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 response of the applicant has been given careful consideration. Rejections of the previous action not repeated below are withdrawn based upon the amendments and arguments of the applicant. Responses to the arguments of the applicant are presented after the first rejection they are directed to.
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 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 16,18,21,22,24-26,28-30 and 36-38 are rejected under 35 U.S.C. 103 as being unpatentable over Sugata et al.JP 2000347414, in view of Ishikawa et al. 20100255429.
Sugata et al. JP 2000347414 (machine translation attached) teaches 2 parts tetra (hydroxymethyl) glycoluril (trade name "Cymel 1172) 98 parts polyvinyl acetal, 6 parts triethylamine 0.05 parts surfactant in 2014 parts water. A resist is made and coated onto a silicon wafer, dried, exposed using a KrF excimer laser, post baked, developed in TMAH, the polyvinyl acetal polymer solution was applied, dried at 85 degrees C, baked at 118 degrees C for 90 seconds, rinsed with water and the hole size was found to be reduced from 0.22 microns to 0.13 microns [0026-0027]. Example 2 is similar, but uses monoethanolamine as the water soluble amine [0028]. Example 3 is similar to example 1, but uses polyvinyl acetal rather than polyvinylpyrrolidone [0029]. Examples of this water-soluble crosslinking agent include melamine derivatives, urea derivatives, ethylene urea derivatives, benzoguanamine derivatives having a hydroxyalkyl group, preferably a hydroxymethyl group or an alkoxyalkyl group, preferably an alkoxymethyl group or both at the N-position. And glycoluril derivatives. These may be used alone or in combination of two or more. Among them, glycoluril in which a hydrogen atom of an imino group is substituted by a hydroxymethyl group, that is, tetra (having four hydroxymethyl groups) (Hydroxymethyl) glycoluril is preferable because it is completely water-soluble, has excellent storage stability, exhibits moderate crosslinking properties, and has excellent miscibility with a water-soluble resin. Such a product can be obtained, for example, as a commercial product “Cymel 1172” (trade name, manufactured by Mitsui Cytec) [0009]. The water-soluble resin of the component (b) is not particularly limited, and conventionally known ones, for example, It can be appropriately selected and used from those described in Japanese Patent No. JP-A-10-73927. Particularly, polyvinyl acetal and polyvinyl pyrrolidone are preferred. As the polyvinyl acetal, for example, commercially available products “S-LEC KW-1” and “S-LEC KW-3” (all manufactured by Sekisui Chemical Co., Ltd., trade names) can be obtained. As polyvinylpyrrolidone, for example, a commercially available product “Luviskol K-60 (weight average molecular weight 160,000) "," Luviskol K-80 (weight average molecular weight unknown) "," Luviskol K-90 (weight average molecular weight 1,200,000) "(B.A.S.F., trade name). These components (ii) may be used alone or in combination of two or more [0010]
Component (A) is a water soluble crosslinking agent (a) a water soluble resin (b) or both [0009] when used in combination 1-35% of the crosslinker and 99-35% of the resin are used.[0011].
The concentration of the water soluble crosslinker component (A) in the aqueous solution is preferably in the range of 2 to 20% by weight, particularly preferably 3 to 10% by weight [0016]. A surfactant having a fluorine atom and a silicon atom in the molecule, if necessary, in order to improve coatability. 0.01 to 1.0 part by weight, preferably 0.03 to 1.0 part by weight, per 100 parts by weight of the component (A) [0017]. As the water-soluble nitrogen-containing organic compound of the component (B), the compound is soluble in an aqueous solvent used for preparing a coating agent for forming a fine resist pattern and has compatibility with the component (A). Anything can be used, and there is no particular limitation. Examples of such water-soluble nitrogen-containing organic compounds include aliphatic amines. Examples of the aliphatic amine include lower alkylamines such as trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine and isopropylamine; monoethanolamine And lower alkanolamines such as diethanolamine, triethanolamine, di-n-propanolamine, tri-n-propanolamine, diisopropanolamine and triisopropanolamine. Among them, lower alkylamines such as diethylamine, triethylamine, monoethanolamine, diethanolamine, and triethanolamine and lower alkanolamines are particularly preferable because they are effective for improving the perpendicularity of the pattern cross-sectional shape and miniaturizing the pattern size. Considering the effect of addition and crosslinking reactivity, the more preferable content of the water soluble component (B) in the solution is 2 to 10% by weight [0014-0015]
Ishikawa et al. 20100255429 in example 1 coats a resist, dries the resist, exposes the resist with an ArF excimer laser with a NA of 0.68, post bakes the resist and develops the pattern using TMAH to yield holes which are 300 nm in diameter. The patterned resist is overcoated with 100 parts polyvinylpyrrilidone, 2.5 parts water soluble urea based crosslinking agent and a surfactant as an aqueous solution with 10% solids using spin coating, baking at 130 degrees C for 60 seconds and washed/rinsed with water. This was then overcoated with a resist, uniformly exposed and developed in TMAH to yield a pattern with holes which are 280 nm is diameter [0151-0154]. The overcoat can include a water soluble resin and a crosslinking agent [0086]. The water soluble resin is not particularly limited as long as it is a resin which can be dissolved in water at room temperature, and is preferably constituted to include at least one selected from an acrylic based resin, a vinyl based resin, a cellulose based resin and an amide based resin, in the present invention. Examples of the acrylic based resin include polymers or copolymers constituted with a monomer such as acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate, N,N-dimethylacrylamide, N,N-dimethylaminopropylmethacrylamide, N,N-dimethylaminopropylacrylamide, N-methylacrylamide, diacetoneacrylamide, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, acryloyl morpholine, and the like. Examples of the vinyl based resin include polymers or copolymers constituted with a monomer such as N-vinylpyrrolidone, vinylimidazolidinone, vinyl acetate or the like. Examples of the cellulose based resin include hydroxypropyl methylcellulose phthalate, hydroxypropyl methylcellulose acetate phthalate, hydroxypropyl methylcellulose hexahydrophthalate, hydroxypropyl methylcellulose acetate succinate, hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, cellulose acetate hexahydrophthalate, carboxymethyl cellulose, ethyl cellulose, methyl cellulose, and the like. Furthermore, among amide based resins, those which are soluble in water can be also used. Of these examples, vinyl based resins are preferred, and particularly polyvinylpyrrolidone and polyvinyl alcohol are preferred. These water soluble resins may be used alone, or two or more thereof may be used as a mixture. In order to provide the coat film having a film thickness that is necessary and sufficient for use, the amount of the water soluble resin included is preferably about 1 to 99% by mass, more preferably about 40 to 99% by mass, and still more preferably about 65 to 99% by mass of the solid content of the material for forming a coat film [0087-0094]. The water soluble crosslinking agent has at least one nitrogen atom in the structure thereof. As such a water soluble crosslinking agent, a nitrogen-containing compound having an amino group and/or imino group in which at least two hydrogen atoms are substituted with a hydroxyalkyl group and/or alkoxyalkyl group is preferably used. Examples of such nitrogen-containing compounds include melamine based derivatives, urea based derivatives, guanamine based derivatives, acetoguanamine based derivatives, benzoguanamine based derivatives and succinyl amide based derivatives in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group or both of these, as well as glycoluril based derivatives and ethylene urea based derivatives in which the hydrogen atom of the imino group is substituted, and the like. Among these nitrogen-containing compounds, at least one or more of: triazine based derivatives such as benzoguanamine based derivatives, guanamine based derivatives, and melamine based derivatives; glycoluril based derivatives; and urea based derivatives, which have an amino group or an imino group in which at least two hydrogen atoms are substituted with a methylol group or a (lower alkoxy)methyl group, or both of these, are preferred in view of the crosslinking reactivity. The amount of the water soluble crosslinking agent included is preferably about 1 to 99% by mass, more preferably about 1 to 60% by mass, and still more preferably 1 to 35% by mass of the solid content of the material for forming a coat film [0095-0097]. The solid content is 3-50 wt% [0098]. Optional components include a surfactant to suppress bubble/foam formation and reduce defects in the coating. The surfactant can be added in amounts of 0.1-10 wt% [0101-0118]. A water soluble fluorine compound can be added [0119-0121]. An amide can be added [0122-0126]. A heterocycle having at least an oxygen and/or nitrogen atom (in the ring) such as an oxazoline, an oxazolidone [0127-0139], a heterocycle with two or more nitrogen in a ring, including pyrazole based compounds such as pyrazole, 3,5-dimethylpyrazole, 2-pyrazoline, 5-pyrazolone, 3-methyl-1-phenyl-5-pyrazolone, 2,3-dimethyl-1-phenyl-5-pyrazolone, 2,3-dimethyl-4-dimethylamino-1-phenyl-5-pyrazolone, and benzopyrazole; imidazole based compounds such as imidazole, methylimidazole, 2,4,5-triphenylimidazole, 4-(2-aminoethyl)imidazole, and 2-amino-3-(4-imidazolyl)propionic acid; imidazoline based compounds such as 2-imidazoline, 2,4,5-triphenyl-2-imidazoline, and 2-(1-naphthylmethyl)-2-imidazoline; imidazolidine based compounds such as imidazolidine, 2-imidazolidone, 2,4-imidazolidinedione, 1-methyl-2,4-imidazolidinedione, 5-methyl-2,4-imidazolidinedione, 5-hydroxy-2,4-imidazolidinedione-5-carboxylic acid, 5-ureide-2,4-imidazolidinedione, 2-imino-1-methyl-4-imidazolidone, and 2-thioxo-4-imidazolidone; benzoimidazole based compounds such as benzoimidazole, 2 phenylbenzoimidazole, and 2-benzoimidazolinone; diazine based compounds such as 1,2-diazine, 1,3-diazine, 1,4-diazine, and 2,5-dimethylpyrazine; hydropyrimidine based compounds such as 2,4(1H, 3H)pyrimidinedione, 5-methyluracil, 5-ethyl-5-phenyl-4,6-perhydropyrimidinedione, 2-thioxo-4(1H, 3H)-pyrimidinone, 4-imino-2(1H, 3H)-pyrimidine, and 2,4,6(1H, 3H, 5H)-pyrimidinetrione; benzodiazine based compounds such as cinnoline, phthalazine, quinazoline, quinoxaline, and luminol; dibenzodiazine based compounds such as benzoshinorine, phenazine, and 5,10-dihydrophenazine; triazole based compounds such as 1H-1,2,3-triazole, 1H-1,2,4-triazole, and 4-amino-1,2,4-triazole; benzotriazole based compounds such as benzotriazole, and 5-methylbenzotriazole; triazine based compounds such as 1,3,5-triazine, 1,3,5-triazine-2,4,6-triol, 2,4,6-trimethoxy-1,3,5-triazine, 1,3,5-triazine-2,4,6-trithiol, 1,3,5-triazine-2,4,6-triamine, and 4,6-diamino-1,3,5-triazine-2-ol, and the like, but not limited thereto. These can be added in amounts of 1-15 wt% [0140-0143]. Water soluble amines can be added amounts of 0.1-30 wt% and useful examples include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethyl ethanolamine, N,N-diethyl ethanolamine, N,N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine; polyalkylenepolyamines such as diethylene triamine, triethylene tetramine, propylenediamine, N,N-diethylethylene diamine, 1,4-butanediamine, N-ethyl-ethylene diamine, 1,2-propane diamine, 1,3-propane diamine, and 1,6-hexanediamine; aliphatic amines such as 2-ethyl-hexylamine, dioctylamine, tributylamine, tripropylamine, triallylamine, heptylamine, and cyclohexylamine; aromatic amines such as benzylamine, and diphenylamine; cyclic amines such as piperazine, N-methyl-piperazine, and hydroxyethylpiperazine, and the like [0144-0146]. Non-amine solvents. [0147-0149]. The wavelength used in the exposure is not particularly limited, and the exposure can be conducted using an actinic radiation such as a KrF excimer laser, an ArF excimer laser, an F.sub.2 excimer laser, EUV, VUV, EB, an X-ray, and a soft X-ray [0003,0057,0080]. In the production of electronic components such as semiconductor devices and liquid crystal devices, lithographic techniques have been used when a support is subjected to an etching treatment, etc. In the lithographic technique, a coat film (resist layer) is formed on a substrate using a resist material responsive to actinic radiation, then the resist layer is selectively irradiated with the actinic radiation, and thereafter a developing treatment is performed to selectively dissolve and remove the resist layer so as to form a resin pattern (resist pattern) on the support. Then, a pattern is formed on the support by carrying out an etching process with this resist pattern as a protective layer (mask pattern) [0002]. There are no particular limitations as the support 1, and conventionally known materials can be used; for example, a substrate for electronic components, a substrate for electronic components on which a predetermined wiring pattern is formed, and the like can be exemplified. More specifically, examples of the substrate include silicon wafers, substrates made of a metal such as copper, chromium, iron or aluminum, glass substrates, and the like. As the material of the wiring pattern, copper, aluminum, nickel, gold or the like is available [0031].
Sugata et al. JP 2000347414 (machine translation attached) teaches 2 parts tetra (hydroxymethyl) glycoluril (trade name "Cymel 1172, crosslinker) 98 parts polyvinyl acetal, 6 parts triethylamine 0.05 parts surfactant in 2014 parts water. The polymer is used in 4.6% including solvent, the amine is present as 0.28 % including solvent and a crosslinker is included at 0.095 wt% and uses this as a resist overcoat to reduce the size of openings. Sugata et al. JP 2000347414 does not teach a cyclic amine compound bounded by formula (I) of the claims or exemplify a composition with a polymer content of 5-30 wt% based upon the entire composition including the solvent.
With respect to claims 16,18,21,22,24,26 and 28-38, it would have been obvious to one skilled in the art to modify the resist overcoating composition of examples 1-3 of Sugata et al. JP 2000347414 by increasing the amount of the polyvinyl acetal from 4.6 wt% to 5-20% based upon the disclosure at [0016] of Sugata et al. JP 2000347414 and replacing the water soluble triethylamine or monoethanolamine with other water soluble amines, such as the hydroxyethylpiperazine disclosed as equivalent to trialkylamines (aliphatic amines) and monoethanolamine at [0144-0146] of Ishikawa et al. 20100255429. Further, it would have been obvious to use the resulting composition in the processes of the examples with a reasonable expectation of forming a useful thinned pattern.
With respect to claims 16,18,21,22,24-26 and 28-38, it would have been obvious to one skilled in the art to modify the resist overcoating composition of examples 1-3 of Sugata et al. JP 2000347414 by increasing the amount of the polyvinyl acetal from 4.6 wt% to 5-19% based upon the disclosure at [0016] of Sugata et al. JP 2000347414, increasing the crosslinker to 1wt% based upon the disclosure at [0009-0011,0016] and replacing the water soluble triethylamine or monoethanolamine with other water soluble amines, such as the hydroxyethylpiperazine disclosed as equivalent to trialkylamines (aliphatic amines) and monoethanolamine at [0144-0146] of Ishikawa et al. 20100255429. Further, it would have been obvious to use the resulting composition in the processes of the examples with a reasonable expectation of forming a useful thinned pattern.
With respect to claims 16,18,21,22,24-26 and 28-38, it would have been obvious to one skilled in the art to modify the resist overcoating composition of examples 1-3 of Sugata et al. JP 2000347414 by increasing the amount of the polyvinyl acetal from 4.6 wt% to 5-19% based upon the disclosure at [0016] of Sugata et al. JP 2000347414, replacing the crosslinker used with other water soluble crosslinkers disclosed and increasing the crosslinker concentration to 1wt% based upon the disclosure at [0009-0011,0016] and replacing the water soluble triethylamine or monoethanolamine with other water soluble amines, such as the hydroxyethylpiperazine disclosed as equivalent to trialkylamines (aliphatic amines) and monoethanolamine at [0144-0146] of Ishikawa et al. 20100255429. Further, it would have been obvious to use the resulting composition in the processes of the examples with a reasonable expectation of forming a useful thinned pattern.
With respect to claims 16,18,21,22,24-26 and 28-37, it would have been obvious to one skilled in the art to modify the resist overcoating composition of examples 1-3 of Sugata et al. JP 2000347414 by increasing the amount of the polyvinyl acetal from 4.6 wt% to 5-19% based upon the disclosure at [0016] of Sugata et al. JP 2000347414, replacing the crosslinker used with other water soluble crosslinkers disclosed and increasing the crosslinker concentration to 1wt% based upon the disclosure at [0009-0011,0016] and replacing the water soluble triethylamine or monoethanolamine with other water soluble amines, such as hydropyrimidine or
4-amino-1,2,4-triazole disclosed as equivalent to trialkylamines (aliphatic amines) and monoethanolamine at [0140-0146] of Ishikawa et al. 20100255429. Further, it would have been obvious to use the resulting composition in the processes of the examples with a reasonable expectation of forming a useful thinned pattern.
In the response of 6/16/2026, the applicant argues that they have merely folded claim 23 into claim 16. The applicant has also folded limitations form claims 17 and 21. In response, the applicant has modified the rejection to more precisely address the amended claims. The closest prior art appears to be Sugata et al.JP 2000347414, which exemplifies a composition including a water soluble polymer slightly outside the weight range, a water soluble crosslinker, a water soluble amine and water as the sole solvent. The Ikeda et al. WO 2019076956 does not disclose the composition of the AX R200 or other overcoatings, The applicant may be able to evidence a materials difference in the functionality based upon the use of compounds bounded by formula (I), rather than the triethylamine or monoethanolamine of Sugata et al.JP 2000347414, but this is not present in the record. The comparison in table 1 is perhaps the closest, but does not include a water soluble amine (such as triethylamine) in place of the pyridine ethanol and so it does not represent a comparison which is equal to or preferable to a direct comparison with \the examples of Sugata et al.JP 2000347414. The substitution of one water soluble amine for another, particularly when listed together in Ishikawa et al. 2010025542, is reasonable and is not impermissible hindsight.
Claims 16,18,21,22 and 24-38 are rejected under 35 U.S.C. 103 as being unpatentable over Sugata et al.JP 2000347414, in view of Ishikawa et al. 20100255429, further in view of Ikeda et al. WO 2019076956.
Ikeda et al. WO 2019076956 in example 1 coats a resist on a silicon wafer, dries the resist, exposes the resist to a mask with a 3.0 line/space pattern using the g and h lines (436 nm and 405nm respectively) in a stepper with a NA of 0.1, the resist was developed, post baked and subjected to a flood exposure using a mixture of i,h, and g lines (436, 405 and 365 nm respectively) and then overcoated with AZ R200 using a spin coater (to thicken/widen the resist patten and reduce the width of the spaces), baked at 100 degrees C for 3 minutes and then treated with a developer to yield a fine (finer) pattern (17.7% decrease). [0046]. Example 3 is similar, but uses AZ R602 for the overcoating and rinses/develops the result with water (9.9 % decrease) [0048]. Examples 7 and 8 are similar to example 1, but a surfactant is added to the AZ R200 (18 or 19.6 % decrease) [0052-0053]. Example 9 is similar to example 1, but crosslinker amount weas increased by 2.09 times and the solid content was 1.37 times that of example 1 (19.6% decrease)[0054]. Example 10 is similar to example 9, but 0.08 parts 1,4-diazabicyclo[2,2,2]octane was added (26% decrease)[0055]. Example 11 is similar to example 9, but 0.08 parts pentaethylenehexamine (basic compound) was added (30.7%) [0056] (see table 1 on page 24). The resist composition layer is exposed for patterning through a desired mask. The exposure wavelength used at this time may be any one of a single wavelength such as g-line (436 nm), h-line (405 nm), and i-line (365 nm), which are conventionally used for exposing the photosensitive composition, wavelength mixture of g-line and h-line, and one in which i-line, h-line and g-line are mixed, which is called broadband, and the like, but it preferably comprises at least wavelength of 300 - 450 nm, more preferably 350 - 450 nm. The exposure amount is preferably 15 - 80 mJ/cm.sup.2, more preferably 20 - 60 mJ/cm.sup.2. In the present invention, an exposure apparatus having a resolution limit of 1.5 - 5.0 μm , preferably 1.5 to 4.0 μm [0023-0024]. The fine pattern forming composition according to the present invention is not particularly limited, but preferably comprises a cross-linking agent, a polymer, and a solvent. As the cross-linking agent, a melamine type cross-linking agent, a urea type cross-linking agent, an amino type cross-linking agent and the like are effectively used, but there is no particular limitation as long as it is a water-soluble cross-linking agent which causes cross-linking by an acid. Suitable examples thereof include methoxymethylol melamine, methoxyethylene urea, glycoluril, isocyanate, benzoguanamine, ethylene urea, ethylene urea carboxylic acid, (N-methoxymethyl)dimethoxyethylene urea, (N-methoxymethyl) methoxyhydroxyethylene urea, N-methoxymethyl urea, or a combination of two or more cross-linking agents selected from these groups. Preferably, it is methoxymethylol melamine, methoxyethylene urea, ( N-methoxymethyl )dimethoxyethylene urea, (N-methoxymethyl) methoxyhydroxyethylene urea, N-methoxymethyl urea, or a combination of two or more cross-linking agents selected from these groups [0031-0031]. As the polymer, polyvinyl acetal resin, polyvinyl alcohol resin, polyacrylic acid resin, water-soluble resin containing oxazoline, aqueous urethane resin, polyallylamine resin, polyethyleneimine resin, polyvinylamine resin, water-soluble phenol resin, water-soluble epoxy resin, polyethyleneimine resin, styrene-maleic acid copolymer, and the like are effectively used, but there is no particular limitation as long as it causes a cross-linking reaction in the presence of an acidic component. Suitable examples include polyvinyl acetal resin, polyallylamine resin, and water-soluble resin containing polyvinyl alcohol oxazoline [0033]. The solvent is water or water and a water soluble solvent which does not dissolver the resist [0034]. Examples of other additives that may be included in the fine pattern forming composition include, for example, surfactant, acid or base, plasticizer, leveling agent and the like. The surfactant is useful for improving coatability and solubility. The content ratio of the surfactant is preferably 0.01 - 5 mass% and more preferably 0.05 - 3 mass %, based on the total mass of the fine pattern forming composition. The acid or base is used to adjust the pH of treating liquid or to improve the solubility of adding component. The acid or base to be used can be optionally selected as long as the effect of the present invention is not impaired, and examples thereof include carboxylic acids, amines and ammonium compounds. These include fatty acids, aromatic carboxylic acids, primary amines, secondary amines, tertiary amines, and ammonium compounds, and these may be substituted by any substituent or not substituted. The content ratio of the acid is preferably 0.005 - 0.1 mass% based on the total mass of the fine pattern forming composition. The content ratio of the base is preferably 0.01 - 0.3 mass% based on the total mass of the fine pattern forming composition [0035-0037]. The processing can be used to manufacture display devices and the modified/narrowed resist pattern can be etched or plated to form wiring [0042-0044].
The combination of Sugata et al.JP 2000347414 and Ishikawa et al. 20100255429 does not teach the use of the resist overcoat with a process where the exposure of the resist is within 300-450nm the NA of the exposure device is 0.08-0.15, the resolution of the exposure apparatus is 1-5 to 5.0 microns, or a plasticizer, base, acid, bacteriacide, antibacterial, antifungal or preservative are added.
With respect to claims 16,18,21,22 and 24-38, in addition to the basis above, it would have been obvious to use the composition rendered obvious by the combination of Sugata et al. JP 2000347414 and Ishikawa et al. 20100255429 with the resists and exposure apparatus of Ikeda et al. WO 2019076956 which uses g and h mercury lamp lines (436 nm and 405nm respectively) in a stepper with a NA of 0.1 [0046], which is disclosed as having a resolution limit of 1.5 - 5.0 μm , preferably 1.5 to 4.0 μm [0023-0024] based upon the disclosure in Sugata et al. JP 2000347414 at [0020] that ultraviolet light, deep-UV or excimer light can be used in the exposure and the prior use of resist overcoats the reduce the size of features in Ikeda et al. WO 2019076956. Further, it would have been obvious to one skilled in the art to use the process for forming display devices, etching the substrate or forming wiring as taught in [0042-0044] of Ikeda et al. WO 2019076956, to use other water soluble polymers such as polyvinyl acetal resin, polyvinyl alcohol resin, polyacrylic acid resin, water-soluble resin containing oxazoline, aqueous urethane resin, polyallylamine resin, polyethyleneimine resin, polyvinylamine resin, water-soluble phenol resin, water-soluble epoxy resin, polyethyleneimine resin, styrene-maleic acid copolymer, and the like are effectively used, but there is no particular limitation as long as it causes a cross-linking reaction in the presence of an acidic component. Suitable examples include polyvinyl acetal resin, polyallylamine resin, and water-soluble resin containing polyvinyl alcohol oxazoline taught at [0033] of Ikeda et al. WO 2019076956 and/or to add acid or base, plasticizer as taught in Ikeda et al. WO 2019076956 at [0035-0037] with a reasonable expectation of forming a useful narrowed resist pattern.
The examiner relies upon the response above to address the arguments as no further arguments were advanced.
Claims 16,18,21,22,24-26,28-30 and 36-39 are rejected under 35 U.S.C. 103 as being unpatentable over Sugata et al.JP 2000347414, in view of Ishikawa et al. 20100255429, further in view of Yoshioda JP 2007078857 and Akashi et al. 20100119975
Yoshioda JP 2007078857 (machine translation attached) teaches the use of vinyl pyrrolidone-modified polyvinyl alcohol obtained by graft polymerization of vinyl pyrrolidone to polyvinyl alcohol [0007]. This is added to resist in the examples. The VP-modified PVA of the present invention obtained as described above preferably has a K value of 12 to 150. The K value is a constant that represents the degree of polymerization proposed by the German chemist Fikencher. If the K value is smaller than this, the adhesion decreases when used in a photoresist, and the K value is larger than this. Solubility in water deteriorates [0016]
Akashi et al. 20100119975 teaches aqueous based composition for reducing resist patterns sizes (see examples and abstract). The pattern-forming composition of the present invention contains a water-soluble resin. There is no particular restriction on the water-soluble resin, provided that the resin is soluble in a solvent described later and that the resin can be crosslinked to form a covering layer by the action of acid generated from an original resist pattern which is to be thickened to form a miniaturized pattern. Examples of the water-soluble resin include polymers comprising N-vinylpyrrolidone, vinyl alcohol, acrylate or methacrylate as a constituting unit. Examples of the polymers comprising N-vinylpyrrolidone as a constituting unit include: N-vinyl-pyrrolidone/hydroxyalkyl acrylate copolymer, N-vinyl-pyrrolidone/hydroxyalkyl methacrylate copolymer, N-vinylpyrrolidone/vinylimidazole copolymer, N-vinylpyrrolidone/vinyl acetate copolymer, N-vinylpyrrolidone/vinyl alcohol copolymer, and N-vinylpyrrolidone-vinyl melamine copolymer. The copolymer comprising N-vinylpyrrolidone as a constituting unit contains N-vinylpyrrolidone in an amount of preferably 20 to 90 mol %, more preferably 50 to 95 mol % based on all the monomers constituting the copolymer. Examples of the polymers comprising vinyl alcohol as a constituting unit are a modified polyvinyl alcohol in which hydroxyl group of polyvinyl alcohol are protected with protecting groups such as acetyl, acetal, formal and butyral. The reaction of protecting the hydroxyl group with the protecting groups such as acetyl, acetal, formal and butyral can be carried out in a known manner. Examples of the polymers comprising acrylate or methacrylate as a constituting unit include: polyacrylic acid, polymethacrylic acid, and copolymers of acrylic or methacrylic acid in combination with acrylic ester or methacrylic ester [0027]
With respect to claims 16,18,21,22,24-26,28-30 and 36-39, in addition to the basis above, it would have been obvious to use the composition rendered obvious by the combination of Sugata et al. JP 2000347414 and Ishikawa et al. 20100255429 by replacing the water soluble polyvinyl acetal or polyvinylpyrrolidone polymer used in the examples with a water soluble polyvinylalcohol/polyvinylpyrrolidone graft copolymer such as that taught by Yoshioda JP 2007078857 at [0007,0016] with a reasonable expectation of success based upon the disclosure of polyvinylpyrrolidone and polyvinyl alcohol at [0087-0094] of Ishikawa et al. 20100255429 and the known use of water soluble polyvinylalcohol/polyvinylpyrrolidone copolymer in resist overcoats for reducing the size of features at [0027] of Akashi et al. 20100119975
The examiner relies upon the response above to address the arguments as no further arguments were advanced.
Claims 16,18,21,22 and 24-39 are rejected under 35 U.S.C. 103 as being unpatentable over Sugata et al.JP 2000347414, in view of Ishikawa et al. 20100255429 and Ikeda et al. WO 2019076956, further in view of Yoshioda JP 2007078857 and Akashi et al. 20100119975
With respect to claims 16,18,21,22 and 24-39, in addition to the basis above, it would have been obvious to use the composition rendered obvious by the combination of Sugata et al. JP 2000347414, Ishikawa et al. 20100255429 and Ikeda et al. WO 2019076956 by replacing the water soluble polyvinyl acetal or polyvinylpyrrolidone polymer used in the examples with a water soluble polyvinylalcohol/polyvinylpyrrolidone graft copolymer such as that taught by Yoshioda JP 2007078857 at [0007,0016] with a reasonable expectation of success based upon the disclosure of polyvinylpyrrolidone and polyvinyl alcohol at [0087-0094] of Ishikawa et al. 20100255429 and the known use of water soluble polyvinylalcohol/polyvinylpyrrolidone copolymer in resist overcoats for reducing the size of features at [0027] of Akashi et al. 20100119975
The examiner relies upon the response above to address the arguments as no further arguments were advanced.
Claims 16,18,21,22,24-26,28-30 and 36-38 are rejected under 35 U.S.C. 103 as being unpatentable over Sugata et al.JP 2000347414, in view of Ishikawa et al. 20100255429 and Ikeda et al. WO 2019076956, further in view of any one of Niikura et al 5518860, Shimoyama WO 2014050626, Uzawa et al. 20160093413, Watanabe et al. JP 2004347735 or Watanabe et al. JP 2004347736.
Niikura et al 5518860 in example 1 combines a novolak resist with 2,3,4,4’-tetrahydroxybenzophenone, a diazide sensitizer and 2-(2-hydroxyethyl)pyridine) dissolved in ethyl lactate and butyl acetate (col. 7/lines 3-18). hydroxyalkyl-substituted pyridine compound represented by the above given general formula (I), in which each symbol has the meaning as defined above. Examples of the pyridine compounds suitable as the component (c) include 2-hydroxymethyl pyridine, 3-hydroxymethyl pyridine, 4-hydroxymethyl pyridine, 2-(2-hydroxyethyl) pyridine, 3-(2-hydroxyethyl) pyridine, 4-(2-hydroxyethyl) pyridine, 2-(3-hydroxypropyl) pyridine, 3-(3-hydroxypropyl) pyridine, 4-(3-hydroxypropyl) pyridine, 2,6-di(hydroxymethyl) pyridine, 2-(3-hydroxypropyl)-6-methyl pyridine and the like. These pyridine compounds can be used either singly or as a combination of two kinds or more according to need. Of the above named pyridine compounds, 2-hydroxymethyl pyridine, 2-(2-hydroxyethyl) pyridine and 2-(3-hydroxypropyl) pyridine are particularly preferable and 2-(2-hydroxyethyl) pyridine is most preferable in respect of the good adhesive bonding strength between the resist layer and the substrate surface as well as little degradation in the photosensitivity and film thickness retention in the lapse of time (4/17-39). Besides the above described essential ingredients, i.e. components (a), (b) and (c), the inventive photoresist composition can optionally be admixed with various kinds of known additives conventionally used in photoresist compositions including auxiliary resins, plasticizers, stabilizers and the like to improve the film properties of the resist layer, coloring agents to improve the visibility of the patterned resist layer formed by development and photosensitizing aids to enhance the photosensitivity of the resist composition each in a limited amount (4/64-5/6)
Shimoyama WO 2014050626 exemplifies C-13 , C14, C-32, C33 and C21-25 in table 4 on pages 84-85.
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These are combined with a polymer, photoacid generator, an alkoxysilane, a sensitizing dye , a basic compound a surfactant, a crosslinking agent, an antioxidant and PGMEA in examples 31.32,39-42, 1-18, 49 and 50 (pages 78-79). These are bounded by formula C-1 where
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, where ring A represents an aromatic ring having one nitrogen atom, sulfur atom or oxygen atom in the ring, and X represents a hydrogen atom, an alkyl group or an aryl group, Y represents a hydroxy group, a carboxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, an alkoxy group, an aryloxy group, a mercapto group or an amino group, m represents an integer of 1 or more, and n is Represents an integer of 1 or more.) [0013,0124]. Ring A represents an aromatic ring having one nitrogen atom, sulfur atom or oxygen atom in the ring. The ring A is not particularly limited as long as it is an aromatic ring, but a 5-membered aromatic heterocyclic compound, a 6-membered aromatic heterocyclic compound, a 5-membered aromatic heterocyclic structure and a 6-membered aromatic heterocyclic structure Polycyclic aromatic heterocyclic compounds containing at least one are preferred. In the present invention, a ring in which ring A, a conjugatable group (such as a carbonyl group) and the ring A are directly bonded to each other to have aromaticity is also included in the aromatic ring. In this case, in addition to one nitrogen atom, sulfur atom or oxygen atom contained in the ring, it may have a nitrogen atom, sulfur atom or oxygen atom directly bonded to the ring. For example, a chromone ring corresponds to this. The polycyclic aromatic heterocyclic compound means a compound (eg, quinoline) in which one or more aromatic rings and one or more aliphatic rings and / or aromatic rings are fused. In the present invention, as long as at least one ring constituting an aromatic ring has a 5-membered aromatic heterocyclic structure or a 6-membered aromatic heterocyclic structure, the other rings may be any ring, The other rings are preferably selected from benzene ring and naphthalene ring. The number of rings forming the polycyclic aromatic heterocyclic compound is preferably two or three in one molecule, and more preferably two [0129]. As a pyridine compound, 2-acetylpyridine, 3-acetylpyridine, 4-acetylpyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-benzoylpyridine, 3-benzoylpyridine, 4-benzoylpyridine 2,3-Diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2-ethoxypyridine, 3 -Ethoxypyridine, 4-ethoxypyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-mercaptopyridine, 3-mercaptopyridine, 2-phenoxypyridine, 3-phenoxypyridine, 4-phenoxypyridine, 2 -Pyridica Bon acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, 2,6-pyridinedicarboxylic acid, 2,4-pyridine thiol and the like are preferable [0133].
Uzawa et al. 20160093413 in example 1 combines poly((2-methoxyaniline-5-sulfonic acid), aminopyridine, water dispersible polyester and water/methanol (see table 1) Specific examples of the water soluble polymer include polyvinyl alcohols such as polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral, a water soluble nylon resin, a water soluble alkyd resin, a water soluble melamine resin, a water soluble urea resin, a water soluble phenol resin, a water soluble epoxy resin, a water soluble polybutadiene resin, a water soluble acrylic resin, a water soluble urethane resin, a water soluble acrylic/styrene resin, a water soluble vinyl acetate/acrylic copolymerization resin, a water soluble polyester resin, a water soluble styrene/maleic acid copolymerization resin, a water soluble fluororesin, a water soluble polyisocyanate resin, and a copolymer thereof [0168]. Examples of the basic compound (B) include a pyridine derivative substituted with a tertiary amino group such as 2-aminopyridine, 3-aminopyridine, 4-aminopyridine; 2,6-diaminopyridine, 2,3-diaminopyridine, 3,4-diaminopyridine [0129]. Examples of the nitrogen-containing heterocyclic derivative in which the primary amino groups are substituted include aminopyridines such as 2-aminopyridine, 3-aminopyridine, or 4-aminopyridine, aminopyrimidines such as 2-aminopyrimidine, 4-aminopyrimidine, or 5-aminopyrimidine, diaminopyrimidines such as 2,4-diaminopyrimidine or 2,5-diaminopyrimidine, triaminopyrimidines such as 2,4,6-triaminopyrimidine, aminopyrazines such as 2-aminopyrazine or 3-aminopyrazine, diaminopyrazines such as 2,4-diaminopyrazine, 2,3-diaminopyrazine, or 2,5-diaminopyrazine, triaminopyrazines such as 2,3,5-triaminopyrazine, triazines such 2-aminotriazine, diaminotriazines such as 2,4-diaminotriazine, triaminotriazines such as 2,4,6-triaminotriazine (common name: melamine), guanamines such as acetoguanamine or benzoguanamine, aminopyrroles such as 2-aminopyrrole or 3-aminopyrrole, aminoquinolines such as 2-aminoquinoline, 3-aminoquinoline, 4-aminoquinoline, 5-aminoquinoline, 6-aminoquinoline, 7-aminoquinoline, or 8-aminoquinoline, aminoanthracenes, and a compound having an amino group substituted with an alkyl group of alkylpyridine like picolylamine [0142]. Among those compounds, from the viewpoint of the water resistance, aminopyridines such as aminopyridine, methylaminopyridine, dimethylaminopyridine, or diaminopyridine, aminopyrimidines, diaminopyrimidines, triaminopyrimidines, aminopyrazines, di aminopyrazines, triaminopyrazines, aminotriazines, diaminotriazines, triaminotriazines, phenanthrolines, and aminoquinolines are particularly preferable. Furthermore, from the viewpoint of the durability and condenser performance, aminopyridines, alkylaminopyridines, dialkylaminopyridines, aminoquinolines, alkylaminoquinolines, and dialkylaminoquinolines are particularly preferable [0145]. Examples of the additives include a crosslinking agent, a plasticizer, a dispersing agent, a fluidity modifying agent, a surfactant, a lubricating agent, a surfactant, a UV absorbing agent, a storage stabilizer, an adhesive aid, a thickening agent, a leveling agent, an anti-static agent, an inorganic filler, a slip agent, and an organic filler. Examples of the crosslinking agent include isocyanates such as block isocyanate, a carbodiimide compound, an epoxy compound, and a melamine compound [0181-0182]
Watanabe et al. JP 2004347735 (machine translation attached) teaches nitrogen containing heterocyclic compounds added to resists. These include
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(see pages 9 and 10). These are combined with polymers, a photoacid generator and solvent (PGMEA and ethyl lactate) and spin coated upon a substrate to a thickness of 550 nm (see tables 1-3) [0091-0102]. These are bounded by formulae 1 and 2,
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, where Wherein A is a nitrogen atom or ΔC—R .sup.7 It is. B is a nitrogen atom or ΔC—R .sup.8 It is. R .sup.1 Is an alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms. Examples of the polar functional group include a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide group, a carbonate group, and a cyano group. Or it contains one or more acetal groups. R .sup.2 , R .sup.3 , R .sup.4 , R .sup.5 Is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, or R .sup.2 And R .sup.3 , R .sup.4 And R .sup.5 May be bonded to each other to form a benzene ring, a naphthalene ring or a pyridine ring together with the carbon atoms to which they are bonded. R .sup.6 Is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. R .sup.7 , R .sup.8 Is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. Or R .sup.6 And R .sup.8 May combine with each other to form a benzene ring or a naphthalene ring together with the carbon atom to which they are attached. )
Here, in the general formula (1) or (2), R .sup.1 An alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms, particularly 2 to 10 carbon atoms represented by a hydroxyl group, a carbonyl group, an ether group, an ester group, a carbonate group as a polar functional group, It contains one or more sulfide group, cyano group or acetal group, and specifically, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 2,3-dihydroxypropyl group 2-hydroxycyclohexyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2- (methoxymethoxy) ethyl group, 2- (2-methoxyethoxy) ethyl group, 2-[(2-methoxyethoxy) methoxy] Ethyl group, 2- [2- (2-methoxyethoxy) ethoxy] ethyl group, 2-methoxymethoxypropyl group, 2,3-bis ( (Toximethoxy) propyl group, tetrahydrofurfuryl group, 2-tetrahydrofuryl group, tetrahydro-2H-pyran-2-yl group, tetrahydro-2H-pyran-4-yl group, 2- (tetrahydro-2H-pyran-2-yl) Yloxy) ethyl group, 2,2-dimethoxyethyl group, 3,3-diethoxypropyl group, 1,3-dioxolan-2-ylmethyl group, 1,3-dioxolan-4-ylmethyl group, 2,2-dimethyl- 1,3-dioxolan-4-ylmethyl group, 2-formyloxyethyl group, 2-acetoxyethyl group, 2-propionyloxyethyl group, 2-butyryloxyethyl group, 2-valeryloxyethyl group, 2-hexa Noyloxyethyl group, 2- (cyclohexanecarbonyloxy) ethyl group, 2- (tetrahydrofuran-2 Carbonyloxy) ethyl group, 2-methoxyacetoxyethyl group, 2-[(2-methoxyethoxy) acetoxy] ethyl group, 3-acetoxypropyl group, 2-acetoxypropyl group, 4-acetoxybutyl group, 2,3-di Acetoxypropyl group, 2-methoxycarbonyloxy group, 2-t-butoxycarbonyloxy group, (2-oxo-1,3-dioxolan-4-yl) methyl group, 2-oxotetrahydrofuran-3-yl group, 5- Oxotetrahydrofuran-3-yl group, 2-oxotetrahydro-2H-pyran-3-yl group, 2- (2-acetoxyethoxy) ethyl group, methoxycarbonylmethyl group, 2- (methoxycarbonyl) ethyl group, 3- (Methoxycarbonyl) propyl group, 4- (methoxycarbonyl) butyl group, ethoxy Carbonylmethyl group, 2- (ethoxycarbonyl) ethyl group, 3- (ethoxycarbonyl) propyl group, 4- (ethoxycarbonyl) butyl group, 3,3-bis (methoxycarbonyl) propyl group, 2-oxopropyl group, A tetrahydrothienyl group, a 2-tetrahydrothenyl group, a 2- (methylthiomethoxy) ethyl group, a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group, and a 3,3-dicyanopropyl group. However, the present invention is not limited to these.
In general formula (1) or (2) and A and B, R .sup.2 , R .sup.3 , R .sup.4 , R .sup.5 , R .sup.6 , R .sup.7 , R .sup.8 As a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Examples include, but are not limited to, isobutyl, t-butyl, pentyl, hexyl, decyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, and naphthyl groups [0015-0018] Examples of the crosslinking agent as the component (F) include compounds having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups, or vinyl ether groups in the molecule, such as substituted glycouril derivatives, urea derivatives, and hexa (methoxymethyl) melamine. Is preferably used. For example, tetraalkoxymethyl-substituted glycolurils such as N, N, N ', N'-tetramethoxymethylurea and hexamethylmelamine, tetrahydroxymethyl-substituted glycolurils and tetramethoxymethylglycoluril, substituted and unsubstituted bis- Examples thereof include phenolic compounds such as hydroxymethylphenols and bisphenol A and condensates such as epichlorohydrin. Particularly suitable crosslinking agents are 1,3,5,7-tetraalkoxymethylglycoluril or 1,3,5,7-tetrahydroxymethylglycoluril, such as 1,3,5,7-tetramethoxymethylglycoluril, 2,6-dihydroxymethyl p-cresol, 2,6-dihydroxymethylphenol, 2,2 ′, 6,6′-tetrahydroxymethylbisphenol A, and 1,4-bis- [2- (2-hydroxypropyl) ] -Benzene, N, N, N ', N'-tetramethoxymethylurea and hexamethoxymethylmelamine. The addition amount is optional, but is 1 to 25 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts of the base resin in the resist material. These may be added alone or in combination of two or more [0069]. A surfactant, an acidic compound, a stabilizer, a dye, and the like can be added to the resist composition of the present invention, if necessary, in addition to the above components [0085].
Watanabe et al. JP 2004347736 (machine translation attached) teaches nitrogen containing heterocyclic compounds added to resists. These include
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on page 13). Examples in table 1 combine these with a polymer, photoaacid generator and solvents (PGMEA, ethyl lactate), and spin coated upon a substrate [0123-0136]. These are embraced by formula 1,
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,
Where R.sup.1Is an alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms. Examples of the polar functional group include a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide group, a carbonate group, and a cyano group. Or it contains one or more acetal groups. R.sup.2, R.sup.3, R.sup.4Is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ) In this case, the basic compound represented by the general formula (1) is preferably a basic compound represented by the following general formulas (2) to (6), and the resist material contains one or more of these. Is preferred. The basic compounds of the formulas (2) to (6) are novel substances.
(Where R.sup.2, R.sup.3, R.sup.4Is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. R.sup.5, R.sup.7, R.sup.9, R.sup.ThirteenIs a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. R.sup.6, R.sup.8Is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and may include one or more hydroxyl groups, carbonyl groups, ester groups, ether groups, sulfide groups, carbonate groups, cyano groups, or acetal groups. R.sup.10Is an alkyl group having 1 to 15 carbon atoms, and may contain one or more hydroxyl groups, carbonyl groups, ester groups, ether groups, sulfide groups, carbonate groups, cyano groups or acetal groups. R.sup.11Is a linear, branched or cyclic n + 1-valent hydrocarbon group having 2 to 10 carbon atoms. R.sup.12Is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms which may be the same or different, and one or more of a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide group, a carbonate group, a cyano group or an acetal group And two R.sup.12They may combine with each other to form a ring. n = 2, 3, 4, or 5. )
Here, in the general formula (1), R.sup.1An alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms, particularly 2 to 10 carbon atoms represented by a hydroxyl group, a carbonyl group, an ether group, an ester group, a carbonate group as a polar functional group, It contains one or more sulfide group, cyano group or acetal group, and specifically, 2-oxotetrahydrofuran-3-yl group, 5-oxotetrahydrofuran-3-yl group, 2-oxotetrahydro-2H-pyran- 3-yl group, 2-tetrahydrofuryl group, tetrahydro-2H-pyran-2-yl group, tetrahydro-2H-pyran-4-yl group, tetrahydrofurfuryl group, 2-tetrahydrothienyl group, 2-tetrahydrothenyl group, 3,3-dicyanopropyl group, 3,3-bis (methoxycarbonyl) propyl group, and R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.Thirteen-R having.sup.5-OR.sup.6, -R.sup.7-OCO-R.sup.8, R.sup.9-COO-R.sup.10, -R.sup.11− (OR.sup.12).sub.n, -R.sup.Thirteen-CN can be exemplified, but not limited thereto.
In the general formulas (1) to (6), R.sup.2, R.sup.3, R.sup.4As a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, specifically, a hydrogen atom, Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, decyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, naphthyl, benzyl, A phenethyl group can be exemplified.
In the general formulas (2), (3), (4) and (6), R.sup.5, R.sup.7, R.sup.9, R.sup.ThirteenSpecific examples of the linear, branched or cyclic alkylene group having 1 to 10 carbon atoms represented by methylene group, ethylene group, ethylidene group, propylene group, isopropylidene group, 1,3-propanediyl group, 1,4-butanediyl group, 1,2-butanediyl group, 1,5-pentanediyl group, 1,2-pentanediyl group, 1,10-decanediyl group, 1,2-cyclopentanediyl group, 1,2-cyclohexanediyl Examples thereof include, but are not limited to, a 1,4-cyclohexanediyl group.
In the general formulas (2) and (3), R.sup.6, R.sup.8A hydrogen atom or an alkyl group having 1 to 15 carbon atoms represented by one or more of a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide group, a carbonate group, a cyano group or an acetal group, Specifically, hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, decyl group, pentadecyl group, cyclopentyl group, cyclohexyl group, 2-tetrahydrofuryl Group, 2-oxo-3-tetrahydrofuryl group, 2-tetrahydro-2H-pyranyl group, tetrahydrofurfuryl group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, (2-methoxyethoxy) methyl group, cyanomethyl group, Methylthiomethyl group, acetoxymethyl group, formyloxymethyl group, , 3-Dioxolan-4-ylmethyl group, (2,2-dimethyl-1,3-dioxolan-4-yl) methyl group, (2-oxo-1,3-dioxolan-4-yl) methyl group, methoxycarbonyl Group, ethoxycarbonyl group, t-butoxycarbonyl group, 2-hydroxyethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-tetrahydro-2H-pyranyloxy) ethyl group, 2-formyloxyethyl group, 2-acetoxyethyl group, 2-propionyloxyethyl group, 2-butyryloxyethyl group 2-valeryloxyethyl group, 2-hexanoyloxyethyl group, 2-cyanoethyl group, 2-methylthioe 2, 2-methoxycarbonyloxyethyl, 2,2-dimethoxyethyl, 2,2-diethoxyethyl, 3,3-dimethoxypropyl, 3,3-diethoxypropyl, 2-hydroxypropyl , A 2-methoxypropyl group, a 2-acetoxypropyl group, a 2-propionyloxypropyl group, a 3-hydroxypropyl group, and a 4-hydroxybutyl group, but are not limited thereto [0014-0020] Examples of the crosslinking agent as the component (F) include compounds having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups, or vinyl ether groups in the molecule, such as substituted glycouril derivatives, urea derivatives, and hexa (methoxymethyl) melamine. Is preferably used. For example, tetraalkoxymethyl-substituted glycolurils such as N, N, N ', N'-tetramethoxymethylurea and hexamethylmelamine, tetrahydroxymethyl-substituted glycolurils and tetramethoxymethylglycoluril, substituted and unsubstituted bis- Examples thereof include phenolic compounds such as hydroxymethylphenols and bisphenol A and condensates such as epichlorohydrin. Particularly suitable crosslinking agents are 1,3,5,7-tetraalkoxymethylglycoluril or 1,3,5,7-tetrahydroxymethylglycoluril, such as 1,3,5,7-tetramethoxymethylglycoluril, 2,6-dihydroxymethyl p-cresol, 2,6-dihydroxymethylphenol, 2,2 ′, 6,6′-tetrahydroxymethylbisphenol A, and 1,4-bis- [2- (2-hydroxypropyl) ] -Benzene, N, N, N ', N'-tetramethoxymethylurea and hexamethoxymethylmelamine. The addition amount is optional, but is 1 to 25 parts, preferably 5 to 20 parts, per 100 parts of the base resin in the resist material. These may be added alone or in combination of two or more. [0077-0078]. Examples of the hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine. Specific examples of the aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5- Dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (for example, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimension Lupyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, -Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.) ), Imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethyl) Lysine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivative, pyrimidine derivative, pyrazine derivative, pyrazoline derivative, pyrazolidine derivative, piperidine Derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g. quinoline, 3-quinolinecarbo) Nitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine Derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like are exemplified [0081]. The resist composition of the present invention may contain a surfactant, an acidic compound, and the like, if necessary, in addition to the above components [0093].
In addition to the basis above, it would have been obvious to modify the compositions rendered obvious by the combination of Sugata et al.JP 2000347414, in view of Ishikawa et al. 20100255429 by replacing the triethylamine with any of the amino, aminoalkyl, hydroxy or hydroxyalkyl substituted pyridine, pyrrole or pyrazine compounds disclosed in any one of Niikura et al 5518860, Shimoyama WO 2014050626, Uzawa et al. 20160093413, Watanabe et al. JP 2004347735 or Watanabe et al. JP 2004347736 to serve as a basic compound and/or crosslinker based upon these being known equivalents as basic/amine compounds and/or amine crosslinkers within resist art as evidenced in the applied references of this heading.
The examiner relies upon the response above to address the arguments as no further arguments were advanced.
Claims 16,18,21,22 and 24-38 are rejected under 35 U.S.C. 103 as being unpatentable over Sugata et al.JP 2000347414, in view of Ishikawa et al. 20100255429 and Ikeda et al. WO 2019076956, further in view of any one of Niikura et al 5518860, Shimoyama WO 2014050626, Uzawa et al. 20160093413, Watanabe et al. JP 2004347735 or Watanabe et al. JP 2004347736.
In addition to the basis above, it would have been obvious to modify the compositions rendered obvious by the combination of Sugata et al.JP 2000347414, in view of Ishikawa et al. 20100255429 and Ikeda et al. WO 2019076956 by replacing the triethylamine with any of the amino, aminoalkyl, hydroxy or hydroxyalkyl substituted pyridine, pyrrole or pyrazine compounds disclosed in any one of Niikura et al 5518860, Shimoyama WO 2014050626, Uzawa et al. 20160093413, Watanabe et al. JP 2004347735 or Watanabe et al. JP 2004347736 to serve as a basic compound and/or crosslinker based upon these being known equivalents as basic/amine compounds and/or amine crosslinkers within resist art as evidenced in the applied references of this heading.
The examiner relies upon the response above to address the arguments as no further arguments were advanced.
Claims 16,18,21,22 and 24-39 are rejected under 35 U.S.C. 103 as being unpatentable over Sugata et al. JP 2000347414, in view of Ishikawa et al. 20100255429, Ikeda et al. WO 2019076956, Yoshioda JP 2007078857 and Akashi et al. 20100119975 , further in view of any one of Niikura et al 5518860, Shimoyama WO 2014050626, Uzawa et al. 20160093413, Watanabe et al. JP 2004347735 or Watanabe et al. JP 2004347736.
In addition to the basis above, it would have been obvious to modify the compositions rendered obvious by the combination of Sugata et al.JP 2000347414,Ishikawa et al. 20100255429, Ikeda et al. WO 2019076956, Yoshioda JP 2007078857 and Akashi et al. 20100119975 by replacing the triethylamine with any of the amino, aminoalkyl, hydroxy or hydroxyalkyl substituted pyridine, pyrrole or pyrazine compounds disclosed in any one of Niikura et al 5518860, Shimoyama WO 2014050626, Uzawa et al. 20160093413, Watanabe et al. JP 2004347735 or Watanabe et al. JP 2004347736 to serve as a basic compound and/or crosslinker based upon these being known equivalents as basic/amine compounds and/or amine crosslinkers within resist art as evidenced in the applied references of this heading.
The examiner relies upon the response above to address the arguments as no further arguments were advanced.
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.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 June 25, 2026
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