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 .
The responses of the applicant has been read and given careful consideration. Rejections of the previous office action, not repeated below are withdrawn based upon the arguments and amendments of the applicant. Responses to the arguments are presented after the first rejection they are directed to.
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
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 8-12 are rejected under 35 U.S.C. 103 as being unpatentable over Shibayama et al. WO 2019082934, in view of Shirakawa et al. WO 2016208300
Shibayama et al. WO 2019082934 in synthesis example 11, charges a 300 ml flask with 22.9 g of tetraethoxysilane, 6.7 g of methyltriethoxysilane, 2.2 g of p-ethoxyethoxyphenyltrimethoxysilane, and 48.2 g of acetone, and the mixed solution is stirred with a magnetic stirrer. A mixed solution of 19.6 g of 0.2 M nitric acid aqueous solution and 0.33 g of dimethylaminopropyltrimethoxysilane was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 85 ° C. and refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added, and acetone, methanol, ethanol and water were distilled off under reduced pressure and concentrated to obtain an aqueous solution of hydrolytic condensate (polymer). Further, propylene glycol monomethyl ether was added, and the solvent ratio of 100% of propylene glycol monomethyl ether was adjusted to be 13% by weight in terms of solid residue at 140 ° C. The obtained polymer corresponds to formula (A-11), and the weight average molecular weight by GPC is Mw 1600 in terms of polystyrene [0123]. The composition for forming a resist underlayer film 11 is prepared by mixing the polysiloxane (polymer) 11, maleic acid and the solvent obtained in the above synthesis example in the proportions shown in Table 1 and filtering with a 0.1 μm fluororesin filter. did. The addition ratio of the polymer in Table 1 indicates the addition amount of the polymer itself, not the addition amount of the polymer solution (page 86, [0136-0137]). The Si-containing resist underlayer film forming compositions prepared in Examples 1 to 22 and Comparative Examples 1 and 2 were coated on a silicon wafer using a spinner. The substrate was heated on a hot plate at 215 ° C. for 1 minute to form a Si-containing resist underlayer film. Thereafter, a solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 7/3 was applied onto the Si-containing resist underlayer film, spin-dried, and the presence or absence of a change in film thickness before and after the solvent application was evaluated. A film thickness change of 1% or less was "good", and a film thickness change of 1% or more was "not cured" [0142]. Specific examples of the hydrolyzable silane represented by the formula (2) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, Tetraacetoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, Methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyl Lychlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltrimethoxysilane Ethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyl triethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyl trichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyPhenyltriacetoxysilane, ethoxyphenyltrichlorosilane, Ethoxybenzyltrimethoxysilane, Ethoxybenzyltriethoxysilane, Ethoxybenzyltriacetoxysilane, Ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyl Trichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyl Triacetoxysilane, t-Butoxyphenyltrichlorosilane, t-Butoki Cybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxycyclohexyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyl Trichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3, 3, 3-Trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-Mercaptopo Ropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldisilane Ethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxy Silane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, acetoxymethyltrimethoxy Silane, acetoxyethyltrimethoxysilane, acetoxypropyltrimethoxysilane, acetoxymethyltriethoxysilane, acetoxyethyltriethoxysilane, acetoxypropyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriacetoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane Silanes, cyclohexyltriacetoxysilane, cyclohexyltributoxysilane, cyclohexyltripropoxysilane, cyclohexyltriyloxysilane, cyclohexyltriphenoxysilane, triethoxysilylpropyldiallylisocyanurate, glycidoxypropyltrimethoxysilane, phenylsulfonylpropyltriethoxy Silane, bicyclo (2, 2, 2 ) Hept-5-en - yl triethoxysilane, cyclohexyl epoxy ethyltrimethoxysilane, trifluoroacetamido triethoxysilane, p-ethoxyethoxy phenyltrimethoxysilane, triethoxy silyl propyl succinic anhydride, and the like [0051]. These are embraced by the formula
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R .sup.1 represents an organic group having a primary amino group, a secondary amino group, or a tertiary amino group, and is bonded to a silicon atom by a Si-C bond . In R .sup.1 , at least one primary amino group, secondary amino group or tertiary amino group is required in the organic group, and for example, 2, 3, 4, 5 amino groups You can have In this case, at least one primary amino group, secondary amino group or tertiary amino group is required. In addition, a hydrolysis condensation product in which a hydrolyzable silane having a tertiary amino group is hydrolyzed with a strong acid to form a counter cation having a tertiary ammonium group can be preferably used [0006]. Other similar containing monomers which are useful are those bounded by formulae 2 and 3 on page 5.
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In the hydrolyzable silane represented by the formula (2), R .sup.4 in the formula (2) is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, an acyloxyalkyl group, Or an organic group which is an organic group having an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, a hydroxyl group, an alkoxy group, an ester group, a sulfonyl group, or a cyano group, or a combination thereof, and R .sup.5 is bonded to a silicon atom through a C bond, R .sup.5 represents an alkoxy group, an acyloxy group or a halogen group, and c represents an integer of 0 to 3 [0006].
In the hydrolyzable silane represented by the formula (3), R .sup.6 represents an alkyl group in the formula (3) and is bonded to a silicon atom by a Si-C bond, and R .sup.7 is an alkoxy group And an acyloxy group or a halogen group, Y represents an alkylene group or an arylene group, d represents an integer of 0 or 1, and e represents an integer of 0 or 1.In addition to the nitrogen atom constituting the amino group, the organic group may contain a hetero atom such as an oxygen atom or a sulfur atom.R .sup.2 represents an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, an acyloxyalkyl group, or an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, a hydroxyl group, an alkoxy group It represents an organic group having a group, an ester group, a sulfonyl group, or a cyano group, or a combination thereof, and is bonded to a silicon atom through a Si—C bond. R .sup.3 represents an alkoxy group, an acyloxy group or a halogen group. a represents an integer of 1, b represents an integer of 0 to 2, and a + b represents an integer of 1 to 3. The hydrolysis catalysts can be used in amounts of 0.0001-10 mol/mol or hydrolysable group [0058]
Shirakawa et al. WO 2016208300 teaches silicon containing resist underlayers and photoresists. The use of filters of polytetrafluoroethylene, polyethylene or nylon with pore sizes of 0.1 micron or less is disclosed [0334, 0368]
Shibayama et al. WO 2019082934 does not exemplify the embodiments of the method claims where the hydrolyzed silane polymer includes a compound of 1-2 to 1-15 or 1-18 to 1-22, the silane (a) is present in amounts of 7-50 mol% of the total silane content or the hydrolyzed silane undercoatings are filtered using a polar group containing filter.
It would have been obvious to one skilled in the art to modify the processes of Shibayama et al. WO 2019082934 by replacing the p-ethoxyethoxy phenyltrimethoxysilane with any of methoxybenzyltrimethoxysilane, methoxybenzyltrimethoxysilane Ethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyl triethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyl trichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyPhenyltriacetoxysilane, ethoxyphenyltrichlorosilane, Ethoxybenzyltrimethoxysilane, Ethoxybenzyltriethoxysilane, Ethoxybenzyltriacetoxysilane, Ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyl Trichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane and isopropoxybenzyltrichlorosilane based upon the equivalence at [0051] and increasing the proportion of this silane from 5 mol% of the total silane content to between 7 and 50 mol% based upon this being within the 99.9 to 30 mol% content for silanes other than the (amino containing) silane of formula (I) disclosed at [0047], reducing the nitric acid content to 0.001-0.1 moles/mole hydrolysable based upon the curing catalyst can be 0.0001 to 10 moles/mole of hydrolysis group [0058] and filtering the underlayer coatings with a nylon filter which is taught by Shirakawa et al. WO 2016208300 as equivalent to polytetrafluoroethylene or polyethylene filters used or disclosed by Ogihara et al. 20160064220 with a reasonable expectation of forming a useful coating solution and patterned resist upon the applied underlayer coating solution.
Further, it would have been obvious to one skilled in the art to replace the other silane monomers used with other monomers bounded by formulae 2 or 3 of on page 5 Shibayama et al. with a reasonable expectation of forming a useful underlayer.
Alternatively, it would have been obvious to one skilled in the art to modify the processes of Shibayama et al. WO 2019082934 by replacing the p-ethoxyethoxy phenyltrimethoxysilane with monomers similar to any of methoxybenzyltrimethoxysilane, methoxybenzyltrimethoxysilane Ethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyl triethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyl trichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyPhenyltriacetoxysilane, ethoxyphenyltrichlorosilane, Ethoxybenzyltrimethoxysilane, Ethoxybenzyltriethoxysilane, Ethoxybenzyltriacetoxysilane, Ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyl Trichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane and isopropoxybenzyltrichlorosilane based upon the equivalence at [0051] where the hydrolysable alkoxy groups bonded directly to the silicon aton are replaced with a hydrolysable acryloxy or hydrolyzable halogen group as discussed at [0006] of WO 2019082934 and increasing the proportion of this silane from 5 mol% of the total silane content to between 7 and 50 mol% based upon this being within the 99.9 to 30 mol% content for silanes other than the (amino containing) silane of formula (I) disclosed at [0047] ], reducing the nitric acid content to 0.001 to 0.1 mole/mole of hydrolysable group based upon the 0.001 to 10 mole./mole or hydrolysable moieties taught at [0058] and filtering the underlayer coatings with a nylon filter which is taught by Shirakawa et al. WO 2016208300 as equivalent to polytetrafluoroethylene or polyethylene filters used or disclosed by Ogihara et al. 20160064220 with a reasonable expectation of forming a useful coating solution and patterned resist upon the applied underlayer coating solution.
Further, it would have been obvious to one skilled in the art to replace the other silane monomers used with other monomers bounded by formulae 2 or 3 of on page 5 Shibayama et al. with a reasonable expectation of forming a useful underlayer.
In the arguments of 6/10/2025, the applicant establishes that the p-ethoxyethoxyphenyltrimethoxysilane is only used in 5% of the total silanes. The calculation appears to ignore the 0.33 g of dimethylaminopropyltrimethoxysilane. The examiner agrees that the example is outside the range currently recited in the claims, but the reference allows for silanes other than embraced by formula (I) of that application to be used in amounts of 99.9 to 30 mol% which embraces the range set forth in the claims. There does not appear to be any criticality for the 7-50 mole% established in the instant specification. The range for the silane of formula (I) of the instant specification is 1-50 mol%, 3-50 mol%, 5-50 mol%, 7-50 mol%, 7-40 mol%, 7-35 mol%, 7-30 mol% or 7-20 mol%, at [0021], but does not seem to establish any unexpected results for the narrower ranges.
In the response of 10/24/2025, the applicant argues the Shibayama fails to describes et al. of the (recited) starting materials with the protected phenolic group . The examiner points out that Shibayama et al. WO 2019082934 in synthesis example 11, charges a 300 ml flask with 22.9 g of tetraethoxysilane, 6.7 g of methyltriethoxysilane, 2.2 g of p-ethoxyethoxyphenyl trimethoxysilane where the last monomer (in bold) includes a phenyl group with a protected phenolic group. Additionally, the examples has specifically identified methoxybenzyltrimethoxysilane, methoxybenzyltrimethoxysilane Ethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyl triethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyl trichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyPhenyltriacetoxysilane, ethoxyphenyltrichlorosilane, Ethoxybenzyltrimethoxysilane, Ethoxybenzyltriethoxysilane, Ethoxybenzyltriacetoxysilane, Ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyl Trichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, which are embraced by the claim language.
In the response of 5/21/2026, the applicant points out that the examiner has calculated the amount of the nitric acid to be 2527 ppm in the cited examples of Shibayama et al. WO 2019082934 and has stated it would have been obvious to reduce the amount of nitric acid used to induce/catalyze the to be within the 100-1000 ppm range based upon the disclosure at that the amounts of hydrolysis catalysts can be 0.001 to 10 moles/mole or hydrolysable moiety at [0058] of Shibayama et al. WO 2019082934. The applicant argues that modifying the amount of nitric acid would not have been obvious in spite of this being the specifically taught in the reference at [0079]. The applicant argues that the amount of nitric acid used to induce/catalyze the hydrolysis is irrelevant. The examiner notes that 19.6 g of 0.2M nitric acid (3.92 g x Mol/L)is added
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(original text at page 78). Example 3 of the instant specification uses 11.7 g of 0.1M nitric acid (1.17 g x Mol/L) and after the hydrolysis, distillation and the combination with maleic acid, TPSML and solvents, the concentration of nitric acid is 50 ppm. Example 6 of the instant specification adds 10.8 g of 1M nitric acid (10.8 g x mol/L), which after the hydrolysis, distillation and the combination with maleic acid, TPSML and solvents, the concentration of nitric acid is 500 ppm. Given that the starting amount of nitric acid in Shibayama et al. WO 2019082934 is between the amounts of the inventive examples 3 and 6 and in in synthesis example 11 of Shibayama et al. WO 2019082934 describes a distillation under reduced pressure using the same language as examples 3 and 6 of the instant specification, and 1 part of the polymers is combined with 100 parts of solvent as are inventive examples 3 and 6, it seems that the distillation of the polymer which is described as removing the water, methanol and ethanol may have an effect on the amount of nitric acid anions in the coating solution (see Nakajima et al. 20100330505 below) and it is reasonable to extrapolate that the solution of synthesis example 11 has a nitric acid content of 50-500 ppm. A 1M nitric acid solution is 63020 ppm. The applicant is invited to provide declaration evidence to address this question of fact, noting that the reference and the instant application share inventors with the instant application. Additionally, It is reasonable for one skilled in the art to accept the 0.0001 to 0.1 mol/mole of hydrolyzable moiety would be suitable absent any evidence to the contrary.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Nakajima et al. 20100330505 describes 4.94 g of phenyltrimethoxysilane, 71.58 g of tetraethoxysilane, 22.20 g of methyltriethoxysilane, 1.20 g of methoxybenzyltrimethoxysilane, 0.68 g of triethoxysilylpropyl-4,5-dihydroimidazole, and 150 g of acetone were charged into a 500 mL flask to be dissolved and the resultant mixed solution was warmed while stirring the mixed solution with a magnetic stirrer to reflux. Next, an aqueous solution in which 0.31 g of nitric acid was dissolved in 33.09 g of ultrapure water was added to the mixed solution. The mixed solution was subjected to the reaction for 240 minutes and the resultant reaction solution was cooled down to room temperature. Subsequently, 200 g of propylene glycol monoethyl ether was added to the reaction solution and ethanol and methanol as reaction by-products, acetone, water, and nitric acid were distilled off under reduced pressure to obtain a hydrolysis-condensation product. The polymer thus obtained corresponds to a polymer containing a group of silane structure units of Formula (VI-15) [0168]. The combination of the polymer, a crosslinker, p-toluenesulfonic acid and surfactant in PGMEA and PGME and filtering the solution is disclosed at [0225].
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.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Martin J Angebranndt whose telephone number is (571)272-1378. The examiner can normally be reached 7-3:30 pm EST.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Ching-Yu (Coris) Fung can be reached on 571-270-5713. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 June 9, 2026
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