WO2011058789A1 - Quinonediazide photosensitizer solution and positive-type resist composition - Google Patents

Quinonediazide photosensitizer solution and positive-type resist composition Download PDF

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Publication number
WO2011058789A1
WO2011058789A1 PCT/JP2010/061537 JP2010061537W WO2011058789A1 WO 2011058789 A1 WO2011058789 A1 WO 2011058789A1 JP 2010061537 W JP2010061537 W JP 2010061537W WO 2011058789 A1 WO2011058789 A1 WO 2011058789A1
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Prior art keywords
quinonediazide
photosensitizer
resist composition
precipitation
thiol compound
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PCT/JP2010/061537
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French (fr)
Japanese (ja)
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紘希 金谷
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ソニーケミカル＆インフォメーションデバイス株式会社
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Priority to CN2010800509276A priority Critical patent/CN102597876A/en
Publication of WO2011058789A1 publication Critical patent/WO2011058789A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/76—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0223—Iminoquinonediazides; Para-quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives

Definitions

  • the present invention relates to a quinonediazide-based photosensitizer solution having excellent temporal stability and a positive resist composition in which precipitation of the quinonediazide-based photosensitizer is suppressed.
  • Positive resist compositions in which an alkali-soluble resin such as a novolak resin is dissolved in an organic solvent and a crosslinking agent such as an epoxy resin, a quinonediazide-based photosensitizer, and the like are widely used in the semiconductor field and the electronic parts field .
  • a positive resist composition is subjected to a foreign matter removal process in which foreign matters are separated into furnaces by a filter at the time of production.
  • Patent Document 1 proposes thermally modify the quinonediazide photosensitizer.
  • the quinonediazide-based photosensitizer when the quinonediazide-based photosensitizer is heat-denatured, although the problem of precipitation is reduced, it may be thermally decomposed during heat denaturation, and the photosensitivity as the photosensitizer may be reduced.
  • the quinonediazide-based photosensitizer is handled as a powdered solid, and there is a problem that it is difficult to dissolve in the composition when preparing a positive resist composition.
  • the present invention is intended to solve the above-described conventional problems, and can suppress or prevent the precipitation of a quinonediazide-based photosensitizer from a positive resist composition without performing heat denaturation treatment. It is an object of the present invention to facilitate the dissolution of a quinonediazide-based photosensitizer in a positive resist composition when preparing a resist composition.
  • the present inventor can suppress or prevent the precipitation of the quinone diazide photosensitizer by allowing the quinone diazide photosensitizer to coexist with the quinone diazide photosensitizer. It has been found that even in a solution in which a compound is dissolved, precipitation of a quinonediazide photosensitizer can be suppressed or prevented, and such a solution can be easily mixed with a positive resist composition, and the present invention has been completed.
  • the present invention relates to a quinonediazide photosensitizer solution in which a quinonediazide photosensitizer is dissolved in an organic solvent, which contains a thiol compound as a quinonediazide photosensitizer precipitation inhibitor, Provide a solution.
  • the present invention also provides a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinonediazide photosensitizer, and an organic solvent, and further comprising a thiol compound as a precipitation inhibitor for the quinonediazide photosensitizer.
  • a positive resist composition is provided.
  • the present invention is a method for suppressing or preventing the precipitation of a quinone diazide photosensitizer from a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinone diazide photosensitizer, and an organic solvent
  • a method for suppressing or preventing quinonediazide-based photosensitizer deposition which comprises adding a thiol compound as a quinonediazide-based photosensitizer precipitation inhibitor to a positive resist composition.
  • quinonediazide photosensitizer solution or positive resist composition of the present invention a quinonediazide photosensitizer and a thiol compound coexist. For this reason, precipitation of a quinonediazide type photosensitizer can be suppressed or prevented in a quinonediazide type photosensitizer solution or a positive resist composition.
  • the quinonediazide photosensitizer solution of the present invention is obtained by dissolving a quinonediazide photosensitizer in an organic solvent and further containing a thiol compound as a precipitation inhibitor. Thereby, precipitation of a quinonediazide type photosensitizer can be suppressed or prevented.
  • a thiol compound is used as an anti-precipitation agent for a quinonediazide photosensitizer.
  • the thiol compound is an aromatic or aliphatic compound having one or more, preferably two or more thiol groups in the molecule.
  • bismuthiol (chemical structural formula (A): MTD, Tokyo Chemical Industry Co., Ltd.) ), 2-methylthio-5-mercaptothiadiazole (chemical structural formula (B): M1384, Tokyo Chemical Industry Co., Ltd.), pentaerythritol-tetrakis-mercaptopropionate (chemical structural formula (C): PEMPII, Sakai Chemical Co., Ltd.) )), Pentaerythritol-tetrakis-mercaptobutyrate (chemical structural formula (D): MTPE1, Showa Denko KK), 2-dibutylamino-4,6-dithio-s-triazine (chemical structural formula (E): Zisnet-DB, Sankyo Kasei Co., Ltd.). Two or more of these may be used in combination. Among these, bismuth thiol having the highest precipitation suppression or prevention effect can be preferably used.
  • the content of the thiol compound as a quinonediazide photosensitizer precipitation inhibitor is too small, the effect of suppressing or preventing the precipitation of the quinonediazide photosensitizer is insufficient.
  • quinonediazide photosensitizers conventionally used as photosensitizers for positive resist compositions can be used.
  • diazonaphthoquinone DNQ
  • 1,2- Ester compounds of naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid and low-molecular aromatic hydroxy compounds such as 2,3,4-trihydroxybenzophenone
  • Examples include 1,3,5-trihydroxybenzene, 2,3,4,4′-tetrahydroxybenzophenone, 2- and 4-methylphenol, esters with 4,4′-hydroxypropane, and the like.
  • Particularly preferred quinonediazide photosensitizers include naphthoquinonediazide derivatives.
  • specific examples of the naphthoquinone diazide derivative include naphthoquinone diazide derivatives represented by the following chemical structural formulas (F), (G), and (H). Two or more of these can be used in combination.
  • the naphthoquinone diazide derivative of the chemical structural formula (G) can be preferably used from the viewpoint of high sensitivity.
  • the content of the quinonediazide photosensitizer in the quinonediazide photosensitizer solution of the present invention varies depending on the type of organic solvent used, but if it is too small, it will be difficult to form a pattern as a photoresist. Therefore, the amount is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the resist solid content.
  • organic solvent used in the quinonediazide-based photosensitizer solution of the present invention various aromatic hydrocarbons, aliphatic or alicyclic esters, polyethers, and the like can be appropriately used. From this viewpoint, it is preferable to use ⁇ -butyrolactone or triglyme. In addition, you may use an organic solvent in mixture of 2 or more types.
  • a quinonediazide-based photosensitizer and a thiol compound as an anti-precipitation agent are charged into an organic solvent, and preferably the mixture is heated at a temperature not higher than the thermal decomposition temperature of the quinonediazide-based photosensitizer for 1 hour.
  • it can prepare by stirring using stirring apparatuses, such as a ball mill, and dissolving them in an organic solvent.
  • the obtained quinonediazide photosensitizer solution may be further subjected to a filtration treatment in order to remove insoluble matters.
  • the quinonediazide photosensitizer solution thus obtained can be preferably used as a photosensitizer for a positive resist composition.
  • This positive resist composition is a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinonediazide-based photosensitizer, and an organic solvent, and further includes a thiol as a precipitation inhibitor for the quinonediazide-based photosensitizer. It contains a compound. Therefore, the positive resist composition of the present invention suppresses or prevents the quinonediazide photosensitizer from precipitating during storage.
  • the positive resist composition of the present invention is basically composed of a conventional positive resist composition (component types, ratios thereof, etc.) except that it contains a thiol compound as a quinonediazide-based photosensitizer precipitation inhibitor.
  • a crosslinking agent that does not substantially react with the thiol compound. Therefore, although it is not impossible, it is preferable to avoid the use of an epoxy-based crosslinking agent that may react with the thiol compound.
  • the kind of quinonediazide-based photosensitizer and the thiol compound that is a precipitation inhibitor thereof are as described in the quinonediazide-based photosensitizer solution of the present invention.
  • the amount of the thiol compound in the positive resist composition is determined according to the amount of the quinone diazide photosensitizer as in the case of the quinone diazide photosensitizer solution, and the amount of the quinone diazide photosensitizer will be described later. It is determined by the blending amount of the alkali-soluble resin.
  • the amount of the quinonediazide-based photosensitizer in the positive resist composition is too small, pattern formation may be difficult, and if it is too large, the physical properties of the film may be lowered.
  • it is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass.
  • alkali-soluble resin constituting the positive resist composition of the present invention examples include phenol novolac resins, cresol novolac resins, alkali-soluble polyimide resins, polybenzoxazole precursors, and the like.
  • the crosslinking agent can be selected from diamines, polyisocyanates, benzoxazines, resoles and the like according to the type of alkali-soluble resin. If the blending amount of the crosslinking agent is too small, the film physical properties may be lowered, and if it is too much, the photosensitivity may be lowered. Therefore, the amount is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. 30 parts by mass, more preferably 1 to 10 parts by mass.
  • Examples of the organic solvent constituting the positive resist composition of the present invention include toluene, ⁇ -butyrolactone, triglyme, diglyme, methyl benzoate, ethyl benzoate, N-methylpyrrolidone, N, N-dimethylacetamide, N, N— Examples include dimethylformamide. Of these, ⁇ -butyrolactone and triglyme having good printability can be preferably used.
  • the amount of the organic solvent used is usually preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the resist solid content.
  • the positive resist composition of the present invention can be prepared by uniformly mixing an alkali-soluble resin, a crosslinking agent, a quinonediazide-based photosensitizer, an organic solvent, and a thiol compound by a conventional method.
  • the quinonediazide photosensitizer and the thiol compound may be dissolved in a part of an organic solvent in advance to obtain a quinonediazide photosensitizer solution, and the solution and other components may be mixed.
  • the quinonediazide-based photosensitizer solution and the positive resist composition of the present invention have been described above.
  • the present invention also has an aspect as a method for suppressing or preventing quinonediazide-based photosensitizer precipitation described below. This method is also encompassed by the present invention.
  • one aspect of the present invention is a method for suppressing or preventing precipitation of a quinone diazide photosensitizer from a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinone diazide photosensitizer, and an organic solvent.
  • a quinonediazide-based photosensitizer deposition inhibiting or preventing method comprising blending a thiol compound as a quinonediazide-based photosensitizer precipitation inhibitor into a positive resist composition.
  • a quinonediazide photosensitizer solution obtained by dissolving a quinonediazide photosensitizer and a thiol compound as an anti-precipitation agent in an organic solvent is used. Can do.
  • Comparative Example 1 an example in which no thiol compound was blended, as Comparative Example 2, in which a compound of the chemical structural formula (I) (CDA-10, ADEKA Co., Ltd.) was blended instead of a thiol compound, An example in which a compound of the structural formula (J) (BF-BXZ, Konishi Chemical Co., Ltd.) is blended in place of the compound is shown.
  • the obtained solution was continuously stirred at room temperature, and the number of days on which the photosensitive agent was deposited on the inner wall of the container was examined visually.
  • the obtained results are shown in Table 1. When no precipitation is observed for 7 days or more, it can be evaluated that there is no precipitation.
  • Example 2 Compared to the case of Comparative Example 1 in which the thiol compound was not blended, in the case of Example 2 in which the monothiol compound was blended, the number of days in which precipitation occurred was 2 to 4 days, and the precipitation suppression effect was sufficiently confirmed. . In Examples 1 and 3 to 5 containing a dithiol compound, no quinonediazide-based photosensitizer was observed even after 7 days.
  • Example 6 the precipitation inhibitory effect by the addition amount of bismuthiol was investigated. That is, as shown in Table 2, 10 g of a naphthoquinonediazide photosensitizer (4NT-300, Toyo Gosei Co., Ltd.) having a chemical structural formula (G), 10 g of ⁇ -butyrolactone, and a thiol having a chemical structural formula (A)
  • the compound (bismuthiol) 0.25 g, 0.5 g, or 1 g was stirred with a ball mill at room temperature for half a day and dissolved uniformly.
  • the obtained solution was continuously stirred at room temperature, and the number of days that the photosensitizer was deposited on the inner wall of the container was examined visually.
  • Table 2 The obtained results are shown in Table 2.
  • Example 7 it was tested whether a photosensitizer other than 4NT-300 also exhibited the effect of suppressing the precipitation of bismuththiol from the viewpoint of water content. That is, as shown in Table 3, 10 g of a naphthoquinone diazide photosensitizer of chemical structural formula (G) or (H), 10 g of ⁇ -butyrolactone, and 1 g of thiol compound (bismuthiol) of chemical structural formula (A) are added at room temperature. Then, the mixture was stirred for half a day with a ball mill and dissolved uniformly. The obtained solution was continuously stirred at room temperature, and the number of days that the photosensitizer was deposited on the inner wall of the container was examined visually. The obtained results are shown in Table 3.
  • G * 1 Photosensitizer of chemical structural formula (G) (4NT-300, Toyo Gosei Co., Ltd.)
  • G * 2 Photosensitizer with chemical structural formula (G) (DTEP-300, Daitokemix Co., Ltd.)
  • G * 3 Photosensitizer with chemical structural formula (G) (DTEP-250, Daitokemix Co., Ltd.)
  • H * 1 Photosensitizer of chemical structural formula (H) (4C-PA-280, Daito Chemix Co., Ltd.)
  • G * 1 , G * 2, and G * 3 have the same chemical structural formula, but different manufacturers. 4NT-300 and DTEP-300 are considered equivalent. Further, G * 2 has a higher naphthoquinonediazosulfonyl group substitution (tetra-substituted product) ratio than G * 3 .
  • the quinonediazide photosensitizer solution or positive resist composition of the present invention a quinonediazide photosensitizer and a thiol compound coexist. For this reason, precipitation of a quinonediazide type photosensitizer can be suppressed or prevented in a quinonediazide type photosensitizer solution or a positive resist composition. Therefore, the quinonediazide-based photosensitizer solution or positive resist composition of the present invention has excellent storage stability and is particularly useful for the production of electronic components.

Abstract

Disclosed is a quinonediazide photosensitizer solution comprising a quinonediazide photosensitizer dissolved in an organic solvent so that the precipitation of the quinonediazide photosensitizer from a positive-type resist composition can be reduced or prevented without requiring any thermal modification treatment and the dissolution of the quinonediazide photosensitizer in the positive-type resist composition can be facilitated in the preparation of the positive-type resist composition. The quinonediazide photosensitizer solution contains a thiol compound as an agent for preventing the precipitation of the quinonediazide photosensitizer. The positive-type resist composition comprises an alkali-soluble resin, a cross-linking agent, a quinonediazide photosensitizer, and a thiol compound as an agent for preventing the precipitation of the quinonediazide photosensitizer.

Description

キノンジアジド系感光剤溶液及びポジ型レジスト組成物Quinonediazide photosensitizer solution and positive resist composition
　本発明は、経時安定性に優れたキノンジアジド系感光剤溶液、キノンジアジド系感光剤の析出が抑制されたポジ型レジスト組成物に関する。 The present invention relates to a quinonediazide-based photosensitizer solution having excellent temporal stability and a positive resist composition in which precipitation of the quinonediazide-based photosensitizer is suppressed.
　有機溶剤にノボラック樹脂等のアルカリ可溶性樹脂を溶解した溶液に、エポキシ樹脂等の架橋剤、キノンジアジド系感光剤等を配合したポジ型レジスト組成物が、半導体分野や電子部品分野で広く使用されている。このようなポジ型レジスト組成物に対しては、製造の際にフィルターで異物を炉別するという異物除去処理が施されている。 Positive resist compositions in which an alkali-soluble resin such as a novolak resin is dissolved in an organic solvent and a crosslinking agent such as an epoxy resin, a quinonediazide-based photosensitizer, and the like are widely used in the semiconductor field and the electronic parts field . Such a positive resist composition is subjected to a foreign matter removal process in which foreign matters are separated into furnaces by a filter at the time of production.
　しかしながら、ポジ型レジスト組成物にそのような異物除去処理を施しても、その保管中にキノンジアジド系感光剤が析出するという問題があった。 However, even when such a foreign matter removal treatment is applied to the positive resist composition, there is a problem that a quinonediazide-based photosensitizer is deposited during storage.
　そこで、キノンジアジド系感光剤の析出を防止するために、キノンジアジド系感光剤を熱変性することが提案されている（特許文献１）。 Therefore, in order to prevent the precipitation of the quinonediazide photosensitizer, it has been proposed to thermally modify the quinonediazide photosensitizer (Patent Document 1).
特開昭６３－１１３４５１号公報Japanese Unexamined Patent Publication No. Sho 63-113451
　しかしながら、キノンジアジド系感光剤を熱変性した場合、析出の問題は軽減されるものの、熱変性時に熱分解し、感光剤としての感光能が低下する場合があった。また、キノンジアジド系感光剤は粉末固体で取り扱われており、ポジ型レジスト組成物の調製の際に、組成物中に溶解し難いという問題もあった。 However, when the quinonediazide-based photosensitizer is heat-denatured, although the problem of precipitation is reduced, it may be thermally decomposed during heat denaturation, and the photosensitivity as the photosensitizer may be reduced. In addition, the quinonediazide-based photosensitizer is handled as a powdered solid, and there is a problem that it is difficult to dissolve in the composition when preparing a positive resist composition.
　本発明は、以上の従来の課題を解決しようとするものであり、熱変性処理をせずとも、ポジ型レジスト組成物からキノンジアジド系感光剤の析出を抑制又は防止できるようにすると共に、ポジ型レジスト組成物の調製の際にポジ型レジスト組成物へのキノンジアジド系感光剤の溶解を容易にすることを目的とする。 The present invention is intended to solve the above-described conventional problems, and can suppress or prevent the precipitation of a quinonediazide-based photosensitizer from a positive resist composition without performing heat denaturation treatment. It is an object of the present invention to facilitate the dissolution of a quinonediazide-based photosensitizer in a positive resist composition when preparing a resist composition.
　本発明者は、ポジ型レジスト組成物中において、キノンジアジド系感光剤に対しチオール化合物を共存させることにより、キノンジアジド系感光剤の析出を抑制又は防止できること、また、有機溶剤にキノンジアジド系感光剤とチオール化合物とを溶解させた溶液においてもキノンジアジド系感光剤の析出を抑制又は防止でき、また、そのような溶液をポジ型レジスト組成物に容易に混合できることを見出し、本発明を完成させるに至った。 In the positive resist composition, the present inventor can suppress or prevent the precipitation of the quinone diazide photosensitizer by allowing the quinone diazide photosensitizer to coexist with the quinone diazide photosensitizer. It has been found that even in a solution in which a compound is dissolved, precipitation of a quinonediazide photosensitizer can be suppressed or prevented, and such a solution can be easily mixed with a positive resist composition, and the present invention has been completed.
　即ち、本発明は、キノンジアジド系感光剤が有機溶剤に溶解してなるキノンジアジド系感光剤溶液であって、キノンジアジド系感光剤の析出防止剤としてチオール化合物を含有することを特徴とするキノンジアジド系感光剤溶液を提供する。 That is, the present invention relates to a quinonediazide photosensitizer solution in which a quinonediazide photosensitizer is dissolved in an organic solvent, which contains a thiol compound as a quinonediazide photosensitizer precipitation inhibitor, Provide a solution.
　また、本発明は、アルカリ可溶性樹脂と、架橋剤と、キノンジアジド系感光剤と、有機溶剤とを含有するポジ型レジスト組成物であって、更に、キノンジアジド系感光剤の析出防止剤としてチオール化合物を含有するポジ型レジスト組成物を提供する。 The present invention also provides a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinonediazide photosensitizer, and an organic solvent, and further comprising a thiol compound as a precipitation inhibitor for the quinonediazide photosensitizer. A positive resist composition is provided.
　更に、本発明は、アルカリ可溶性樹脂と、架橋剤と、キノンジアジド系感光剤と、有機溶剤とを含有するポジ型レジスト組成物から、キノンジアジド系感光剤の析出を抑制又は防止する方法であって、ポジ型レジスト組成物に、キノンジアジド系感光剤の析出防止剤としてチオール化合物を配合することを特徴とするキノンジアジド系感光剤析出抑制又は防止方法を提供する。 Furthermore, the present invention is a method for suppressing or preventing the precipitation of a quinone diazide photosensitizer from a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinone diazide photosensitizer, and an organic solvent, Provided is a method for suppressing or preventing quinonediazide-based photosensitizer deposition, which comprises adding a thiol compound as a quinonediazide-based photosensitizer precipitation inhibitor to a positive resist composition.
　本発明のキノンジアジド系感光剤溶液又はポジ型レジスト組成物においては、キノンジアジド系感光剤とチオール化合物とを共存させている。このため、キノンジアジド系感光剤溶液又はポジ型レジスト組成物において、キノンジアジド系感光剤の析出を抑制又は防止することができる。 In the quinonediazide photosensitizer solution or positive resist composition of the present invention, a quinonediazide photosensitizer and a thiol compound coexist. For this reason, precipitation of a quinonediazide type photosensitizer can be suppressed or prevented in a quinonediazide type photosensitizer solution or a positive resist composition.
　本発明のキノンジアジド系感光剤溶液は、有機溶剤にキノンジアジド系感光剤を溶解させ、更に、その析出防止剤としてチオール化合物を含有させたものである。これにより、キノンジアジド系感光剤の析出を抑制又は防止することができる。 The quinonediazide photosensitizer solution of the present invention is obtained by dissolving a quinonediazide photosensitizer in an organic solvent and further containing a thiol compound as a precipitation inhibitor. Thereby, precipitation of a quinonediazide type photosensitizer can be suppressed or prevented.
　本発明において、キノンジアジド系感光剤の析出防止剤としてチオール化合物を使用する。チオール化合物としては、分子中に１以上、好ましくは２以上のチオール基を有する芳香族もしくは脂肪族化合物であり、具体的には、ビスムチオール（化学構造式（Ａ）：ＭＴＤ，東京化成（株））、２－メチルチオ－５－メルカプトチアジアゾール（化学構造式（Ｂ）：Ｍ１３８４，東京化成（株））、ペンタエリスリトール－テトラキス－メルカプトプロピオネート（化学構造式（Ｃ）：ＰＥＭＰＩＩ，堺化学（株））、ペンタエリスリトール－テトラキス－メルカプトブチレート（化学構造式（Ｄ）：ＭＴＰＥ１，昭和電工（株））、２－ジブチルアミノ－４，６－ジチオ－ｓ－トリアジン（化学構造式（Ｅ）：Ｚｉｓｎｅｔ－ＤＢ，三協化成（株））等を挙げることができる。これらは２種以上を併用してもよい。これらの中でも、析出抑制又は防止効果が最も高いビスムチオールを好ましく使用することができる。 In the present invention, a thiol compound is used as an anti-precipitation agent for a quinonediazide photosensitizer. The thiol compound is an aromatic or aliphatic compound having one or more, preferably two or more thiol groups in the molecule. Specifically, bismuthiol (chemical structural formula (A): MTD, Tokyo Chemical Industry Co., Ltd.) ), 2-methylthio-5-mercaptothiadiazole (chemical structural formula (B): M1384, Tokyo Chemical Industry Co., Ltd.), pentaerythritol-tetrakis-mercaptopropionate (chemical structural formula (C): PEMPII, Sakai Chemical Co., Ltd.) )), Pentaerythritol-tetrakis-mercaptobutyrate (chemical structural formula (D): MTPE1, Showa Denko KK), 2-dibutylamino-4,6-dithio-s-triazine (chemical structural formula (E): Zisnet-DB, Sankyo Kasei Co., Ltd.). Two or more of these may be used in combination. Among these, bismuth thiol having the highest precipitation suppression or prevention effect can be preferably used.
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-I000002
　本発明のキノンジアジド系感光剤溶液における、キノンジアジド系感光剤の析出防止剤としてのチオール化合物の含有量は、少な過ぎるとキノンジアジド系感光剤の析出抑制又は防止効果が不十分となり、多すぎると現像特性の低下を引き起こすので、キノンジアジド系感光剤１００質量部に対し、好ましくは０．０１～１０質量部、より好ましくは０．１～５質量部である。 In the quinonediazide photosensitizer solution of the present invention, if the content of the thiol compound as a quinonediazide photosensitizer precipitation inhibitor is too small, the effect of suppressing or preventing the precipitation of the quinonediazide photosensitizer is insufficient. Is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the quinonediazide photosensitizer.
　本発明で使用するキノンジアジド系感光剤としては、従来よりポジ型レジスト組成物の感光剤として使用されているキノンジアジド系感光剤を使用することができ、例えば、ジアゾナフトキノン（ＤＮＱ）、１，２－ナフトキノン－２－ジアジド－５－スルホン酸または１，２－ナフトキノン－２－ジアジド－４－スルホン酸と、低分子芳香族ヒドロキシ化合物とのエステル化合物、例えば、２，３，４－トリヒドロキシベンゾフェノン、１，３，５－トリヒドロキシベンゼン、２，３，４，４’－テトラヒドロキシベンゾフェノン、２－及び４－メチルフェノール、４，４’－ヒドロキシプロパンとのエステルなどが挙げられるが、これらに限定されるものではない。特に好ましいキノンジアジド系感光剤としてはナフトキノンジアジド誘導体を挙げることができる。ここで、ナフトキノンジアジド誘導体の具体例としては、以下の化学構造式（Ｆ）、（Ｇ）、（Ｈ）で表されるナフトキノンジアジド誘導体等を挙げることができる。これらは二種以上を併用することができる。これらの中でも、高感度であるという点から化学構造式（Ｇ）のナフトキノンジアジド誘導体を好ましく使用することができる。 As the quinonediazide photosensitizer used in the present invention, quinonediazide photosensitizers conventionally used as photosensitizers for positive resist compositions can be used. For example, diazonaphthoquinone (DNQ), 1,2- Ester compounds of naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid and low-molecular aromatic hydroxy compounds, such as 2,3,4-trihydroxybenzophenone, Examples include 1,3,5-trihydroxybenzene, 2,3,4,4′-tetrahydroxybenzophenone, 2- and 4-methylphenol, esters with 4,4′-hydroxypropane, and the like. Is not to be done. Particularly preferred quinonediazide photosensitizers include naphthoquinonediazide derivatives. Here, specific examples of the naphthoquinone diazide derivative include naphthoquinone diazide derivatives represented by the following chemical structural formulas (F), (G), and (H). Two or more of these can be used in combination. Among these, the naphthoquinone diazide derivative of the chemical structural formula (G) can be preferably used from the viewpoint of high sensitivity.
Figure JPOXMLDOC01-appb-I000003
Figure JPOXMLDOC01-appb-I000003
　なお、これらの化学構造式（Ｆ）、（Ｇ）及び（Ｈ）のそれぞれにおいて、複数存在する置換基Ｒの全てがナフトキノンジアジドスルホニル基であることが好ましい。他方、すべてのＲがＨであることはない。 In addition, in each of these chemical structural formulas (F), (G), and (H), it is preferable that all of the plurality of substituents R are naphthoquinonediazidosulfonyl groups. On the other hand, not all R are H.
　本発明のキノンジアジド系感光剤溶液におけるキノンジアジド系感光剤の含有量は、使用する有機溶剤の種類などにより異なるが、少なすぎるとフォトレジストとしてのパターン形成が困難となり、多すぎるとレジスト膜物性の低下を引き起こすおそれがあるので、レジスト固形分１００質量部に対し、好ましくは５～５０質量部、より好ましくは１０～３０質量部である。 The content of the quinonediazide photosensitizer in the quinonediazide photosensitizer solution of the present invention varies depending on the type of organic solvent used, but if it is too small, it will be difficult to form a pattern as a photoresist. Therefore, the amount is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the resist solid content.
　本発明のキノンジアジド系感光剤溶液で使用する有機溶剤としては、種々の芳香族炭化水素類、脂肪族又は脂環式エステル類、ポリエーテル類等を適宜使用することができるが、中でもレジスト印刷性の観点からγ－ブチロラクトン、トリグライムを使用することが好ましい。なお、有機溶剤は二種以上を混合して使用してもよい。 As the organic solvent used in the quinonediazide-based photosensitizer solution of the present invention, various aromatic hydrocarbons, aliphatic or alicyclic esters, polyethers, and the like can be appropriately used. From this viewpoint, it is preferable to use γ-butyrolactone or triglyme. In addition, you may use an organic solvent in mixture of 2 or more types.
　本発明のキノンジアジド系感光剤溶液は、キノンジアジド系感光剤とその析出防止剤としてのチオール化合物とを有機溶剤中に投入し、好ましくは混合物をキノンジアジド系感光剤の熱分解温度以下の温度で１時間以上、ボールミル等の撹拌装置を用いて撹拌し、それらを有機溶剤中に溶解させることにより調製することができる。得られたキノンジアジド系感光剤溶液は、更に、不溶解物を除去するために、濾過処理してもよい。 In the quinonediazide-based photosensitizer solution of the present invention, a quinonediazide-based photosensitizer and a thiol compound as an anti-precipitation agent are charged into an organic solvent, and preferably the mixture is heated at a temperature not higher than the thermal decomposition temperature of the quinonediazide-based photosensitizer for 1 hour. As mentioned above, it can prepare by stirring using stirring apparatuses, such as a ball mill, and dissolving them in an organic solvent. The obtained quinonediazide photosensitizer solution may be further subjected to a filtration treatment in order to remove insoluble matters.
　このようにして得られたキノンジアジド系感光剤溶液は、ポジ型レジスト組成物の感光剤として好ましく使用することができる。 The quinonediazide photosensitizer solution thus obtained can be preferably used as a photosensitizer for a positive resist composition.
　次に、本発明のポジ型レジスト組成物について説明する。このポジ型レジスト組成物は、アルカリ可溶性樹脂と、架橋剤と、キノンジアジド系感光剤と、有機溶剤とを含有するポジ型レジスト組成物であって、更に、キノンジアジド系感光剤の析出防止剤としてチオール化合物を含有するものである。従って、本発明のポジ型レジスト組成物は、その保存時に、キノンジアジド系感光剤が析出することが抑制又は防止される。 Next, the positive resist composition of the present invention will be described. This positive resist composition is a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinonediazide-based photosensitizer, and an organic solvent, and further includes a thiol as a precipitation inhibitor for the quinonediazide-based photosensitizer. It contains a compound. Therefore, the positive resist composition of the present invention suppresses or prevents the quinonediazide photosensitizer from precipitating during storage.
　本発明のポジ型レジスト組成物は、キノンジアジド系感光剤の析出防止剤としてチオール化合物を含有すること以外、基本的に従来のポジ型レジスト組成物の構成（成分の種類、それらの量比等）と同様に構成することができるが、架橋剤としてチオール化合物と実質的に反応してないものを選択することが求められる。従って、チオール化合物と反応するおそれのあるエポキシ系架橋剤を使用することは、不可能ではないが、避けることが好ましい。 The positive resist composition of the present invention is basically composed of a conventional positive resist composition (component types, ratios thereof, etc.) except that it contains a thiol compound as a quinonediazide-based photosensitizer precipitation inhibitor. However, it is required to select a crosslinking agent that does not substantially react with the thiol compound. Therefore, although it is not impossible, it is preferable to avoid the use of an epoxy-based crosslinking agent that may react with the thiol compound.
　また、キノンジアジド系感光剤及びその析出防止剤であるチオール化合物の種類については、本発明のキノンジアジド系感光剤溶液で既に説明したとおりである。また、ポジ型レジスト組成物におけるチオール化合物の配合量は、キノンジアジド系感光剤溶液の場合と同様に、キノンジアジド系感光剤の配合量に応じて決定され、キノンジアジド系感光剤の配合量は、後述するアルカリ可溶性樹脂の配合量によって決定される。例えば、ポジ型レジスト組成物におけるキノンジアジド系感光剤の配合量は、少なすぎるとパターン形成が困難となるおそれがあり、多すぎると膜物性の低下を引き起こすおそれがあるので、アルカリ可溶性樹脂１００質量部に対し、好ましくは５～５０質量部、より好ましくは１０～３０質量部である。 Further, the kind of quinonediazide-based photosensitizer and the thiol compound that is a precipitation inhibitor thereof are as described in the quinonediazide-based photosensitizer solution of the present invention. The amount of the thiol compound in the positive resist composition is determined according to the amount of the quinone diazide photosensitizer as in the case of the quinone diazide photosensitizer solution, and the amount of the quinone diazide photosensitizer will be described later. It is determined by the blending amount of the alkali-soluble resin. For example, if the amount of the quinonediazide-based photosensitizer in the positive resist composition is too small, pattern formation may be difficult, and if it is too large, the physical properties of the film may be lowered. On the other hand, it is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass.
　本発明のポジ型レジスト組成物を構成するアルカリ可溶性樹脂としては、例えば、フェノールノボラック系樹脂、クレゾールノボラック系樹脂、アルカリ可溶性ポリイミド樹脂、ポリベンゾオキサゾール前駆体などが挙げられる。 Examples of the alkali-soluble resin constituting the positive resist composition of the present invention include phenol novolac resins, cresol novolac resins, alkali-soluble polyimide resins, polybenzoxazole precursors, and the like.
　架橋剤としては、アルカリ可溶性樹脂の種類に応じて、ジアミン類、ポリイソシアネート類、ベンゾオキサジン類、レゾール類などから選択することができる。また、架橋剤の配合量は、少なすぎると膜物性の低下を引き起こすおそれがあり、多すぎると感光性が低下するおそれがあるので、アルカリ可溶性樹脂１００質量部に対し、好ましくは０．１～３０質量部、より好ましくは１～１０質量部である。 The crosslinking agent can be selected from diamines, polyisocyanates, benzoxazines, resoles and the like according to the type of alkali-soluble resin. If the blending amount of the crosslinking agent is too small, the film physical properties may be lowered, and if it is too much, the photosensitivity may be lowered. Therefore, the amount is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. 30 parts by mass, more preferably 1 to 10 parts by mass.
　本発明のポジ型レジスト組成物を構成する有機溶剤としては、トルエン、γ－ブチロラクトン、トリグライム、ジグライム、安息香酸メチル、安息香酸エチル、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド等を挙げることができる。中でも、印刷性が良好なγ－ブチロラクトン、トリグライムを好ましく使用することができる。なお、有機溶剤の使用量は、通常、レジスト固形分１００質量部に対し、好ましくは１０～１０００質量部、より好ましくは２０～５００質量部である。 Examples of the organic solvent constituting the positive resist composition of the present invention include toluene, γ-butyrolactone, triglyme, diglyme, methyl benzoate, ethyl benzoate, N-methylpyrrolidone, N, N-dimethylacetamide, N, N— Examples include dimethylformamide. Of these, γ-butyrolactone and triglyme having good printability can be preferably used. The amount of the organic solvent used is usually preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the resist solid content.
　本発明のポジ型レジスト組成物は、アルカリ可溶性樹脂と、架橋剤と、キノンジアジド系感光剤と、有機溶剤と、チオール化合物とを、常法により均一に混合することにより調製することができる。この場合、キノンジアジド系感光剤とチオール化合物とを、予め有機溶剤の一部に溶解させてキノンジアジド系感光剤溶液としておき、その溶液と他の成分とを混合してもよい。 The positive resist composition of the present invention can be prepared by uniformly mixing an alkali-soluble resin, a crosslinking agent, a quinonediazide-based photosensitizer, an organic solvent, and a thiol compound by a conventional method. In this case, the quinonediazide photosensitizer and the thiol compound may be dissolved in a part of an organic solvent in advance to obtain a quinonediazide photosensitizer solution, and the solution and other components may be mixed.
　以上、本発明のキノンジアジド系感光剤溶液とポジ型レジスト組成物とを説明したが、本発明は、また、以下に説明するキノンジアジド系感光剤析出抑制又は防止方法としての側面も有する。この方法も本発明に包含される。 The quinonediazide-based photosensitizer solution and the positive resist composition of the present invention have been described above. However, the present invention also has an aspect as a method for suppressing or preventing quinonediazide-based photosensitizer precipitation described below. This method is also encompassed by the present invention.
　即ち、本発明の一つの側面は、アルカリ可溶性樹脂と、架橋剤と、キノンジアジド系感光剤と、有機溶剤とを含有するポジ型レジスト組成物から、キノンジアジド系感光剤の析出を抑制又は防止する方法であって、ポジ型レジスト組成物に、キノンジアジド系感光剤の析出防止剤としてチオール化合物を配合することを特徴とするキノンジアジド系感光剤析出抑制又は防止方法である。 That is, one aspect of the present invention is a method for suppressing or preventing precipitation of a quinone diazide photosensitizer from a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinone diazide photosensitizer, and an organic solvent. A quinonediazide-based photosensitizer deposition inhibiting or preventing method comprising blending a thiol compound as a quinonediazide-based photosensitizer precipitation inhibitor into a positive resist composition.
　この方法においても、ポジ型レジスト組成物へチオール化合物を配合する際に、キノンジアジド系感光剤とその析出防止剤としてのチオール化合物とを有機溶剤に溶解してなるキノンジアジド系感光剤溶液を使用することができる。 Also in this method, when a thiol compound is added to a positive resist composition, a quinonediazide photosensitizer solution obtained by dissolving a quinonediazide photosensitizer and a thiol compound as an anti-precipitation agent in an organic solvent is used. Can do.
　以下、発明を実施例により具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
　　実施例１～５、比較例１～３
　表１に示す、化学構造式（Ｇ）のナフトキノンジアジド系感光剤（４ＮＴ－３００，東洋合成工業（株））１０ｇと、γ－ブチロラクトン１０ｇと、必要に応じ添加剤として化学構造式（Ａ）～（Ｅ）のチオール化合物１ｇとを、室温下、ボールミルで半日撹拌し、均一に溶解させた。 Examples 1 to 5, Comparative Examples 1 to 3
As shown in Table 1, 10 g of naphthoquinone diazide photosensitizer (4NT-300, Toyo Gosei Co., Ltd.) of chemical structural formula (G), 10 g of γ-butyrolactone, and chemical structural formula (A) as an additive as necessary 1 g of the thiol compound of (E) was stirred with a ball mill at room temperature for half a day and dissolved uniformly.
　なお、比較例１としてチオール化合物を配合しない例、比較例２としてチオール化合物に代えて化学構造式（Ｉ）の化合物（ＣＤＡ－１０、ＡＤＥＫＡ（株））を配合した例、比較例３としてチオール化合物に代えて化学構造式（Ｊ）の化合物（ＢＦ－ＢＸＺ，小西化学（株））を配合した例を示す。 In addition, as Comparative Example 1, an example in which no thiol compound was blended, as Comparative Example 2, in which a compound of the chemical structural formula (I) (CDA-10, ADEKA Co., Ltd.) was blended instead of a thiol compound, An example in which a compound of the structural formula (J) (BF-BXZ, Konishi Chemical Co., Ltd.) is blended in place of the compound is shown.
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-I000004
　得られた溶液を室温下で撹拌を続け、感光剤が容器の内壁に析出する日数を目視にて調べた。得られた結果を表１に示す。７日以上析出が観察されない場合は析出なしと評価できる。 The obtained solution was continuously stirred at room temperature, and the number of days on which the photosensitive agent was deposited on the inner wall of the container was examined visually. The obtained results are shown in Table 1. When no precipitation is observed for 7 days or more, it can be evaluated that there is no precipitation.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　チオール化合物を配合しなかった比較例１の場合に比べ、モノチオール化合物を配合した実施例２の場合、析出発生日数が２日から４日となっており、充分に析出抑制効果が確認できた。また、ジチオール化合物を配合した実施例１、３～５の場合には、キノンジアジド系感光剤の析出が７日経ても観察されなかった。 Compared to the case of Comparative Example 1 in which the thiol compound was not blended, in the case of Example 2 in which the monothiol compound was blended, the number of days in which precipitation occurred was 2 to 4 days, and the precipitation suppression effect was sufficiently confirmed. . In Examples 1 and 3 to 5 containing a dithiol compound, no quinonediazide-based photosensitizer was observed even after 7 days.
　なお、比較例２，３の場合、化学構造式（Ｉ）又は（Ｊ）の化合物を配合しても、それらにメルカプト基が存在しないために、析出抑制効果が観察できなかった。 In addition, in the case of Comparative Examples 2 and 3, even when the compound of the chemical structural formula (I) or (J) was blended, the effect of suppressing the precipitation could not be observed because no mercapto group was present in them.
　　実施例６
　本実施例では、ビスムチオールの添加量による析出抑制効果を調べた。即ち、表２に示すように、化学構造式（Ｇ）のナフトキノンジアジド系感光剤（４ＮＴ－３００，東洋合成工業（株））１０ｇと、γ－ブチロラクトン１０ｇと、化学構造式（Ａ）のチオール化合物（ビスムチオール）０．２５ｇ、０．５ｇ又は１ｇを、室温下、ボールミルで半日撹拌し、均一に溶解させた。得られた溶液を室温下で撹拌を続け、感光剤が容器の内壁に析出する日数を目視にて調べた。得られた結果を表２に示す。 Example 6
In the present Example, the precipitation inhibitory effect by the addition amount of bismuthiol was investigated. That is, as shown in Table 2, 10 g of a naphthoquinonediazide photosensitizer (4NT-300, Toyo Gosei Co., Ltd.) having a chemical structural formula (G), 10 g of γ-butyrolactone, and a thiol having a chemical structural formula (A) The compound (bismuthiol) 0.25 g, 0.5 g, or 1 g was stirred with a ball mill at room temperature for half a day and dissolved uniformly. The obtained solution was continuously stirred at room temperature, and the number of days that the photosensitizer was deposited on the inner wall of the container was examined visually. The obtained results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表２から分かるように、ビスムチオールの添加量を増大させると、析出抑制効果が強化されることがわかる。 As can be seen from Table 2, it can be seen that the precipitation suppressing effect is enhanced when the amount of bismuththiol added is increased.
　　実施例７
　本実施例では、４ＮＴ－３００以外の感光剤についても、水分量の観点からビスムチオールの析出抑制効果が現れるかを試験した。即ち、表３に示すように、化学構造式（Ｇ）又は（Ｈ）のナフトキノンジアジド系感光剤１０ｇと、γ－ブチロラクトン１０ｇと、化学構造式（Ａ）のチオール化合物（ビスムチオール）１ｇを、室温下、ボールミルで半日撹拌し、均一に溶解させた。得られた溶液を室温下で撹拌を続け、感光剤が容器の内壁に析出する日数を目視にて調べた。得られた結果を表３に示す。 Example 7
In this example, it was tested whether a photosensitizer other than 4NT-300 also exhibited the effect of suppressing the precipitation of bismuththiol from the viewpoint of water content. That is, as shown in Table 3, 10 g of a naphthoquinone diazide photosensitizer of chemical structural formula (G) or (H), 10 g of γ-butyrolactone, and 1 g of thiol compound (bismuthiol) of chemical structural formula (A) are added at room temperature. Then, the mixture was stirred for half a day with a ball mill and dissolved uniformly. The obtained solution was continuously stirred at room temperature, and the number of days that the photosensitizer was deposited on the inner wall of the container was examined visually. The obtained results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000007
 G*1：化学構造式（Ｇ）の感光剤（４ＮＴ－３００、東洋合成工業（株））
G*2：化学構造式（Ｇ）の感光剤（ＤＴＥＰ－３００、ダイトーケミックス（株））
G*3：化学構造式（Ｇ）の感光剤（ＤＴＥＰ－２５０、ダイトーケミックス（株））
H*1：化学構造式（Ｈ）の感光剤（４Ｃ－ＰＡ－２８０、ダイトーケミックス（株））
Figure JPOXMLDOC01-appb-T000007
 G * 1 : Photosensitizer of chemical structural formula (G) (4NT-300, Toyo Gosei Co., Ltd.)
G * 2 : Photosensitizer with chemical structural formula (G) (DTEP-300, Daitokemix Co., Ltd.)
G * 3 : Photosensitizer with chemical structural formula (G) (DTEP-250, Daitokemix Co., Ltd.)
H * 1 : Photosensitizer of chemical structural formula (H) (4C-PA-280, Daito Chemix Co., Ltd.)
　Ｇ＊１とＧ＊２及びＧ＊３とは同じ化学構造式を有するが、製造会社が異なる。４ＮＴ－３００とＤＴＥＰ－３００とは、同等のものと考えられている。また、Ｇ＊２は、Ｇ＊３よりもナフトキノンジアゾスルホニル基の置換（テトラ置換体）割合が高いものである。 G * 1 , G * 2, and G * 3 have the same chemical structural formula, but different manufacturers. 4NT-300 and DTEP-300 are considered equivalent. Further, G * 2 has a higher naphthoquinonediazosulfonyl group substitution (tetra-substituted product) ratio than G * 3 .
　試験７－２、７－４、７－６、７－８の結果から、ビスムチオールを配合すると、感光剤が代わっても析出防止効果が維持されていることがわかる。なお、試験７－３が７－１よりも早く析出しているのは、水分量が多いためと考えられる。 From the results of Tests 7-2, 7-4, 7-6, and 7-8, it can be seen that the addition of bismuthiol maintains the effect of preventing precipitation even when the photosensitizer is replaced. Note that the reason why Test 7-3 is precipitated earlier than 7-1 is thought to be due to the large amount of water.
　本発明のキノンジアジド系感光剤溶液又はポジ型レジスト組成物においては、キノンジアジド系感光剤とチオール化合物とを共存させている。このため、キノンジアジド系感光剤溶液又はポジ型レジスト組成物において、キノンジアジド系感光剤の析出を抑制又は防止することができる。従って、本発明のキノンジアジド系感光剤溶液又はポジ型レジスト組成物は、保存安定性に優れたものとなり、特に、電子部品の製造に有用である。 In the quinonediazide photosensitizer solution or positive resist composition of the present invention, a quinonediazide photosensitizer and a thiol compound coexist. For this reason, precipitation of a quinonediazide type photosensitizer can be suppressed or prevented in a quinonediazide type photosensitizer solution or a positive resist composition. Therefore, the quinonediazide-based photosensitizer solution or positive resist composition of the present invention has excellent storage stability and is particularly useful for the production of electronic components.

Claims (9)

  1. 　キノンジアジド系感光剤が有機溶剤に溶解してなるキノンジアジド系感光剤溶液であって、キノンジアジド系感光剤の析出防止剤としてチオール化合物を含有することを特徴とするキノンジアジド系感光剤溶液。 A quinonediazide-based photosensitizer solution obtained by dissolving a quinonediazide-based photosensitizer in an organic solvent, which contains a thiol compound as a quinonediazide-based photosensitizer precipitation inhibitor.
  2. 　チオール化合物が、ビスムチオール、２－メチルチオ－５－メルカプトチアジアゾール、ペンタエリスリトール－テトラキス－メルカプトプロピオネート、ペンタエリスリトール－テトラキス－メルカプトブチレート、及び２－ブチルアミノ－４，６－ジチオ－ｓ－トリアジンからなる群より選択された一種以上の化合物である請求項１記載のキノンジアジド系感光剤溶液。 The thiol compound is from bismuthiol, 2-methylthio-5-mercaptothiadiazole, pentaerythritol-tetrakis-mercaptopropionate, pentaerythritol-tetrakis-mercaptobutyrate, and 2-butylamino-4,6-dithio-s-triazine The quinonediazide photosensitizer solution according to claim 1, which is one or more compounds selected from the group consisting of:
  3. 　キノンジアジド系感光剤が、以下の化学構造式で表されるナフトキノンジアジド誘導体の少なくとも一種である請求項１又は２記載のキノンジアジド系感光剤溶液。
    Figure JPOXMLDOC01-appb-I000001
    The quinonediazide photosensitizer solution according to claim 1 or 2, wherein the quinonediazide photosensitizer is at least one naphthoquinonediazide derivative represented by the following chemical structural formula.
    Figure JPOXMLDOC01-appb-I000001
  4. 　キノンジアジド系感光剤１００質量部に対し、チオール化合物を０．０１～１０質量部含有する請求項１～３のいずれかに記載のキノンジアジド系感光剤溶液。 The quinonediazide photosensitizer solution according to any one of claims 1 to 3, comprising 0.01 to 10 parts by mass of a thiol compound with respect to 100 parts by mass of the quinonediazide photosensitizer.
  5. 　有機溶剤が、γ－ブチロラクトン及び／又はトリグライムを含有する請求項１～４のいずれかに記載のキノンジアジド系感光剤溶液。 The quinonediazide photosensitizer solution according to any one of claims 1 to 4, wherein the organic solvent contains γ-butyrolactone and / or triglyme.
  6. 　アルカリ可溶性樹脂と、架橋剤と、キノンジアジド系感光剤と、有機溶剤とを含有するポジ型レジスト組成物であって、更に、キノンジアジド系感光剤の析出防止剤としてチオール化合物を含有するポジ型レジスト組成物。 A positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinonediazide-based photosensitizer, and an organic solvent, and further containing a thiol compound as a precipitation inhibitor for the quinonediazide-based photosensitizer object.
  7. 　アルカリ可溶性樹脂が、フェノールノボラック系樹脂、クレゾールノボラック系樹脂、アルカリ可溶性ポリイミド樹脂又はポリベンゾオキサゾール前駆体である請求項６記載のポジ型レジスト組成物。 The positive resist composition according to claim 6, wherein the alkali-soluble resin is a phenol novolac resin, a cresol novolac resin, an alkali-soluble polyimide resin, or a polybenzoxazole precursor.
  8. 　アルカリ可溶性樹脂と、架橋剤と、キノンジアジド系感光剤と、有機溶剤とを含有するポジ型レジスト組成物から、キノンジアジド系感光剤の析出を抑制又は防止する方法であって、ポジ型レジスト組成物に、キノンジアジド系感光剤の析出防止剤としてチオール化合物を配合することを特徴とするキノンジアジド系感光剤析出抑制又は防止方法。 A method for suppressing or preventing the precipitation of a quinone diazide photosensitizer from a positive resist composition containing an alkali-soluble resin, a cross-linking agent, a quinone diazide photosensitizer, and an organic solvent. A method for inhibiting or preventing quinonediazide-based photosensitizer precipitation, comprising blending a thiol compound as a precipitation-preventing agent for a quinonediazide-based photosensitizer.
  9. 　ポジ型レジスト組成物へのチオール化合物の配合が、キノンジアジド系感光剤とチオール化合物とを有機溶剤に溶解してなるキノンジアジド系感光剤溶液を使用することにより行われる請求項８記載のキノンジアジド系感光剤析出抑制又は防止方法。 9. The quinonediazide photosensitizer according to claim 8, wherein the thiol compound is added to the positive resist composition by using a quinonediazide photosensitizer solution obtained by dissolving a quinonediazide photosensitizer and a thiol compound in an organic solvent. Precipitation suppression or prevention method.
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