent mass of hydrophilic group/(sum of weight of hydrophilic group/molecular weight of surfactant) Relationship 1”
to read:
“The Griffin formula for determining HLB is represented by the following Relationship 1:
HLB value = 20 x (molecular weight of hydrophilic group portion)/(molecular weight of surfactant)”
Basis for this amendment can be found on page 16, paragraph beginning at line 2 of the specification as originally filed. Appropriate correction is required.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1, 3, 7-9, 12-13, 16-17 are rejected under 35 U.S.C. 103 as being unpatentable over Hasegawa et al, US 2014/0036010 A1 (Hasegawa ‘010) in view of Kato, JP 2005/023253A (Kato) and Suzuki et al, US 2019/0077978 A1 (Suzuki).
Kato was cited in the PTO-892, Notice of References Cited, mailed 12/30/2024. The machine English translation of Kato provided with the PTO-892 mailed 12/30/2024 is referenced below. Table 1 of the original JP document is also referenced below.
With respect to claims 1, 7, 9 and 16-17, Hasegawa ‘010 teaches an ink set comprising a cyan ink, a magenta ink, a yellow ink and a black ink, wherein each ink contains at least a pigment, a surfactant, water, a water-soluble organic solvent, and an anionic self-emulsifying ether-based polyurethane, wherein each ink contains, as the pigment, a combination of (i) pigment dispersion liquid wherein the pigment is dispersed by means of a surfactant, and (ii) an aqueous resinous polymer-coated pigment dispersion liquid (Hasegawa ‘010; [0056]). The image density, ejection stability, and liquid stability can be simultaneously realized without sacrificing the dispersion stability by using an anionic self-emulsifying ether-based polyurethane as the resin for the resin emulsion, and a sodium naphthalene sulfonate-formalin condensate (i.e., the claimed compound of Chemical Formula 1), or a compound represented by formula (1), as the surfactant:
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(Hasegawa ‘010; [0065-0066]).
The above compound of General Formula (1) overlaps in scope with the compound of Chemical Formula 2 as claimed when R = a C1-20 alkyl group, an aralkyl group having 7 or 8 carbon atoms, or an allyl group; when l is an integer from 0 to 7; and when n is an integer from 20 to 200.
Glycerin is a preferred water-soluble organic because the presence of it in the ink can offer excellent effects on the prevention of clogging attributable to ink drying, i.e., the prevention of failure of ink-jetting caused by water evaporation, and improved image density (Hasegawa ‘010; [0108]).
Regarding claim 7, film-forming resins include copolymers of styrene and acrylic acid (Hasegawa ‘010; 0086-0089]). See, also, the various examples discussed below wherein the pigments are coated with styrene-acrylic resins as claimed.
Regarding claim 9, carbon black, Pigment Blue 15:3, Pigment Red 122, and Pigment Yellow 74 are both taught and exemplified as preferred inks for use in the ink sets (Hasegawa ‘010; [0095-0100] and Examples as discussed below).
Regarding the Examples:
The Black Pigment Dispersion Liquid comprises carbon black, sodium naphthalene sulfonate-formalin condensate (i.e., a compound of Chemical Formula 1), and water (Hasegawa ‘010; [0143-0144]). The Resinous Polymer-Coated Black Pigment Dispersion Liquid comprises carbon black coated with a styrene-acrylic resin (claim 7) (Hasegawa ‘010; [0145-0146]).
The Cyan Pigment Dispersion Liquid comprises Pigment Blue 15:3, a compound of formula (2) wherein n=40 and water (Hasegawa ‘010; [0147-0148]), wherein the compound of Formula (2) is:
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(i.e., a compound of Chemical Formula 2 as claimed) (Hasegawa ‘010; [0074]).
The Resinous Polymer-Coated Cyan Pigment Dispersion Liquid comprises Pigment Blue 15:3 coated with a styrene-acrylic resin (claim 7) (Hasegawa ‘010; [0149-0150]).
The Magenta Pigment Dispersion Liquid comprises Pigment Red 122, a compound of formula (2) wherein n=40 (i.e., a compound of Chemical Formula 2 as claimed), and water (Hasegawa ‘010; [0151-0152]). The Resinous Polymer-Coated Magenta Pigment Dispersion Liquid comprises Pigment Red 122 coated with a styrene-acrylic resin (claim 7) (Hasegawa ‘010; [0153-0154]).
The Yellow Pigment Dispersion Liquid comprises Pigment Yellow 74, a compound of formula (2) wherein n=40, and water (i.e., a compound of Chemical Formula 2 as claimed) (Hasegawa ‘010; [0155-0156]). The Resinous Polymer-Coated Yellow Pigment Dispersion Liquid comprises Pigment Yellow 74 coated with a styrene-acrylic resin (claim 7) (Hasegawa ‘010; [0157-0158]).
Various variations of these dispersions were made (Hasegawa ‘010; [0159-0242]). The pigment dispersions were then used to make inks, wherein the inks comprise glycerin, an anionic self-emulsifying ether polyurethane XW-75-W920, and water (Hasegawa ‘010; [0244]; [0247], Table 2, “resin emulsion a”; and Tables 3-1 and 3-2, Examples 1-61).
Inkjet printing was performed on gloss paper (Hasegawa ‘010; [0248-0249]). Hasegawa ‘010 further teaches that if the molecular weight of the urethane resin is too high, the effect of imparting gloss is lowered ((Hasegawa ‘010; [0125]).
The inks and prints of the examples were evaluated for image density, ejection stability, and storage stability (Hasegawa ‘010; [0250-0264]). The image density, ejection stability and liquid stability can be realized with the inks of Hasegawa ‘010 ((Hasegawa ‘010; [0054] and [0060]).
Hasegawa ‘010 teaches that additional nonionic surfactants may be used, specifically nonionic surfactants including those of the SURFYNOL series, and silicone-based surfactants (Hasegawa ‘010; [0101-0102]).
Hasegawa ‘010 does not explicitly teach:
a surfactant comprising a first silicone-based compound having a hydrophilic lipophilic balance (HLB) value of from 7.0 to 9.0 and a second silicone-based compound having an HLB value of from 14.0 to 18.0; or
an acetylene-based compound having an HLB value of from 3.0 to 5.0 or 2,4,7,9- tetramethyldecyne-4,7-diol.
With respect to difference 1), Kato teaches a water-based pigment ink for ink-jet recording comprising two or more polysiloxane-based surfactants having different HLB values. At least one is a polysiloxane-based surfactant having an HLB ≥ 8, and at least one is a polysiloxane-based surfactant having an HLB ≤ 8. A recorded image with improved luster and distinctness can be formed using the inks (Kato; Abstract).
By incorporating two or more kinds of polysiloxane-based surfactant having different HLB values into the aqueous inks for inkjet recording, the glossiness and sharpness of the recording image is improved (Kato; page 2, line 45-page 3-line 4, and page 9, lines 4-8). According to a preferred embodiment, a lipophilic polysiloxane-based surfactant having an HLB of 6-8 is used in combination with a hydrophilic polysiloxane-based surfactant having an HLB of 9-25 (Kato; page 3, lines 4-7). Preferably, the recording medium is a glossy media (Kato; page 3, lines 10-11 and page 9, lines 8-12).
The polysiloxane surfactant having an HLB of 6-8 of Kato overlaps in scope with the claimed first silicone-based compound having a hydrophilic lipophilic balance (HLB) value of from 7.0 to 9.0, and the hydrophilic polysiloxane surfactant having an HLB of 9-25 of Kato overlaps in scope with the claimed second silicone-based compound having an HLB value of from 14.0 to 18.0.
As set forth in MPEP 2144.05, in the case where the claimed range “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists, In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
Further, in Table 1, Examples 2 and 4, Kato exemplifies inks comprising a mixture of Silwet L-7002 (HLB=7) (corresponding to the first silicone-based compound having an HLB of from 7-9), and Silwet L-7607N (HLB = 17) (corresponding to the second silicone-based compound having an HLB of from 14-18) (Kato; original JP document; [0047], Table 1, Examples 2 and 4).
When the water-based ink is ejected onto a recording medium, which is preferably a glossy medium, the recording is performed by the action of the lipophilic polysiloxane having a low HLB, and spreads smoothly on the surface of the medium. Because the ink quickly penetrates into the ink receiving layer by the action of the hydrophilic polysiloxane surfactant having a high HLB, the occurrence of uneven gloss is prevented or reduced (Kato; page 10, lines 15-22).
Kato is analogous art as it teaches mixtures of silicone-based surfactants with different HLB’s for use in aqueous pigment-containing inkjet inks.
In light of the motivation provided by Kato, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to add the polysiloxane surfactant mixture of Kato, including a lipophilic polysiloxane surfactant having an HLB of 6 to 8 and a hydrophilic polysiloxane surfactant having an HLB of 9 to 25, such as a mixture of polysiloxane surfactants having HLB’s of 7 and 17 as exemplified by Kato, as the additional nonionic silicone-based surfactant in the inks of Hasegawa ‘010, in order to obtain improved glossiness and sharpness of the recorded image, and thereby arrive at the claimed invention. Because Hasegawa ‘010 recognizes the importance of glossiness and exemplifies printing on glossy paper, those skilled in the art would have been motivated to use the polysiloxane surfactant mixtures of Kato in the inks of Hasegawa ‘010.
With respect to difference 2), Suzuki teaches a water-based ink comprising a pigment, a water-soluble organic solvent, and a surfactant (A), wherein surfactant (A) comprises an acetylenediol-based surfactant (a1) having an HLB value determined by Griffin’s method of 3 or less (Suzuki; [0014]). In one embodiment, the surfactant (A) also contains a polysiloxane-based surfactant (a3) having an HLB of 8-20 (Suzuki; [0016]).
The acetylenediol-based surfactant (a1) having an HLB of 3 or less orients at the surface of the ink droplets within an extremely short period of time of not more than tens of microseconds from the point when the ink impacts the printing substrate, thereby dramatically improving the ink wetting properties and enabling suppression of coalescence of the ink droplets in the initial period following the impact. Further, the acetylenediol-based surfactant (a1) allows the ink droplets to undergo rapid wet spreading that yields an increase in surface area, thereby improving the efficiency of the drying process and penetration into the substrate, also contributing better suppression of coalescence of the ink droplets (Suzuki; [0035] and [0040]). Suzuki teaches 2,4,7,9-tetramethyl-5-decyne-4,7-diol as a preferred acetylenediol-based surfactant (claims 16-17) (Suzuki; [0042-0043] and [0129]). As is evidenced on page 18, lines 19-21, of Applicant’s specification, 2,4,7,9-tetramethyl-5-decyne-4,7-diol is sold under the trade name Surfynol AD01, i.e., it is a SURFYNOL series surfactant.
The pigments include Pigment Blue 15:3; Pigment Yellow 74, Pigment Red 122 and carbon black, wherein the pigments may be coated with styrene/acrylic resins (Suzuki; [0111-0114], [0119] and [0120]).
Suzuki is analogous art as it teaches aqueous, pigment-containing inks comprising an acetylene-based compound having an HLB of 3 or 2,4,7,9-tetramethyldecyne-4,7-diol as claimed.
In light of the motivation provided by Suzuki, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to add an acetylenediol-based surfactant having an HLB of 3 or less as the additional nonionic surfactant in the inks of Hasegawa ‘010 in view of Kato, wherein said acetylenediol-based surfactants overlap in scope with the claimed acetylene-based compounds having an HLB of 3 to 5, in order to dramatically improve the ink wetting properties and enable suppression of coalescence of the ink droplets in the initial period following the impact, and in order to improve the efficiency of the drying process and penetration into the substrate.
As set forth in MPEP 2144.05, in the case where the claimed range “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists, In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
Further, given that Suzuki discloses the acetylenediol-based surfactants that includes the presently claimed Surfynol series 2,4,7,9-tetramethyl-5-decyne-4,7-diol, it therefore would be obvious to one of ordinary skill in the art to use the 2,4,7,9-tetramethyl-5-decyne-4,7-diol, which is both disclosed by Suzuki and encompassed within the scope of the present claims, and thereby arrive at the claimed invention.
Regarding claim 3, Hasegawa ‘010 in view of Kato and Suzuki are relied upon as teaching the limitations of claim 1 as discussed above. Kato teaches that the weight ratio of the hydrophilic polysiloxane surfactant content / lipophilic polysiloxane surfactant content is 1/2 to 2/1 (Kato; page 3, lines 7-10). Therefore, a ratio of the second silicone-based compound to the first silicone-based compound as claimed is 1/2 to 2/1. Reversing, a ratio of the first silicone-based compound to the second silicone-based compound is 2/1 to 1/2 (i.e., 0.5-2.0), which overlaps in scope with the claimed ratios of 2:8 to 4:6 (i.e., 0.25-0.67). If the ratio is less than 1/2 or exceeds 2/1, the effect of improving good glossiness and sharpness may be reduced (Kato; page 3, line 48-page 4, line 2).
In Table 1, Example 4, Kato exemplifies inks comprising a mixture comprising 0.1 parts Silwet L-7002 (HLB=7) (corresponding to the first silicone-based compound having an HLB of from 7-9), and 0.2 parts Silwet L-7607N (HLB = 17) (corresponding to the second silicone-based compound having an HLB of from 14-18) (Kato; original JP document; [0047], Table 1, Example 4). Therefore, Kato exemplifies a ratio of the first silicone-based compound to the second silicone-based compound of 0.1:0.2 or 0.5, which falls within the claimed mass ratios.
Regarding claim 8, Hasegawa ‘010 in view of Kato and Suzuki are relied upon as teaching the limitations of claim 1 as discussed above. Suzuki teaches that the pigment may be dispersed without a dispersant by modifying the surface of pigment using a resin coating (Suzuki; [0119]). The weight ratio between the pigment and the dispersing resin is preferably from 2/1 to 100/1. By maintaining these ratios, the dispersibility, viscosity and dispersion stability is improved. The most preferred ratio of pigment/resin is 20/7 to 20/1 (Suzuki; [0125]). Therefore, the ratio of resin to pigment is 7/20 to 1/20, or 0.35 to 0.05. This range is equivalent to the claimed range of 0.05 to 0.35.
Regarding claims 12-13, Hasegawa ‘010 in view of Kato and Suzuki are relied upon as teaching the limitations of claim 1 as discussed above. Hasegawa ‘010 teaches the ink is housed in an ink cartridge (i.e., a container accommodating the ink). The inks are fed into a recording head (i.e., an inkjet head) from the cartridge (Hasegawa ‘010; [0132]). The nozzle plate has a silicone resin-containing ink repellent layer, whereby fixation to a nozzle plate can be prevented and ejection stability improved (Hasegawa ‘010; [0127]). In the examples, the inks are inkjet printed with an inkjet printer, wherein a nozzle check pattern was printed (i.e., the inks are ejected through a nozzle in a pattern to enable a nozzle check) onto gloss paper (i.e., a substrate) (Hasegawa ‘010; [0248-0249]). From the teachings of Hasegawa ‘010, it is clear that the nozzle plate of Hasegawa ‘010 has a nozzle through which the ink is discharged and an ink repulsion layer on the discharge surface because fixation of the ink to the nozzle plate can be prevented and ejection stability through the nozzle is improved.
Claim 2 is rejected under 35 U.S.C. 103 as being unpatentable over Hasegawa ‘010 in view of Kato and Suzuki as applied to claim 1 above, and further in view Unemura et al, US 2019/0185690 A1 (Unemura).
Unemura was cited in the PTO-892, Notice of References Cited, mailed 12/30/2024.
Regarding claim 2, Hasegawa ‘010 in view of Kato and Suzuki are relied upon as teaching the limitations of claim 1 as discussed above, wherein the inks comprise a lipophilic polysiloxane-based surfactant having an HLB of 6 to 8 and a hydrophilic polysiloxane-based surfactant having an HLB of 9-25 (Kato; page 3, lines 4-7). The polysiloxane is preferably represented by formula (1):
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wherein R1 to R9 are each independently an alkyl group having 1-4 carbon atoms, R10 is a C1-4 alkyl group or hydrogen, and a, b, m and n are each an integer of 0 or more (Kato; page 4, lines 1-10). These polysiloxanes overlap in scope with those of Chemical Formula 3 as claimed when R1 to R9 is methyl, a is 0-23, b is 0-23, and R10 is a C1-4 alkyl group or hydrogen.
Given that Sato discloses polysiloxane surfactants the that overlap the presently claimed first silicone-based compounds, including those of Chemical Formula 3 as claimed, it therefore would be obvious to one of ordinary skill in the art to use a silicone-based compound of Chemical Formula 3 as a silicone-based surfactant in the inks of Hasegawa ‘010 in view of Kato and Suzuki, which is both disclosed by Sato and encompassed within the scope of the present claims, and thereby arrive at the claimed invention.
Hasegawa ‘010 in view of Kato and Suzuki does not explicitly teach a second silicone-based compound of Chemical Formula 4 as claimed.
With respect to the difference, Umemura teaches inks comprising at least one polyether-modified siloxane compound and at least one aliphatic alcohol alkylene oxide compound (Umemura; [0017]). The polyether-modified siloxanes include at least one compound of Chemical formula I:
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(Umemura; [0019-0020]). Inclusion of the polyether-modified siloxane improves discharge stability by reducing ink attachment to the nozzle, and reduces beading on printing paper, including plain paper (Umemura; [0055]).
A polyether-modified siloxane other than the compound of Chemical formula I can be used to maintain: 1) dispersion stability, 2) low dynamic surface tension, 3) permeability, and 4) leveling properties, irrespective of the kind of coloring material and organic solvent used (Umemura; [0056-0057]). The additional polyether-modified siloxane includes compounds of Chemical Formula IX (Umemura; [0058]):
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Chemical Formula IX is equivalent to the claimed second silicone-based compound of Chemical formula 4 as claimed.
Umemura’s preferred commercially available siloxanes include SILFACE SAG 503A (Umemura; [0080]). As is evidenced on page 29, lines 27-28 of Applicant’s specification, SAG 503A is a compound represented by Chemical Formula 4 with an HLB=14.0.
Umemura is analogous art in that it teaches inkjet printing inks comprising polysiloxane surfactant mixtures.
In light of the motivation provided by Umemura, it would have been obvious to one of ordinary skill in the art to add a siloxane compound of Chemical IX (i.e., a silicone of Chemical Formula 4 as claimed), such as the preferred SAG 503A, as one of the polysiloxane surfactants in the inks of Hasegawa ‘010 in view of Kato and Suzuki, in order to obtain dispersion stability, low dynamic surface tensions, permeability, and good leveling properties, irrespective of the kind of coloring material and organic solvent used, and thereby arrive at the claimed invention.
Claims 5-6 are rejected under 35 U.S.C. 103 as being unpatentable over Hasegawa ‘010 in view of Kato and Suzuki as applied to claim 1 above, and further in view Hasegawa et al, US 2012/0062646 A1 (Hasegawa ‘646).
Regarding claims 5-6, Hasegawa ‘010 in view of Kato and Suzuki are relied upon as teaching the limitations of claim 1 as discussed above. Hasegawa ‘010
teaches that the inks contain an anionic self-emulsifying ether-based polyurethane in order to thicken or agglomerate the ink upon impact on a recording medium such as paper, suppress the penetration of colorant ingredients, accelerate the fixation of the colorant ingredients on the paper, obtain improved film-forming on paper, improved rub-fastness, and improved dispersion stability of the pigment (Hasegawa ‘010; Abstract and [0114]). Hasegawa ‘001 teaches that the acid value of the anionic self-emulsifying ether polyurethane resin is preferably 40 or more, more preferably 70 or more from the viewpoint of storage and ejection stability (Hasegawa ‘010; [0125]). Hasegawa ’01 exemplifies using the commercially available XW-75-W930 with an acid value of 66 as the polyurethane resin (Hasegawa ‘010; [0247] and Table 2).
Hasegawa ‘010 Kato and Suzuki does not explicitly teach a polyether-based urethane resin of Chemical Formula 5 (claim 5), wherein the polyether-based urethane resin of Chemical Formula 5 has an acid value of form 48 to 80 KOH.
With respect to the difference, Hasegawa ‘646 teaches an ink set comprising at least a black ink and a color pigment ink, wherein the black pigment ink contains a first anionic self-emulsifying ether polyurethane resin having an acid value of 65 mgKOH/g to 85 mgKOH/g, and the at least one color pigment ink of every color contains a second anionic self-emulsifying ether polyurethane resin having an acid value 10 mgKOH/g to 40 mgKOH/g lower than that of the first anionic self-emulsifying ether polyurethane resin contained in the black pigment ink (Hasegawa ‘646; Abstract).
In Table 1, Hasegawa ‘646 lists the commercially available anionic self-emulsifying ether polyurethane resin XW-75-“W932” of Mitsui Chemical with an acid value of 80, and “W5661” of Mitsui Chemical with an acid value of 48 (Hasegawa ‘646; Table 1 on page 6, col. 1). As is evidenced on page 14, lines 11-13 and page 29, lines 5-8 of Applicant’s specification, TAKELAC “W5661” and “W932” manufactured by Mitsui Chemicals are procurable polyether-based resins of Chemical Formula 5 as claimed, having acid values of 48 and 80 KOHmg/g respectively.
Hasegawa ‘646 is analogous art as it teaches aqueous inkjet inks comprising pigments and an anionic self-emulsifying ether polyurethane resin.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to select a commercially available anionic self-emulsifying ether polyurethane resin having an acid value of 40 KOHmg/g or more, preferably 70 or more from the viewpoint of ejection and storage stability, for use in the inks of Hasegawa ‘010 in view of Kato and Suzuki. In doing so, one skilled in the art would have looked to Hasegawa ‘646 which teaches that commercially available anionic self-emulsifying ether polyurethane resins for use in aqueous inkjet inks include “W5661” which has an acid value of 48 KOH mg/g and XW-75-“W932” which has an acid value of 80 KOH mg/g. It would have been obvious to one of ordinary skill in the art to therefore select the commercially available W5661 or W932 as the anionic self-emulsifying polyether polyurethane resin in the inks of Hasegawa ‘010 in view of Kato and Suzuki because such commercially available polyurethane resins fall within the preferred acid values as taught by Hasegawa ‘010.
Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over Hasegawa ‘010 in view of Kato and Suzuki as applied to claim 9 above, and further in view of Kato et al, US 2008/0079793 A1 (Kato ‘793).
Kato ‘793 was cited in the PTO-892, Notice of References Cited, mailed 12/30/2024.
Regarding claim 10, Hasegawa ‘010 in view of Kato and Suzuki are relied upon as teaching the limitations of claim 9 as discussed above.
Hasegawa ‘010 in view of Kato and Suzuki does not teach an ink set wherein the surface tension of the black ink is at least 3 mN/m greater than a surface tension of each of the cyan, magenta and yellow inks.
With respect to the difference, Kato ‘793 teaches ink sets having black, yellow, magenta and cyan inks, wherein the dynamic surface tension of the yellow, magenta and cyan inks is from 35-40mN/m, and the dynamic surface tension of the black ink is from 40-45mN/m (Kato; Abstract). These surface tensions overlap with the claimed range wherein the cyan, magenta and yellow ink each independently have a surface tension by 3mN/m or greater less than that of the black ink. By using a black ink with said surface tensions, feathering may be restrained and good drying is obtained (Kato; [0008] and [0017]. By using color inks with surface tensions of 35-40mN/m, print quality is improved, drying properties are improved, and there is reduced bleeding between the black and color inks (Kato [0018]). Kato exemplifies inks using carbon black, C.I. Yellow 74, C.I. Pigment Red 122, and C.I. Pigment Blue 15:3 (Kato; pages 4-5, Tables 1-2).
Kato ‘793 is analogous art in that it teaches ink sets for ink jet printing comprising carbon black, C.I. Yellow 74, C.I. Pigment Red 122, and C.I. Pigment Blue 15:3.
In light of the motivation provided by Kato ‘793, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to adjust the surface tensions of the color inks of Hasegawa ‘010 in view of Kato and Suzuki to 35-40mN/m, and the black ink to 40-45mN/m, in order to obtain reduced feathering, improved drying properties, improved print quality and reduced bleeding between the black and color inks.
As set forth in MPEP 2144.05, in the case where the claimed range “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists, In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over Hasegawa ‘010 in view of Kato and Suzuki as applied to claim 9 above, and further in view Koga et al, US 2002/0180856 A1 (Koga).
Koga was cited in the PTO-892, Notice of References Cited, mailed 12/30/2024.
Regarding claim 11, Hasegawa ‘010 in view of Kato and Suzuki are relied upon as teaching the limitations of claim 9 as discussed above.
Hasegawa ‘010 in view of Kato and Suzuki does not teach an ink set wherein a solubility parameter of the black ink is at least 1.0 (J/cm3)0.5 greater than a solubility parameter of each of the cyan, magenta and yellow inks.
With respect to the difference, Koga teaches an ink set for ink jet recording comprising a first ink containing water, a coloring agent, and a water-soluble organic solvent, and a second ink containing water, a second coloring agent, and a water-soluble organic solvent (Koga; 0008-0010]). The solubility parameter of the organic solvent of the first and second inks satisfy the relationship 4>l δ1- δ2 l, wherein δ1 is the solubility parameter of the organic solvent in the first ink and δ2 is the solubility parameter of the organic solvent in the second ink, and wherein the first ink is a black ink and the second ink is a color ink (Koga; [0011-0012]). In other words, the difference between the solubility parameter of the black ink and the color ink is at least four, wherein the black ink has the higher solubility parameter. The ink set may further comprise third and fourth coloring agents, wherein the coloring agents may be pigments (Koga; [0012], [0018-0020]). By adjusting the solubility parameters of the inks, bleeding between the black ink and the color ink is reduced, even when recorded on plain paper (Koga; Abstract and [0012]). Although no units are given for the solubility parameters, because the difference is at least 4 (regardless of units), it is clear that Koga meets the claimed limitation wherein the black ink is at least 1.0 (J/cm3)0.5 greater than a solubility parameter of each of the color inks.
Koga is analogous art as it teaches aqueous ink sets for inkjet printing.
In light of the motivation to adjust the solubility parameters of the inks as taught by Koga, it would have been prima facie obvious to one of ordinary skill in the art to adjust the solubility parameters of the black and color inks of the ink sets of Hasegawa ‘010 in view of Kato and Suzuki such that the difference between the black and color ink solubility parameters is at least 4, thereby arriving at the claimed invention, in order to obtain decreased color bleeding between the black and color inks, even when printed on plain paper.
Claim 18 is rejected under 35 U.S.C. 103 as being unpatentable over Hasegawa et al, US 2014/0036010 A1 (Hasegawa ‘010) in view of Kato, JP 2005/023253A (Kato).
With respect to claim 18, Hasegawa ‘010 teaches an ink set comprising a cyan ink, a magenta ink, a yellow ink and a black ink, wherein each ink contains at least a pigment, a surfactant, water, a water-soluble organic solvent, and an anionic self-emulsifying ether-based polyurethane, wherein each ink contains, as the pigment, a combination of (i) pigment dispersion liquid wherein the pigment is dispersed by means of a surfactant, and (ii) an aqueous resinous polymer-coated pigment dispersion liquid (Hasegawa ‘010; [0056]). The image density, ejection stability, and liquid stability can be simultaneously realized without sacrificing the dispersion stability by using an anionic self-emulsifying ether-based polyurethane as the resin for the resin emulsion, and a sodium naphthalene sulfonate-formalin condensate (i.e., the claimed compound of Chemical Formula 1), or a compound represented by formula (1), as the surfactant (Hasegawa ‘010; [0065-0066]):
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The above compound of General Formula (1) overlaps in scope with the compound of Chemical Formula 2 as claimed when R = a C1-20 alkyl group, an aralkyl group having 7 or 8 carbon atoms, or an allyl group; when l is an integer from 0 to 7; and when n is an integer from 20 to 200.
Glycerin is a preferred water-soluble organic because the presence of it in the ink can offer excellent effects on the prevention of clogging attributable to ink drying, i.e., the prevention of failure of inkjetting caused by water evaporation, and improved image density (Hasegawa ‘010; [0108]).
Hasegawa ‘010 exemplifies making various pigment dispersions comprising a pigment, water, and either sodium naphthalene sulfonate-formalin condensate (i.e., a compound of Chemical Formula 1 as claimed) (Hasegawa ‘010; [0143-0146]), or a compound of Formula (2):
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(i.e., a compound of Chemical Formula 2 as claimed) (Hasegawa ‘010; [0074] and [0149-0158]).
Various variations of these dispersions were made (Hasegawa ‘010; [0159-0242]). The pigment dispersions were then used to make inks, wherein the inks comprise glycerin, an anionic self-emulsifying ether polyurethane XW-75-W920, and water (Hasegawa ‘010; [0244]; [0247], Table 2, “resin emulsion a”; and Tables 3-1 and 3-2, Examples 1-61).
Inkjet printing was performed on gloss paper (Hasegawa ‘010; [0248-0249]). Hasegawa ‘010 further teaches that if the molecular weight of the urethane resin is too high, the effect of imparting gloss is lowered ((Hasegawa ‘010; [0125]).
The inks and prints of the examples were evaluated for image density, ejection stability, and storage stability (Hasegawa ‘010; [0250-0264]). The image density, ejection stability and liquid stability can be realized with the inks of Hasegawa ‘010 ((Hasegawa ‘010; [0054] and [0060]).
Hasegawa ‘010 teaches that additional nonionic surfactants may be used, specifically nonionic surfactants including silicone-based surfactants (Hasegawa ‘010; [0101-0102]).
Hasegawa ‘010 does not explicitly teach a surfactant comprising a first silicone-based compound having a hydrophilic lipophilic balance (HLB) value of from 7.0 to 9.0 and a second silicone-based compound having an HLB value of from 14.0 to 18.0.
With respect to difference, Kato teaches a water-based pigment ink for ink-jet recording comprising two or more polysiloxane-based surfactants having different HLB values. At least one is a polysiloxane-based surfactant having an HLB ≥ 8, and at least one is a polysiloxane-based surfactant having an HLB ≤ 8. A recorded image with improved luster and distinctness can be formed using the inks (Kato; Abstract).
By incorporating two or more kinds of polysiloxane-based surfactants having different HLB values into the aqueous inks for inkjet recording, the glossiness and sharpness of the recording image is improved (Kato; page 2, line 45-page 3-line 4, and page 9, lines 4-8). According to a preferred embodiment, a lipophilic polysiloxane-based surfactant having an HLB of 6 to 8 is used in combination with a hydrophilic polysiloxane-based surfactant having an HLB of 9-25 (Kato; page 3, lines 4-7). Preferably, the recording medium is a glossy media (Kato; page 3, lines 10-11 and page 9, lines 8-12).
The polysiloxane surfactant having an HLB of 6 to 8 of Kato overlaps in scope with the claimed first silicone-based compound having a hydrophilic lipophilic balance (HLB) value of from 7.0 to 9.0, and the hydrophilic polysiloxane surfactant having an HLB of 9 to 25 of Kato overlaps in scope with the claimed second silicone-based compound having an HLB value of from 14.0 to 18.0.
As set forth in MPEP 2144.05, in the case where the claimed range “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists, In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
Further, in Table 1, Examples 2 and 4, Kato exemplifies inks comprising a mixture of Silwet L-7002 (HLB=7) (corresponding to the first silicone-based compound having an HLB of from 7-9), and Silwet L-7607N (HLB = 17) (corresponding to the second silicone-based compound having an HLB of from 14-18) (Kato; original JP document; [0047], Table 1, Examples 2 and 4).
When the water-based ink is ejected onto a recording medium, which is preferably a glossy medium, the recording is performed by the action of the lipophilic polysiloxane having a low HLB, and spreads smoothly on the surface of the medium. Because the ink quickly penetrates into the ink receiving layer by the action of the hydrophilic polysiloxane surfactant having a high HLB, the occurrence of uneven gloss is prevented or reduced (Kato; page 10, lines 15-22).
Kato is analogous art as it teaches mixtures of silicone-based surfactants with different HLB’s for use in aqueous, pigment-containing inkjet inks.
In light of the motivation provided by Kato, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to add the polysiloxane surfactant mixture of Kato, including a lipophilic polysiloxane surfactant having an HLB of 6 to 8 and a hydrophilic polysiloxane surfactant having an HLB of 9 to 25, such as a mixture of polysiloxane surfactants having HLB’s of 7 and 17 as exemplified by Kato, as the additional nonionic silicone-based surfactant in the inks of Hasegawa ‘010, in order to obtain improved glossiness and sharpness of the recorded image, and thereby arrive at the claimed invention. Because Hasegawa ‘010 recognizes the importance of glossiness and exemplifies printing on glossy paper as discussed above, those skilled in the art would have been motivated to use the polysiloxane surfactant mixtures of Kato in the inks of Hasegawa ‘010.
Response to Arguments
Applicant’s Remarks regarding the 35 U.S.C. §103 rejections over Aoyama et al. U.S. 2013/0115431 in view of Yokohama et al. U.S. 2009/0041940; and the 35 U.S.C. §103 rejections over Aoyama in view of Yokohama, and further view of Umemura et al. U.S. 2019/0185690, are deemed persuasive to overcome the rejections previously of record.
Specifically, claims 1 and 9 as amended, and new claim 18, require that the water-soluble organic solvent comprises glycerin. As Aoyama discloses at paragraph [0070]:
“The ink composition of the invention does not substantially contain alkyl polyols having a boiling point at one atmosphere of 280.degree. C. or more. If an ink composition contains alkyl polyols having a boiling point at one atmosphere of 280.degree. C. or more, the drying property of the ink composition is considerably decreased not only to cause considerable uneven density defects in an image recorded on various recording media, in particular, on a non-ink-absorbing or low-ink-absorbing recording medium but also to cause a decrease in fixability of the image. Examples of the alkyl polyols having a boiling point at one atmosphere of 280.degree. C. or more include glycerin having a boiling point at one atmosphere of 290.degree. C.”
It is clear that Aoyama does not include glycerin as currently claimed in the ink compositions. Therefore, the above cited rejections have been withdrawn.
Applicant’s arguments with respect to the 35 U.S.C. §103 rejection over Hasegawa et al. U.S. 2013/0258007 in view of Aoyama et al. U.S. 2013/0115431, 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.
With respect to the 35 U.S.C. §103 rejections over Hasegawa in view of Aoyama and in further view of Umemura et al. U.S. 2019/0185690, Kato et al. U.S. 2008/0079793, or Koga et al. U.S. 2002/0180856, Applicant primarily argues that Umemura, Kato and Koga cannot cure the deficiencies of Hasegawa and Aoyama. Because the new grounds of rejection does not rely upon Hasegawa et al. U.S. 2013/0258007 or Aoyama et al. U.S. 2013/0115431, these remarks are also considered moot.
See, however, the new grounds of rejection under 35 U.S.C. §103 over Hasegawa et al, US 2014/0036010 A1 (Hasegawa ‘010) in view of Kato, JP 2005/023253A (Kato) and Suzuki et al, US 2019/0077978 A1 (Suzuki); and over Hasegawa in view of Kato and Suzuki, and further in view Umemura, Hasegawa ‘646, Kato ‘793 or Koga, as set forth above.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. However, rejections using these references would be cumulative to the above rejections.
Namba et al, US 2010/0279035 A1, exemplifies an ink composition comprising a compound of Chemical formula 2, Pigment Red 122, the polyether urethane emulsion W-5661 and glycerin ([0248-0249] and [0294]).
JP 2017190418 A, exemplifies inks comprising pigments, polyoxyethylene (n=40)-β-naphthyl ether as a dispersant, polyether polyurethane particles Takelac W-5661, and glycerin (Examples 1-7). The compositions may also comprise a silicone surfactant including those of Formula (S-1) (page 9, lines 1-20).
Wakabayashi et al, US 2015/0337149 A1, teaches that 2,4,7,9-tetramethyl-5-decyne-4,7-diol improves the wetting spread of water-based ink and suppresses image unevenness of printed images when printing on low-water absorbing recording media [0029-0030].
Hasegawa et al, US 2013/0258005 A1, teaches W-5661 as a commercially available anionic self-emulsifying polyether-modified polyurethane resin for use in inkjet inks [0067-0068].
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/CDL/Examiner, Art Unit 1732
/CORIS FUNG/Supervisory Patent Examiner, Art Unit 1732