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 Rejections of the previous office action, not repeated below are withdrawn based upon the arguments and amendments of the applicant.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.
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 from 2527.4 ppm to 100-1000 ppm which is 0.01 to 0.1 wt% based upon the curing catalyst can be 0.01 to 10 parts by mass, with preferences of 0.01 to 3 parts taught at [0079] 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 modify the amount of nitric acid to be within the 0.001-10 moles/mole of the hydrolysable groups based upon the disclosure at [0058] and/or 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 from 2527.4 ppm to 100-1000 ppm which is 0.01 to 0.1 wt% based upon the curing catalyst can be 0.01 to 10 parts by mass, with preferences of 0.01 to 3 parts taught at [0079] 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 modify the amount of nitric acid to be within the 0.001-10 moles/mole of the hydrolysable groups based upon the disclosure at [0058] and/or 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 3/4/2026, the applicant argues that the claim requires the amount of nitric acid to be 1-1000 ppm. The applicant calculates the 19.6 g of 0.2M nitric acid as being 12,600 ppm. 0.2 M nitric acid is (ppm = M x MW x 1000) is 12,602 ppm for the 0.2 M solution added. The concentration (ppm) of nitric acid in the solution is 12602 x (19.6/(19.6 + 48.2 + 6.7 +22.9 +0.33 which reduces to 12602 x (19.6/97.73) which yields 2527.4 ppm. The content of the curing catalyst can be 0.01 to 10 parts by mass, with preferences of 0.01 to 3 parts [0079]. (ppm = wt% x 10,000), which yields a range of 100-100,000 with a preference to 100-30,000.
The applicant argues that comparative example provides comparative data evidencing that high concentrations (10,000 ppm) induces gelation. Comparative example 2 does not include a silane including a protected phenyl group bounded by silane (a) of the claims and the concentration of the nitric acid is 4 times that of example 11 of Shibayama et al. WO 2019082934. The examiner holds that comparative example 2 does not represent a comparison which is equal or preferable to a direct comparison with the closest prior art, specifically example 11 of Shibayama et al. WO 2019082934.
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, Mark F Huff can be reached on 571-272-1385. 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 March 20, 2026