WO2021177250A1 - Positive-type photosensitive resin composition - Google Patents

Positive-type photosensitive resin composition Download PDF

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Publication number
WO2021177250A1
WO2021177250A1 PCT/JP2021/007782 JP2021007782W WO2021177250A1 WO 2021177250 A1 WO2021177250 A1 WO 2021177250A1 JP 2021007782 W JP2021007782 W JP 2021007782W WO 2021177250 A1 WO2021177250 A1 WO 2021177250A1
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WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
positive photosensitive
compound
composition according
Prior art date
Application number
PCT/JP2021/007782
Other languages
French (fr)
Japanese (ja)
Inventor
川島　正行
高橋　秀幸
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to CN202180018155.6A priority Critical patent/CN115244462A/en
Priority to KR1020227030026A priority patent/KR20220149671A/en
Priority to JP2022504364A priority patent/JPWO2021177250A1/ja
Publication of WO2021177250A1 publication Critical patent/WO2021177250A1/en

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Classifications

    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • 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
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers

Definitions

  • the present invention relates to a positive photosensitive resin composition.
  • the positive photosensitive resin composition is used for forming a color filter, an organic EL element, a partition wall for forming a pixel used in manufacturing a TFT array, an interlayer insulating film, a flattening film, and further for forming a macro lens (for example, a patent).
  • the present invention includes the following aspects. 1.
  • It contains an alkali-soluble resin (A), a photosensitizer (B), a cross-linking agent (C), and a surfactant (D), and the cross-linking agent (C) contains a carboxyl group, a phenolic hydroxyl group, a sulfo group and phosphorus as acidic groups.
  • the positive photosensitive resin composition according to any one of 1 to 8 above, which further contains a solvent (E) and the proportion of the compound having a boiling point of 170 ° C. or higher in the solvent is in the range of 10 to 70% by mass.
  • the positive photosensitive resin composition of the present invention comprises a combination of an essential component and an optional component.
  • the essential component is essentially contained in the positive photosensitive resin composition and provides a main function of performance.
  • Optional ingredients are used as needed.
  • % means mass%.
  • the mass-based ratio percentage, part, etc.
  • the numerical range includes the rounded range. Further, when the numerical range is indicated as "X to Y", it means "X or more and Y or less”.
  • the essential components are an alkali-soluble resin (A), a photosensitizer (B), a cross-linking agent (C) and a surfactant (D).
  • the alkali-soluble resin (A) is a resin that dissolves in the alkali used in the developing process, and is a resin that is the main component of the partition wall used in the pixel portion and the like.
  • a known resin used in the positive photosensitive resin composition can be used.
  • the alkali-soluble resin (A) Japanese Patent No. 6177495, Japanese Patent No. 5447384, Japanese Patent No. 4770985, Japanese Patent No. 4600477, Japanese Patent No. 5444749
  • the alkali-soluble resin described in Japanese Patent Application Laid-Open No. 2019/156000 is shown, but the alkali-soluble resin (A) is not limited thereto.
  • the following resins are shown as specific examples of the preferred alkali-soluble resin (A), but the alkali-soluble resin (A) is not limited thereto.
  • the alkali-soluble resin (A) is preferably a phenol resin.
  • a phenol resin is used, the curability of the obtained positive photosensitive resin composition is improved, and the generation of outgas is reduced.
  • an orthocresol resin is particularly preferable because the molecular weight of the resin can be controlled to be small.
  • the mass average molecular weight of the alkali-soluble resin (A) is preferably in the range of 500 to 10000, more preferably in the range of 1000 to 5000, and preferably in the range of 1000 to 3000. Especially preferable.
  • the mass average molecular weight means the mass average molecular weight converted with reference to standard polystyrene, which is measured by gel permeation chromatography (GPC) with tetrahydrofuran as the mobile phase.
  • the amount of the alkali-soluble resin (A) used is preferably in the range of 40 to 80%, preferably 50 to 75% of the total of (A) + (B) + (C) + (D) in terms of mass ratio. It is more preferably in the range of%, and particularly preferably in the range of 55 to 72%. When the amount used is within this range, the effect of the present invention can be more effectively exhibited.
  • the photosensitizer (B) is a compound that reacts with light during exposure to change the solubility of the positive photosensitive resin composition in an alkaline solution.
  • Examples of the photosensitizer (B) used in the present invention include known photosensitizers used in positive photosensitive resin compositions.
  • a compound having a quinone diazide group hereinafter, also referred to as a quinone diazide compound is preferable because it has excellent photosensitivity.
  • the amount of the photosensitizer (B) used is preferably in the range of 10 to 35%, preferably 15 to 30%, based on the total of (A) + (B) + (C) + (D) in terms of mass ratio. It is more preferably in the range of 17 to 22%, and particularly preferably in the range of 17 to 22%. When the amount used is within this range, the effect of the present invention can be more effectively exhibited.
  • the cross-linking agent (C) is a compound that contributes to the curability of the positive photosensitive resin composition and has two or more photocurable functional groups.
  • the photocurable functional group is preferably the same type of functional group as the photocurable functional group contained in the alkali-soluble resin (A). Specifically, an ethylenic double bond is preferable as the photocurable functional group.
  • the number of photocurable functional groups contained in the cross-linking agent (C) is 2 or more in one molecule, preferably 3 or more, more preferably 4 or more, and particularly preferably 5 or more. As the number of photocurable functional groups increases, the curability of the coating film surface improves, and the solvent resistance of the cured product and the reliability of outgas and the like improve.
  • the cross-linking agent (C) used in the present invention is a compound having one or more selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfo group and a phosphoric acid group as an acidic group (hereinafter, also referred to as a compound having an acidic group). ), And preferably contains a compound having a carboxyl group.
  • the number of acidic groups contained in the compound having an acidic group is 1 or more in one molecule, preferably 1 to 3, and particularly preferably 1. When the compound having an acidic group has the structure, the effect of the present invention can be more effectively exhibited.
  • the cross-linking agent is uniformly dispersed in the cured film, and the permeability of the developing solution can be improved.
  • the mass average molecular weight of the compound having an acidic group is preferably 100 to 1500, more preferably 300 to 1000, and particularly preferably 400 to 800, from the viewpoint of permeation of the developing solution and diffusion into the solution.
  • Compounds having an acidic group include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, and a polyisocyanate compound and a (meth) acryloyl-containing hydroxy compound.
  • a compound in which an acidic group is introduced by leaving two or more unsaturated bonds (ethylenic double bonds) in an ethylenic compound having a urethane skeleton obtained by reacting with the above is preferable.
  • the compound having an acidic group has an isocyanurate skeleton, a trimethylolpropane skeleton, a phthalic acid skeleton, a pentaerythritol skeleton, a dipentaerythritol skeleton, or a trypentaerythritol skeleton from the viewpoint of the introduction ratio of the ethylenic double bond.
  • Compounds are preferred, and compounds having a dipentaerythritol skeleton are particularly preferred.
  • a compound having an acidic group is acidic by substituting five hydroxy groups of dipentaerythritol with (meth) acryloyloxy groups and ester-bonding the remaining one hydroxy group with, for example, succinic acid.
  • Compounds with introduced groups are particularly preferred.
  • These compounds contain photocurable functional groups, preferably ethylenic double bonds, more preferably 2 or more, preferably 3 or more, more preferably 4 or more, particularly preferably 5 acrylates in one molecule.
  • photocurable functional groups preferably ethylenic double bonds, more preferably 2 or more, preferably 3 or more, more preferably 4 or more, particularly preferably 5 acrylates in one molecule.
  • the acid value of the cross-linking agent (C) is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and even more preferably 50 mgKOH / g or more.
  • the acid value is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and even more preferably 100 mgKOH / g or less.
  • the acid value is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, and particularly preferably 50 to 100 mgKOH / g.
  • cross-linking agent (C) the above-mentioned compound having an acidic group may be used alone or in combination with other cross-linking agents.
  • the ratio of the compound having an acidic group in the cross-linking agent (C) is preferably 30% or more, more preferably 50% or more, and particularly preferably 60% or more in terms of mass ratio.
  • the amount of the compound having an acidic group used is in the range of 5 to 35% with respect to the total of (A) + (B) + (C) + (D) in terms of mass ratio.
  • the amount used is preferably 6% or more, more preferably 8% or more.
  • the amount used is preferably 25% or less, more preferably 20% or less.
  • the amount used is preferably 6 to 25%, particularly preferably 8 to 20%.
  • the amount used is within this range, the effect of the present invention can be more effectively exhibited. More specifically, when the amount of the compound having an acidic group used is at least the above lower limit value, it is easy to achieve both excellent solvent resistance and the effect of reducing development residue. When the amount used is not more than the above upper limit value, the adhesion to the substrate tends to be good.
  • the ratio of the cross-linking agent (C) to the alkali-soluble resin (A) is preferably 8% or more, more preferably 10% or more, further preferably 12% or more, and particularly preferably 14% or more. .. Further, such a ratio is preferably 40% or less, more preferably 35% or less, further preferably 30% or less, and particularly preferably 26% or less. Such a ratio is preferably 8 to 40%, more preferably 10 to 35%, particularly preferably 12 to 30%, and most preferably 14 to 26%. When the ratio of the cross-linking agent (C) is in this range with respect to the alkali-soluble resin (A), the balance between the developer solubility and the pattern shape is excellent.
  • the surfactant (D) improves the coatability of the positive photosensitive resin composition and also improves the residue removability during development.
  • the surfactant (D) of the present invention does not have an F atom. Since the surfactant (D) does not have an F atom, the ink repellency is weakened, which makes it suitable for applications requiring affinity with ink. On the other hand, when an ink-repellent agent is used, the ink-repellent property is generated at the portion where the ink is applied, and the ink applicability is greatly reduced. Therefore, as the surfactant (D), a compound used as an ink repellent is not preferable.
  • surfactant (D) examples include silicone-based surfactants, nonionic, anionic, cationic and amphoteric surfactants, and polyether-modified silicone-based surfactants are preferable. More specifically, as a silicone-based surfactant, "Torre Silicone DC3PA”, “Torre Silicone SH7PA”, “Torre Silicone DC11PA”, “Torre Silicone SH21PA”, “Torre Silicone SH28PA”, “Torre Silicone SH28PA” manufactured by Dow Toray Co., Ltd.
  • the amount of the surfactant (D) used is preferably in the range of 0.1 to 1.0% with respect to the total of (A) + (B) + (C) + (D) in terms of mass ratio. .. When the amount used is within this range, the effect of the present invention can be more effectively exhibited.
  • the positive photosensitive resin composition of the present invention may contain a solvent (E).
  • a solvent (E) By containing the solvent (E), the coatability, adhesion to the substrate, and stability of the positive photosensitive resin composition are more excellent.
  • the solvent (E) a known solvent used for the positive photosensitive resin composition can be used. Specific examples of the solvent (E) include alcohols, ethers, aromatics, and hydrocarbons, but the solvent (E) is not limited thereto.
  • the proportion of the compound having a boiling point of 170 ° C. or higher in the solvent (E) is in the range of 10 to 70% by mass. Especially preferable.
  • the blending amount of the solvent (E) is preferably in the range of 60 to 90%, particularly preferably in the range of 75 to 85% in terms of mass ratio in the positive photosensitive resin composition.
  • the positive photosensitive resin composition of the present invention is a thermosetting agent, a thermosetting accelerator, a colorant, a silane coupling agent, fine particles, a thickener, and a plasticizer as long as the effects of the present invention are not impaired.
  • Known components added as a positive photosensitive resin composition such as an agent, a defoaming agent, a leveling agent, an anti-repellent agent, and an ultraviolet absorber, may be added. More specifically, the components described in Japanese Patent No. 6098635, paragraphs 0080 to 0995 may be added.
  • the positive photosensitive resin composition contains the alkali-soluble resin (A), the photosensitive agent (B), the cross-linking agent (C) and the surfactant (D), and if necessary, the solvent and other components until they become uniform. Prepared by mixing.
  • the positive photosensitive resin composition of the present invention is suitably used for forming a pixel-forming partition wall, an interlayer insulating film, a flattening film, and further a microlens in an optical element such as an organic EL element, a color filter, and a TFT array.
  • an optical element such as an organic EL element, a color filter, and a TFT array.
  • the application is not limited to these.
  • a cured product obtained by curing the positive photosensitive resin composition of the present invention can be suitably used for the above-mentioned applications and the like.
  • an organic EL element As an example, a method for manufacturing an organic EL element is shown.
  • a transparent electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by a sputtering method or the like, and if necessary, the transparent electrode is etched into a desired pattern.
  • a partition wall (cured product) is formed using the positive photosensitive resin composition of the present invention, a banking agent having a liquid-repellent surface is formed, and then holes are transported to the dots by an inkjet method.
  • a solution of the material and the light emitting material is sequentially applied and dried to form a hole transport layer and a light emitting layer.
  • the pixels of the organic EL element can be obtained by forming an electrode of aluminum or the like by a vapor deposition method or the like.
  • Examples 1 to 10 are examples, and examples 11 to 13 are comparative examples.
  • evaluation sample Using the positive photosensitive resin composition shown in Table 1, a cured film was prepared on an ITO substrate and used as an evaluation sample. Two types of evaluation samples 1 and 2 were prepared as evaluation samples. Adhesion and solvent resistance were evaluated using the evaluation sample 1. The amount of development residue was evaluated using the evaluation sample 2.
  • Photomask A light-shielding portion that repeats the following 18 types of line patterns in a range of 20 mm ⁇ 20 mm. Shape of light-shielding part: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 30, 40, 50 ⁇ m ⁇ 1000 ⁇ m, respectively Pattern interval: 50 ⁇ m [Lamp]: Ushio, Inc.
  • the exposed ITO substrate was immersed in a tetramethylammonium hydroxide aqueous solution (0.4% by mass) for 40 seconds for development. Then, it was washed with water and dried. The dried substrate was heated on a hot plate (220 ° C., 60 minutes) to prepare an ITO substrate having a cured film having a specific pattern (evaluation sample 1).
  • Evaluation sample 2 was prepared in the same manner as evaluation sample 1 except that the photomask used was changed.
  • Photomask An opening is provided in a range of 20 mm ⁇ 20 mm in the following pattern. Opening shape: 100 ⁇ m x 200 ⁇ m Pattern interval: 20 ⁇ m
  • the amount of residue was measured for the unbanked portion of the cured film of the evaluation sample 2.
  • the bank-extracted portion means a portion from which the film has been removed by a developing operation.
  • the amount of residue on the ITO surface of the unbanked portion was measured by the ⁇ -XPS method and evaluated according to the following criteria.
  • Examples and Comparative Examples The raw materials were stirred (about 30 minutes) at the ratios shown in Table 1 until they became uniform to prepare a positive photosensitive resin composition. Using this, evaluation samples 1 and 2 were prepared and evaluated, respectively. The evaluation results are shown in Table 1. The numbers in the table show significant figures as the first decimal place. In addition, the blanks in the table indicate that the components in the corresponding column are not contained.
  • C1 Polybasic acid-modified acrylic oligomer (mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinate of dipentaerythritol pentaacrylate (acid value 92 mgKOH / g, molecular weight 612))
  • C2 2,2,2-triacryloyloxymethylethylphthalic acid (acid value 87 mgKOH / g, molecular weight 446)
  • C3 Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention relates to a positive-type photosensitive resin composition containing an alkali-soluble resin (A), a photosensitizer (B), a crosslinking agent (C), and a surfactant (D), wherein the crosslinking agent (C) includes a compound having one or more acidic moieties selected from the group consisting of the carboxyl moiety, the phenolic hydroxy moiety, the sulfo moiety and the phosphate moiety; the proportion of the compound having the acidic moiety relative to the total amount of (A)+(B)+(C)+(D) is in the range of 5-35% by mass; and the surfactant (D) does not contain a F atom.

Description

ポジ型感光性樹脂組成物Positive photosensitive resin composition
　本発明は、ポジ型感光性樹脂組成物に関する。 The present invention relates to a positive photosensitive resin composition.
　ポジ型感光性樹脂組成物は、カラーフィルタ、有機ＥＬ素子、ＴＦＴアレイ製造に用いられる画素形成用隔壁、層間絶縁膜、平坦化膜、さらにはマクロレンズ形成用に用いられている（例えば、特許文献１、２）。 The positive photosensitive resin composition is used for forming a color filter, an organic EL element, a partition wall for forming a pixel used in manufacturing a TFT array, an interlayer insulating film, a flattening film, and further for forming a macro lens (for example, a patent). Documents 1 and 2).
日本国特許第６３８４６７８号公報Japanese Patent No. 6384678 日本国特開２０１０－１３４４２２号公報Japanese Patent Application Laid-Open No. 2010-134422
　近年は製品の要求性能が上がっており、従来のポジ型感光性樹脂組成物では性能が不十分である。
　このような状況下、基板との密着性が高く、現像残渣が少なく、かつ耐溶剤性に優れるポジ型感光性樹脂組成物が求められている。 In recent years, the required performance of products has increased, and the performance of conventional positive photosensitive resin compositions is insufficient.
Under such circumstances, there is a demand for a positive photosensitive resin composition having high adhesion to a substrate, little development residue, and excellent solvent resistance.
　本発明は、以下の態様を包含する。
１．アルカリ可溶性樹脂（Ａ）、感光剤（Ｂ）、架橋剤（Ｃ）、界面活性剤（Ｄ）を含有し、前記架橋剤（Ｃ）が酸性基としてカルボキシル基、フェノール性水酸基、スルホ基及びリン酸基からなる群より選ばれる１以上を有する化合物を含有し、
　前記酸性基を有する化合物の割合が、質量比で、（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）の合計に対して５～３５％の範囲にあり、
　前記界面活性剤（Ｄ）がＦ原子を有さないポジ型感光性樹脂組成物。
２．前記感光剤（Ｂ）がキノンジアジド化合物を含有する前記１に記載のポジ型感光性樹脂組成物。
３．前記アルカリ可溶性樹脂（Ａ）の質量平均分子量が５００～１００００の範囲にある前記１又は２に記載のポジ型感光性樹脂組成物。
４．前記アルカリ可溶性樹脂（Ａ）がフェノール樹脂である前記１～３のいずれか１に記載のポジ型感光性樹脂組成物。
５．前記フェノール樹脂がオルトクレゾール樹脂である前記４に記載のポジ型感光性樹脂組成物。
６．前記酸性基がカルボキシル基である前記１～５のいずれか１に記載のポジ型感光性樹脂組成物。
７．前記架橋剤（Ｃ）が１分子中に前記カルボキシル基を１～３個有する化合物を含有する前記６に記載のポジ型感光性樹脂組成物。
８．前記架橋剤（Ｃ）中の前記酸性基を有する化合物の割合が、質量比で３０％以上である前記１～７のいずれか１に記載のポジ型感光性樹脂組成物。
９．更に溶媒（Ｅ）を含有し、前記溶媒における沸点が１７０℃以上の化合物の割合が１０～７０質量％の範囲にある前記１～８のいずれか１に記載のポジ型感光性樹脂組成物。
１０．前記１～９のいずれか１に記載のポジ型感光性樹脂組成物を硬化した硬化物。
１１．前記１０に記載の硬化物を隔壁として含む光学素子。 The present invention includes the following aspects.
1. 1. It contains an alkali-soluble resin (A), a photosensitizer (B), a cross-linking agent (C), and a surfactant (D), and the cross-linking agent (C) contains a carboxyl group, a phenolic hydroxyl group, a sulfo group and phosphorus as acidic groups. Contains a compound having one or more selected from the group consisting of acid groups,
The ratio of the compound having an acidic group is in the range of 5 to 35% with respect to the total of (A) + (B) + (C) + (D) in terms of mass ratio.
A positive photosensitive resin composition in which the surfactant (D) does not have an F atom.
2. The positive photosensitive resin composition according to 1 above, wherein the photosensitive agent (B) contains a quinonediazide compound.
3. 3. The positive photosensitive resin composition according to 1 or 2, wherein the alkali-soluble resin (A) has a mass average molecular weight in the range of 500 to 10000.
4. The positive photosensitive resin composition according to any one of 1 to 3 above, wherein the alkali-soluble resin (A) is a phenol resin.
5. The positive photosensitive resin composition according to 4 above, wherein the phenol resin is an orthocresol resin.
6. The positive photosensitive resin composition according to any one of 1 to 5 above, wherein the acidic group is a carboxyl group.
7. The positive photosensitive resin composition according to 6 above, wherein the cross-linking agent (C) contains a compound having 1 to 3 carboxyl groups in one molecule.
8. The positive photosensitive resin composition according to any one of 1 to 7, wherein the ratio of the compound having an acidic group in the cross-linking agent (C) is 30% or more by mass ratio.
9. The positive photosensitive resin composition according to any one of 1 to 8 above, which further contains a solvent (E) and the proportion of the compound having a boiling point of 170 ° C. or higher in the solvent is in the range of 10 to 70% by mass.
10. A cured product obtained by curing the positive photosensitive resin composition according to any one of 1 to 9 above.
11. An optical element containing the cured product according to 10 as a partition wall.
　本発明によれば、基板との密着性が高く、現像残渣が少なく、かつ耐溶剤性に優れるポジ型感光性樹脂組成物を提供できる。 According to the present invention, it is possible to provide a positive photosensitive resin composition having high adhesion to a substrate, little development residue, and excellent solvent resistance.
　以下、本発明のポジ型感光性樹脂組成物について説明する。
［ポジ型感光性樹脂組成物］
　本発明のポジ型感光性樹脂組成物は、必須成分と任意成分の組み合わせからなる。必須成分はポジ型感光性樹脂組成物に必須に含有されるものであり、性能の主要な機能を与える。任意成分は必要に応じて使用される。
　本明細書において特段の記載がない場合、％は質量％を意味する。ただし、本明細書において、質量基準の割合（百分率、部など）は重量基準の割合（百分率、部など）と同じである。数値範囲は四捨五入した範囲を含む。また、数値範囲を「Ｘ～Ｙ」と示す場合「Ｘ以上Ｙ以下」を意味する。 Hereinafter, the positive photosensitive resin composition of the present invention will be described.
[Positive photosensitive resin composition]
The positive photosensitive resin composition of the present invention comprises a combination of an essential component and an optional component. The essential component is essentially contained in the positive photosensitive resin composition and provides a main function of performance. Optional ingredients are used as needed.
Unless otherwise stated in this specification,% means mass%. However, in the present specification, the mass-based ratio (percentage, part, etc.) is the same as the weight-based ratio (percentage, part, etc.). The numerical range includes the rounded range. Further, when the numerical range is indicated as "X to Y", it means "X or more and Y or less".
［必須成分］
　必須成分はアルカリ可溶性樹脂（Ａ）、感光剤（Ｂ）、架橋剤（Ｃ）及び界面活性剤（Ｄ）である。 [Essential ingredients]
The essential components are an alkali-soluble resin (A), a photosensitizer (B), a cross-linking agent (C) and a surfactant (D).
＜アルカリ可溶性樹脂（Ａ）＞
　アルカリ可溶性樹脂（Ａ）は、現像工程で使用されるアルカリに対し溶解する樹脂であり、画素部等で使用される隔壁の主成分となる樹脂である。
　本発明で使用されるアルカリ可溶性樹脂（Ａ）としては、ポジ型感光性樹脂組成物に使用される公知の樹脂が使用できる。
　具体例として、アルカリ可溶性樹脂（Ａ）としては日本国特許第６１７７４９５号公報、日本国特許第５４４７３８４号公報、日本国特許第４７７０９８５号公報、日本国特許第４６００４７７号公報、日本国特許第５４４４７４９号公報、及び国際公開第２０１９／１５６０００号に記載のアルカリ可溶性樹脂が示されるが、アルカリ可溶性樹脂（Ａ）はこれらに限定されない。 <Alkali-soluble resin (A)>
The alkali-soluble resin (A) is a resin that dissolves in the alkali used in the developing process, and is a resin that is the main component of the partition wall used in the pixel portion and the like.
As the alkali-soluble resin (A) used in the present invention, a known resin used in the positive photosensitive resin composition can be used.
As specific examples, as the alkali-soluble resin (A), Japanese Patent No. 6177495, Japanese Patent No. 5447384, Japanese Patent No. 4770985, Japanese Patent No. 4600477, Japanese Patent No. 5444749 The alkali-soluble resin described in Japanese Patent Application Laid-Open No. 2019/156000 is shown, but the alkali-soluble resin (A) is not limited thereto.
　好ましいアルカリ可溶性樹脂（Ａ）の具体例として、以下の樹脂が示されるが、アルカリ可溶性樹脂（Ａ）はこれらに限定されない。
　アルカリ可溶性樹脂（Ａ）としてはフェノール樹脂が好ましい。フェノール樹脂を使用すると、得られるポジ型感光性樹脂組成物の硬化性が向上し、またアウトガスの発生が低減される。フェノール樹脂としては、樹脂の分子量を小さくコントロール可能であるためオルトクレゾール樹脂が特に好ましい。 The following resins are shown as specific examples of the preferred alkali-soluble resin (A), but the alkali-soluble resin (A) is not limited thereto.
The alkali-soluble resin (A) is preferably a phenol resin. When a phenol resin is used, the curability of the obtained positive photosensitive resin composition is improved, and the generation of outgas is reduced. As the phenol resin, an orthocresol resin is particularly preferable because the molecular weight of the resin can be controlled to be small.
　残渣除去性が優れるため、アルカリ可溶性樹脂（Ａ）の質量平均分子量は５００～１００００の範囲にあることが好ましく、１０００～５０００の範囲にあることが更に好ましく、１０００～３０００の範囲にあることが特に好ましい。 Since the residue removing property is excellent, the mass average molecular weight of the alkali-soluble resin (A) is preferably in the range of 500 to 10000, more preferably in the range of 1000 to 5000, and preferably in the range of 1000 to 3000. Especially preferable.
　本明細書において質量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）によりテトラヒドロフランを移動相として測定される、標準ポリスチレンを基準として換算した質量平均分子量を意味する。 In the present specification, the mass average molecular weight (Mw) means the mass average molecular weight converted with reference to standard polystyrene, which is measured by gel permeation chromatography (GPC) with tetrahydrofuran as the mobile phase.
　アルカリ可溶性樹脂（Ａ）の使用量は、質量比で、（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）の合計に対して４０～８０％の範囲にあることが好ましく、５０～７５％の範囲にあることが更に好ましく、５５～７２％の範囲にあることが特に好ましい。使用量がこの範囲にあることで、本発明の効果をより効果的に発揮することができる。 The amount of the alkali-soluble resin (A) used is preferably in the range of 40 to 80%, preferably 50 to 75% of the total of (A) + (B) + (C) + (D) in terms of mass ratio. It is more preferably in the range of%, and particularly preferably in the range of 55 to 72%. When the amount used is within this range, the effect of the present invention can be more effectively exhibited.
＜感光剤（Ｂ）＞
　感光剤（Ｂ）は、露光時に光と反応してポジ型感光性樹脂組成物のアルカリ溶液への溶解性を変化させる化合物である。
　本発明で使用される感光剤（Ｂ）として、ポジ型感光性樹脂組成物に用いられる公知の感光剤が挙げられる。
　感光剤（Ｂ）として、感光性に優れるためキノンジアジド基を有する化合物（以下キノンジアジド化合物ともいう）が好ましい。 <Photosensitizer (B)>
The photosensitizer (B) is a compound that reacts with light during exposure to change the solubility of the positive photosensitive resin composition in an alkaline solution.
Examples of the photosensitizer (B) used in the present invention include known photosensitizers used in positive photosensitive resin compositions.
As the photosensitizer (B), a compound having a quinone diazide group (hereinafter, also referred to as a quinone diazide compound) is preferable because it has excellent photosensitivity.
　感光剤（Ｂ）の使用量は、質量比で、（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）の合計に対して１０～３５％の範囲にあることが好ましく、１５～３０％の範囲にあることが更に好ましく、１７～２２％の範囲にあることが特に好ましい。使用量がこの範囲にあることで、本発明の効果をより効果的に発揮することができる。 The amount of the photosensitizer (B) used is preferably in the range of 10 to 35%, preferably 15 to 30%, based on the total of (A) + (B) + (C) + (D) in terms of mass ratio. It is more preferably in the range of 17 to 22%, and particularly preferably in the range of 17 to 22%. When the amount used is within this range, the effect of the present invention can be more effectively exhibited.
＜架橋剤（Ｃ）＞
　架橋剤（Ｃ）は、ポジ型感光性樹脂組成物の硬化性に寄与する化合物であり２個以上の光硬化性官能基を有する。光硬化性官能基は、アルカリ可溶性樹脂（Ａ）が有する光硬化性官能基と同じ種類の官能基が好ましい。具体的には、光硬化性官能基としてはエチレン性二重結合が好ましい。
　架橋剤（Ｃ）が持つ光硬化性官能基の数は、１分子中、２個以上であり、３個以上が好ましく、４個以上がより好ましく、５個以上が特に好ましい。光硬化性官能基の数が多いほど、塗膜表面の硬化性が向上し、硬化物の耐溶剤性やアウトガス等の信頼性が向上する。 <Crosslinking agent (C)>
The cross-linking agent (C) is a compound that contributes to the curability of the positive photosensitive resin composition and has two or more photocurable functional groups. The photocurable functional group is preferably the same type of functional group as the photocurable functional group contained in the alkali-soluble resin (A). Specifically, an ethylenic double bond is preferable as the photocurable functional group.
The number of photocurable functional groups contained in the cross-linking agent (C) is 2 or more in one molecule, preferably 3 or more, more preferably 4 or more, and particularly preferably 5 or more. As the number of photocurable functional groups increases, the curability of the coating film surface improves, and the solvent resistance of the cured product and the reliability of outgas and the like improve.
　本発明で使用される架橋剤（Ｃ）は、酸性基としてカルボキシル基、フェノール性水酸基、スルホ基及びリン酸基からなる群より選ばれる１以上を有する化合物（以下、酸性基を有する化合物ともいう）を含有し、好ましくはカルボキシル基を有する化合物を含有する。前記酸性基を有する化合物が持つ酸性基の数は、１分子中１個以上であり、好ましくは１～３個であり、特に好ましくは１個である。
　前記酸性基を有する化合物が前記構造を持つことで本発明の効果をより効果的に発揮することができる。また、架橋剤が硬化膜中に均一に分散し、現像液の浸透性を上げることができる。 The cross-linking agent (C) used in the present invention is a compound having one or more selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfo group and a phosphoric acid group as an acidic group (hereinafter, also referred to as a compound having an acidic group). ), And preferably contains a compound having a carboxyl group. The number of acidic groups contained in the compound having an acidic group is 1 or more in one molecule, preferably 1 to 3, and particularly preferably 1.
When the compound having an acidic group has the structure, the effect of the present invention can be more effectively exhibited. In addition, the cross-linking agent is uniformly dispersed in the cured film, and the permeability of the developing solution can be improved.
　前記酸性基を有する化合物の質量平均分子量は、現像液の浸透および液中への拡散の観点から１００～１５００が好ましく、３００～１０００が更に好ましく、４００～８００が特に好ましい。 The mass average molecular weight of the compound having an acidic group is preferably 100 to 1500, more preferably 300 to 1000, and particularly preferably 400 to 800, from the viewpoint of permeation of the developing solution and diffusion into the solution.
　前記酸性基を有する化合物の具体例を以下に挙げるが、酸性基を有する化合物はこれらに限定されない。
　酸性基を有する化合物は例えば、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル、芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル、及び、ポリイソシアネート化合物と（メタ）アクリロイル含有ヒドロキシ化合物とを反応させたウレタン骨格を有するエチレン性化合物等に、不飽和結合（エチレン性二重結合）を２個以上残すようにして、酸性基を導入した化合物が好ましい。
　また、酸性基を有する化合物は、エチレン性二重結合の導入比率の観点から、イソシアヌレート骨格、トリメチロールプロパン骨格、フタル酸骨格、ペンタエリスリトール骨格、ジペンタエリスリトール骨格、又はトリペンタエリスリトール骨格を有する化合物が好ましく、特にジペンタエリスリトール骨格を有する化合物が好ましい。
　より具体的には、酸性基を有する化合物は、ジペンタエリスリトールの５つのヒドロキシ基が（メタ）アクリロイルオキシ基に置換され、残りの１つのヒドロキシ基が例えばコハク酸とエステル結合することで、酸性基が導入された化合物が特に好ましい。 Specific examples of the compound having an acidic group are given below, but the compound having an acidic group is not limited thereto.
Compounds having an acidic group include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, and a polyisocyanate compound and a (meth) acryloyl-containing hydroxy compound. A compound in which an acidic group is introduced by leaving two or more unsaturated bonds (ethylenic double bonds) in an ethylenic compound having a urethane skeleton obtained by reacting with the above is preferable.
Further, the compound having an acidic group has an isocyanurate skeleton, a trimethylolpropane skeleton, a phthalic acid skeleton, a pentaerythritol skeleton, a dipentaerythritol skeleton, or a trypentaerythritol skeleton from the viewpoint of the introduction ratio of the ethylenic double bond. Compounds are preferred, and compounds having a dipentaerythritol skeleton are particularly preferred.
More specifically, a compound having an acidic group is acidic by substituting five hydroxy groups of dipentaerythritol with (meth) acryloyloxy groups and ester-bonding the remaining one hydroxy group with, for example, succinic acid. Compounds with introduced groups are particularly preferred.
　これらの化合物が１分子中に光硬化性官能基、好ましくはエチレン性二重結合、より好ましくはアクリレートを、２個以上、好ましくは３個以上、より好ましくは４個以上、特に好ましくは５個以上有し、さらに酸性基を併有することにより、耐溶剤性と現像残渣の低減効果が高いレベルで両立可能となる。 These compounds contain photocurable functional groups, preferably ethylenic double bonds, more preferably 2 or more, preferably 3 or more, more preferably 4 or more, particularly preferably 5 acrylates in one molecule. By having the above and further having an acidic group, it is possible to achieve both solvent resistance and the effect of reducing development residue at a high level.
　架橋剤（Ｃ）の酸価は、１０ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／ｇ以上がより好ましく、５０ｍｇＫＯＨ／ｇ以上がさらに好ましい。また、酸価は２００ｍｇＫＯＨ／ｇ以下が好ましく、１５０ｍｇＫＯＨ／ｇ以下がより好ましく、１００ｍｇＫＯＨ／ｇ以下がさらに好ましい。酸価は、１０～２００ｍｇＫＯＨ／ｇが好ましく、２０～１５０ｍｇＫＯＨ／ｇが更に好ましく、５０～１００ｍｇＫＯＨ／ｇが特に好ましい。架橋剤（Ｃ）の酸価が上記下限値以上であると、ポジ型感光性樹脂組成物においてより良好な現像液への溶解性を得ることができる。 The acid value of the cross-linking agent (C) is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and even more preferably 50 mgKOH / g or more. The acid value is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. The acid value is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, and particularly preferably 50 to 100 mgKOH / g. When the acid value of the cross-linking agent (C) is at least the above lower limit value, better solubility in a developing solution can be obtained in the positive photosensitive resin composition.
　架橋剤（Ｃ）は、前記酸性基を有する化合物１種を単独で用いても、その他の架橋剤と併用してもよい。 As the cross-linking agent (C), the above-mentioned compound having an acidic group may be used alone or in combination with other cross-linking agents.
　架橋剤（Ｃ）中の酸性基を有する化合物の割合は質量比で３０％以上であることが好ましく、５０％以上であることが更に好ましく、６０％以上であることが特に好ましい。 The ratio of the compound having an acidic group in the cross-linking agent (C) is preferably 30% or more, more preferably 50% or more, and particularly preferably 60% or more in terms of mass ratio.
　前記酸性基を有する化合物の使用量は、質量比で、（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）の合計に対して５～３５％の範囲にある。かかる使用量は、６％以上が好ましく、８％以上がより好ましい。また、使用量は、２５％以下が好ましく、２０％以下がより好ましい。また、使用量は６～２５％が好ましく、８～２０％が特に好ましい。使用量がこの範囲にあることで、本発明の効果をより効果的に発揮することができる。より具体的には、酸性基を有する化合物の使用量が上記下限値以上であることで、優れた耐溶剤性と現像残渣の低減効果とを両立しやすい。使用量が上記上限値以下であることで、基板との密着性が良好となりやすい。
　また、架橋剤（Ｃ）の割合は、アルカリ可溶性樹脂（Ａ）に対して質量比で、８％以上が好ましく、１０％以上がより好ましく、１２％以上がさらに好ましく、１４％以上が特に好ましい。また、かかる割合は４０％以下が好ましく、３５％以下がより好ましく、３０％以下がさらに好ましく、２６％以下が特に好ましい。かかる割合は好ましくは８～４０％、更に好ましくは１０～３５％、特に好ましくは１２～３０％、最も好ましくは１４～２６％である。架橋剤（Ｃ）の割合がアルカリ可溶性樹脂（Ａ）に対してこの範囲にあることで現像液溶解性とパターン形状のバランスに優れる。 The amount of the compound having an acidic group used is in the range of 5 to 35% with respect to the total of (A) + (B) + (C) + (D) in terms of mass ratio. The amount used is preferably 6% or more, more preferably 8% or more. The amount used is preferably 25% or less, more preferably 20% or less. The amount used is preferably 6 to 25%, particularly preferably 8 to 20%. When the amount used is within this range, the effect of the present invention can be more effectively exhibited. More specifically, when the amount of the compound having an acidic group used is at least the above lower limit value, it is easy to achieve both excellent solvent resistance and the effect of reducing development residue. When the amount used is not more than the above upper limit value, the adhesion to the substrate tends to be good.
The ratio of the cross-linking agent (C) to the alkali-soluble resin (A) is preferably 8% or more, more preferably 10% or more, further preferably 12% or more, and particularly preferably 14% or more. .. Further, such a ratio is preferably 40% or less, more preferably 35% or less, further preferably 30% or less, and particularly preferably 26% or less. Such a ratio is preferably 8 to 40%, more preferably 10 to 35%, particularly preferably 12 to 30%, and most preferably 14 to 26%. When the ratio of the cross-linking agent (C) is in this range with respect to the alkali-soluble resin (A), the balance between the developer solubility and the pattern shape is excellent.
＜界面活性剤（Ｄ）＞
　界面活性剤（Ｄ）は、ポジ型感光性樹脂組成物の塗布性を向上させ、また現像の際の残渣除去性を向上させる。
　本発明の界面活性剤（Ｄ）はＦ原子を有さない。界面活性剤（Ｄ）がＦ原子を有さないことで撥インク性を弱め、インクとの親和性が必要な用途に好適になる。一方で、撥インク剤を使用した場合、インクを塗布する箇所に撥インク性が生じてインクの塗布性が大きく低下する。そのため、界面活性剤（Ｄ）としては、撥インク剤として使用される化合物は好ましくない。 <Surfactant (D)>
The surfactant (D) improves the coatability of the positive photosensitive resin composition and also improves the residue removability during development.
The surfactant (D) of the present invention does not have an F atom. Since the surfactant (D) does not have an F atom, the ink repellency is weakened, which makes it suitable for applications requiring affinity with ink. On the other hand, when an ink-repellent agent is used, the ink-repellent property is generated at the portion where the ink is applied, and the ink applicability is greatly reduced. Therefore, as the surfactant (D), a compound used as an ink repellent is not preferable.
　界面活性剤（Ｄ）の具体例を以下に挙げるが、これらに限定されない。
　界面活性剤（Ｄ）としては、シリコーン系界面活性剤、ノニオン性、アニオン性、カチオン性及び両性界面活性剤が挙げられ、ポリエーテル変性シリコーン系界面活性剤が好ましい。
　シリコーン系界面活性剤としてより具体的には、ダウ・東レ株式会社製「トーレシリコーンＤＣ３ＰＡ」、「トーレシリコーンＳＨ７ＰＡ」、「トーレシリコーンＤＣ１１ＰＡ」、「トーレシリコーンＳＨ２１ＰＡ」、「トーレシリコーンＳＨ２８ＰＡ」、「トーレシリコーンＳＨ２９ＰＡ」、「トーレシリコーンＳＨ３０ＰＡ」、「トーレシリコーンＳＨ８４００」、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＴＳＦ－４４４０」、「ＴＳＦ－４３００」、「ＴＳＦ－４４４５」、「ＴＳＦ－４４４（４）（５）（６）（７）」、「ＴＳＦ－４４６０」、「ＴＳＦ－４４５２」、信越化学工業株式会社製「ＫＰ３４１」、ビッグケミー社製「ＢＹＫ３２３」、「ＢＹＫ３３０」などの市販品を挙げることができる。 Specific examples of the surfactant (D) are given below, but the present invention is not limited thereto.
Examples of the surfactant (D) include silicone-based surfactants, nonionic, anionic, cationic and amphoteric surfactants, and polyether-modified silicone-based surfactants are preferable.
More specifically, as a silicone-based surfactant, "Torre Silicone DC3PA", "Torre Silicone SH7PA", "Torre Silicone DC11PA", "Torre Silicone SH21PA", "Torre Silicone SH28PA", "Torre Silicone SH28PA" manufactured by Dow Toray Co., Ltd. Silicone SH29PA "," Torre Silicone SH30PA "," Torre Silicone SH8400 "," TSF-4440 "," TSF-4300 "," TSF-4445 "," TSF-444 "manufactured by Momentive Performance Materials Japan GK. 4) (5) (6) (7) ”,“ TSF-4460 ”,“ TSF-4452 ”,“ KP341 ”manufactured by Shin-Etsu Chemical Co., Ltd.,“ BYK323 ”,“ BYK330 ”manufactured by Big Chemie, etc. Can be mentioned.
　界面活性剤（Ｄ）の使用量は、質量比で、（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）の合計に対して０．１～１．０％の範囲にあることが好ましい。使用量がこの範囲にあることで、本発明の効果をより効果的に発揮することができる。 The amount of the surfactant (D) used is preferably in the range of 0.1 to 1.0% with respect to the total of (A) + (B) + (C) + (D) in terms of mass ratio. .. When the amount used is within this range, the effect of the present invention can be more effectively exhibited.
［任意成分］
＜溶媒（Ｅ）＞
　本発明のポジ型感光性樹脂組成物は、溶媒（Ｅ）を含有してもよい。
　溶媒（Ｅ）を含有することで、ポジ型感光性樹脂組成物の塗工性、基板への密着性、安定性がより優れる。
　溶媒（Ｅ）としては、ポジ型感光性樹脂組成物に用いられる公知の溶媒を使用できる。溶媒（Ｅ）としては、具体的にはアルコール類、エーテル類、芳香族類、及び炭化水素が挙げられるが、溶媒（Ｅ）はこれらに限定されない。 [Arbitrary ingredient]
<Solvent (E)>
The positive photosensitive resin composition of the present invention may contain a solvent (E).
By containing the solvent (E), the coatability, adhesion to the substrate, and stability of the positive photosensitive resin composition are more excellent.
As the solvent (E), a known solvent used for the positive photosensitive resin composition can be used. Specific examples of the solvent (E) include alcohols, ethers, aromatics, and hydrocarbons, but the solvent (E) is not limited thereto.
　ポジ型感光性樹脂組成物の塗膜の均一性が向上し、かつ層分離に優れるため、溶媒（Ｅ）における沸点が１７０℃以上の化合物の割合は１０～７０質量％の範囲にあることが特に好ましい。 Since the uniformity of the coating film of the positive photosensitive resin composition is improved and the layer separation is excellent, the proportion of the compound having a boiling point of 170 ° C. or higher in the solvent (E) is in the range of 10 to 70% by mass. Especially preferable.
　また、溶媒（Ｅ）の配合量は、ポジ型感光性樹脂組成物中、質量比で、６０～９０％の範囲が好ましく、７５～８５％の範囲が特に好ましい。 Further, the blending amount of the solvent (E) is preferably in the range of 60 to 90%, particularly preferably in the range of 75 to 85% in terms of mass ratio in the positive photosensitive resin composition.
＜その他の成分＞
　本発明のポジ型感光性樹脂組成物は、必要に応じて本発明の効果を損なわない範囲で、熱硬化剤、熱硬化促進剤、着色剤、シランカップリング剤、微粒子、増粘剤、可塑剤、消泡剤、レベリング剤、ハジキ防止剤及び紫外線吸収剤など、ポジ型感光性樹脂組成物として添加される公知の成分を添加してもよい。より具体的には、日本国特許第６０９８６３５号公報、段落００８０～００９５に記載の成分等を加えてもよい。 <Other ingredients>
The positive photosensitive resin composition of the present invention is a thermosetting agent, a thermosetting accelerator, a colorant, a silane coupling agent, fine particles, a thickener, and a plasticizer as long as the effects of the present invention are not impaired. Known components added as a positive photosensitive resin composition, such as an agent, a defoaming agent, a leveling agent, an anti-repellent agent, and an ultraviolet absorber, may be added. More specifically, the components described in Japanese Patent No. 6098635, paragraphs 0080 to 0995 may be added.
［ポジ型感光性樹脂組成物の調製方法］
　ポジ型感光性樹脂組成物は、アルカリ可溶性樹脂（Ａ）、感光剤（Ｂ）、架橋剤（Ｃ）及び界面活性剤（Ｄ）、並びに必要に応じて溶媒及びその他の成分を均一になるまで混合して調製される。 [Method for preparing positive photosensitive resin composition]
The positive photosensitive resin composition contains the alkali-soluble resin (A), the photosensitive agent (B), the cross-linking agent (C) and the surfactant (D), and if necessary, the solvent and other components until they become uniform. Prepared by mixing.
　本発明のポジ型感光性樹脂組成物は、有機ＥＬ素子、カラーフィルタ、及びＴＦＴアレイ等の光学素子における画素形成用隔壁、層間絶縁膜、平坦化膜、さらにはマイクロレンズ形成用として好適に使用されるが、用途はこれらに限定されない。例えば、本発明のポジ型感光性樹脂組成物を硬化した硬化物を上記用途等に好適に使用できる。 The positive photosensitive resin composition of the present invention is suitably used for forming a pixel-forming partition wall, an interlayer insulating film, a flattening film, and further a microlens in an optical element such as an organic EL element, a color filter, and a TFT array. However, the application is not limited to these. For example, a cured product obtained by curing the positive photosensitive resin composition of the present invention can be suitably used for the above-mentioned applications and the like.
　一例として有機ＥＬ素子の製造方法を示す。
　ガラス等の透明基板にスズドープ酸化インジウム（ＩＴＯ）等の透明電極をスパッタ法等によって製膜し、必要に応じて、所望のパターンに透明電極をエッチングする。次に、本発明のポジ型感光性樹脂組成物を用いて隔壁（硬化物）を形成し、さらには表面が撥液性を有するバンク剤を形成後、インクジェット法を用いてドットに正孔輸送材料、発光材料の溶液を順次塗布し、乾燥して、正孔輸送層、及び発光層を形成する。その後、アルミニウム等の電極を蒸着法等によって形成することによって、有機ＥＬ素子の画素が得られる。 As an example, a method for manufacturing an organic EL element is shown.
A transparent electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by a sputtering method or the like, and if necessary, the transparent electrode is etched into a desired pattern. Next, a partition wall (cured product) is formed using the positive photosensitive resin composition of the present invention, a banking agent having a liquid-repellent surface is formed, and then holes are transported to the dots by an inkjet method. A solution of the material and the light emitting material is sequentially applied and dried to form a hole transport layer and a light emitting layer. After that, the pixels of the organic EL element can be obtained by forming an electrode of aluminum or the like by a vapor deposition method or the like.
　実施例及び比較例により本発明を具体的に説明するが、本発明の効果を奏する限りにおいて実施形態を適宜変更することができる。例１～例１０は実施例であり、例１１～例１３は比較例である。 Although the present invention will be specifically described with reference to Examples and Comparative Examples, the embodiments can be appropriately changed as long as the effects of the present invention are exhibited. Examples 1 to 10 are examples, and examples 11 to 13 are comparative examples.
＜測定条件・評価条件＞
［評価用サンプル］
　表１に記載のポジ型感光性樹脂組成物を用いて、ＩＴＯ基板上に硬化膜を作製し評価用サンプルとした。評価用サンプルとして評価用サンプル１と２の２種類用意した。
　評価用サンプル１を用いて密着性と耐溶剤性を評価した。
　評価用サンプル２を用いて現像残渣量を評価した。 <Measurement conditions / evaluation conditions>
[Evaluation sample]
Using the positive photosensitive resin composition shown in Table 1, a cured film was prepared on an ITO substrate and used as an evaluation sample. Two types of evaluation samples 1 and 2 were prepared as evaluation samples.
Adhesion and solvent resistance were evaluated using the evaluation sample 1.
The amount of development residue was evaluated using the evaluation sample 2.
［評価用サンプル１］
　ＩＴＯ基板（株式会社倉元製作所製の抵抗値１０Ω／ｓｑ以下のＩＴＯ品、寸法７．５ｃｍ×７．５ｃｍ×０．７ｍｍ）をエタノール中で超音波洗浄（３０分間）した。
　次いで５分間紫外線／オゾン洗浄（装置：ＰＬ７－２００　センエジニアリング株式会社製）を行った。
　洗浄後の基板表面に、スピンナ（ミカサ株式会社製　ＩＨ－ＤＸ２）を用いて、ポジ型感光性樹脂組成物をスピン塗布（回転数６１０ｒｐｍ、１０秒間）した。次に１００℃で２分間ホットプレート上で乾燥させ、膜厚１．３μｍの膜を形成した。得られた膜の表面を、以下の条件で露光した。
＜条件＞
［フォトマスク］：２０ｍｍ×２０ｍｍの範囲に以下の１８種類のラインパターンを繰り返す遮光部を有する。
　遮光部の形状：それぞれ１、２、３、４、５、６、７、８、９、１０、１２、１４、１６、１８、２０、３０、４０、５０μｍ×１０００μｍ
　パターン間隔：５０μｍ
［ランプ］：ウシオ電機社製ＵＳＨ－２５５ＢＹ、３６５ｎｍ換算の露光パワー（露光出力）２５ｍＷ／ｃｍ２
［照射条件］：３３０ｎｍ以下の光はカットし、その際５０μｍの間隙をあけ、２５ｍＷ／ｃｍ２で８秒間照射した。 [Evaluation sample 1]
An ITO substrate (IT product with a resistance value of 10 Ω / sq or less manufactured by Kuramoto Co., Ltd., dimensions 7.5 cm × 7.5 cm × 0.7 mm) was ultrasonically cleaned (30 minutes) in ethanol.
Then, ultraviolet / ozone cleaning (apparatus: PL7-200 manufactured by Sen Engineering Co., Ltd.) was performed for 5 minutes.
A positive photosensitive resin composition was spin-coated (rotation speed: 610 rpm, 10 seconds) on the surface of the substrate after cleaning using a spinner (IH-DX2 manufactured by Mikasa Sports Co., Ltd.). Next, it was dried on a hot plate at 100 ° C. for 2 minutes to form a film having a film thickness of 1.3 μm. The surface of the obtained film was exposed under the following conditions.
<Conditions>
[Photomask]: A light-shielding portion that repeats the following 18 types of line patterns in a range of 20 mm × 20 mm.
Shape of light-shielding part: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 30, 40, 50 μm × 1000 μm, respectively
Pattern interval: 50 μm
[Lamp]: Ushio, Inc. USH-255BY, 365 nm equivalent exposure power (exposure output) 25 mW / cm 2
[Irradiation conditions]: Light of 330 nm or less was cut, and at that time, a gap of 50 μm was formed, and irradiation was performed at 25 mW / cm 2 for 8 seconds.
　露光後のＩＴＯ基板をテトラメチル水酸化アンモニウム水溶液（０．４質量％）に４０秒間浸漬して現像した。その後、水洗と乾燥を行った。乾燥後の基板をホットプレート上で加熱（２２０℃、６０分間）し、特定のパターンを有する硬化膜を有するＩＴＯ基板を作製した（評価用サンプル１）。 The exposed ITO substrate was immersed in a tetramethylammonium hydroxide aqueous solution (0.4% by mass) for 40 seconds for development. Then, it was washed with water and dried. The dried substrate was heated on a hot plate (220 ° C., 60 minutes) to prepare an ITO substrate having a cured film having a specific pattern (evaluation sample 1).
［評価用サンプル２］
　使用するフォトマスクを変更した以外は評価用サンプル１と同様の方法で評価用サンプル２を作製した。
［フォトマスク］：２０ｍｍ×２０ｍｍの範囲に以下のパターンで開口部を有する。
　開口部の形状：１００μｍ×２００μｍ
　パターン間隔：２０μｍ [Sample 2 for evaluation]
Evaluation sample 2 was prepared in the same manner as evaluation sample 1 except that the photomask used was changed.
[Photomask]: An opening is provided in a range of 20 mm × 20 mm in the following pattern.
Opening shape: 100 μm x 200 μm
Pattern interval: 20 μm
［密着性］
　評価用サンプル１の硬化膜のパターンを顕微鏡で観察し、洗浄工程で剥離せずに残存した硬化膜のラインの欠損の有無から以下の基準で密着性を判断した。
　良：幅が１０μｍ未満のラインに欠損がなかった。
　不可：幅が１０μｍ未満のラインに欠損があった。
　良を合格とした。 [Adhesion]
The pattern of the cured film of the evaluation sample 1 was observed with a microscope, and the adhesion was judged based on the following criteria based on the presence or absence of defects in the lines of the cured film that remained without peeling in the washing step.
Good: There was no defect in the line with a width of less than 10 μm.
Impossible: There was a defect in the line with a width of less than 10 μm.
Good was passed.
［現像残渣］
　評価用サンプル２の硬化膜のバンク抜き部について残渣量測定を行った。なお、バンク抜き部とは、現像操作で、膜を除去した部分のことを意味する。
　バンク抜き部のＩＴＯ面の残渣量をμ－ＸＰＳ法で測定し、以下の基準で評価した。
＜測定条件＞
測定装置：アルバック・ファイ社製　ＱｕａｎｔｅｒａＳＸＭＸ線
条件：５０μｍΦ、１２．５Ｗ、１５ｋＶ
ラスターサイズ：ｐｏｉｎｔ
試料角度：４５度
Ａｃｑｕｉｓｉｔｉｏｎ　ｃｙｃｌｅ　：１８
Ｐａｓｓ　Ｅｎｅｒｇｙ　Ｓｔｅｐ　：０．４ｅＶで測定を行い、測定データをＣ／Ｉｎで数値化した。
　優：残渣量が４以下であった。
　良：残渣量が４より大きく、５以下であった。
　可：残渣量が５より大きく、８以下であった。
　不可：残渣量が８より大きかった。
　優、良、可を合格とした。 [Development residue]
The amount of residue was measured for the unbanked portion of the cured film of the evaluation sample 2. The bank-extracted portion means a portion from which the film has been removed by a developing operation.
The amount of residue on the ITO surface of the unbanked portion was measured by the μ-XPS method and evaluated according to the following criteria.
<Measurement conditions>
Measuring device: ULVAC-PHI QuanteraSXMX line Condition: 50 μmΦ, 12.5 W, 15 kV
Raster size: point
Sample angle: 45 degrees Acquisition cycle: 18
Pass Energy Step: Measurement was performed at 0.4 eV, and the measurement data was quantified by C / In.
Excellent: The amount of residue was 4 or less.
Good: The amount of residue was greater than 4 and less than 5.
Possible: The amount of residue was larger than 5 and 8 or less.
Impossible: The amount of residue was greater than 8.
Excellent, good, and acceptable were accepted.
［耐溶剤性］
　評価用サンプル１の硬化膜にＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）２．５μｌを滴下し、６０秒放置した。
　その後ＰＧＭＥＡをウェス（ベンコットＭ－３ＩＩ　旭化成株式会社製）で拭き取り、膜上面の溶解痕の有無を目視で確認し、以下の基準で評価した。
　良：溶解痕が無かった。
　可：僅かに表面に円形の跡が残った。
　不可：溶解痕が有った。
　良及び、可を合格とした。 [Solvent resistance]
2.5 μl of PGMEA (propylene glycol monomethyl ether acetate) was added dropwise to the cured film of sample 1 for evaluation, and the mixture was allowed to stand for 60 seconds.
After that, PGMEA was wiped off with a waste cloth (manufactured by Bencot M-3II Asahi Kasei Corporation), and the presence or absence of dissolution marks on the upper surface of the film was visually confirmed and evaluated according to the following criteria.
Good: There were no dissolution marks.
Yes: A slight circular mark was left on the surface.
Impossible: There was a dissolution mark.
Good and acceptable were accepted.
［実施例及び比較例］
　表１に記載の割合で原料を均一になるまで撹拌（約３０分）して、ポジ型感光性樹脂組成物を調製した。これを用いてそれぞれ評価用サンプル１、２を作製して評価を行った。評価結果を表１に示す。
　表中の数字は、有効数字を小数点第一位として表示している。また、表中の空欄は該当列の成分を含有しないことを示す。 [Examples and Comparative Examples]
The raw materials were stirred (about 30 minutes) at the ratios shown in Table 1 until they became uniform to prepare a positive photosensitive resin composition. Using this, evaluation samples 1 and 2 were prepared and evaluated, respectively. The evaluation results are shown in Table 1.
The numbers in the table show significant figures as the first decimal place. In addition, the blanks in the table indicate that the components in the corresponding column are not contained.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＜略語の説明＞
［アルカリ可溶性樹脂（Ａ）］
Ａ１：オルソクレゾールノボラック樹脂（Ｍｗ：１７４０）
Ａ２：オルソクレゾールノボラック樹脂（Ｍｗ：２４７０） <Explanation of abbreviations>
[Alkali-soluble resin (A)]
A1: Orthocresol novolak resin (Mw: 1740)
A2: Orthocresol novolak resin (Mw: 2470)
［感光剤（Ｂ）］
Ｂ１：２，３，４，４’－テトラヒドロキシベンゾフェノンと６－ジアゾ－５，６－ジヒドロ－５－オキソ－ナフタレン－１－スルホン酸との（モノ～テトラ）エステル [Photosensitizer (B)]
(Mono-tetra) ester of B1: 2,3,4,4'-tetrahydroxybenzophenone and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid
［架橋剤（Ｃ）］
Ｃ１：多塩基酸変性アクリルオリゴマー（ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート及び、ジペンタエリスリトールペンタアクリレートのコハク酸エステル（酸価９２ｍｇＫＯＨ／ｇ、分子量６１２）の混合物）
Ｃ２：２，２，２－トリアクリロイロオキシメチルエチルフタル酸（酸価８７ｍｇＫＯＨ／ｇ、分子量４４６）
Ｃ３：ジペンタエリスリトールヘキサアクリレート及びジペンタエリスリトールペンタアクリレートの混合物 [Crosslinking agent (C)]
C1: Polybasic acid-modified acrylic oligomer (mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinate of dipentaerythritol pentaacrylate (acid value 92 mgKOH / g, molecular weight 612))
C2: 2,2,2-triacryloyloxymethylethylphthalic acid (acid value 87 mgKOH / g, molecular weight 446)
C3: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate
［界面活性剤（Ｄ）］
Ｄ１：ポリエーテル変性ポリジメチルシロキサンのキシレン／フェニルグリコール混合溶液（固形分１２．５％） [Surfactant (D)]
D1: Xylene / phenylglycol mixed solution of polyether-modified polydimethylsiloxane (solid content 12.5%)
［溶媒（Ｅ）］
ＥＤＭ：ジエチレングリコールエチルメチルエーテル（沸点１７６℃）
ＰＧＭＥ：プロピレングリコールモノメチルエーテル（沸点１２０℃）
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート（沸点１４６℃） [Solvent (E)]
EDM: Diethylene glycol ethyl methyl ether (boiling point 176 ° C)
PGME: Propylene glycol monomethyl ether (boiling point 120 ° C)
PGMEA: Propylene glycol monomethyl ether acetate (boiling point 146 ° C)
　本発明を詳細にまた特定の実施形態を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は、２０２０年３月４日出願の日本特許出願（特願２０２０－０３７１７０）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on March 4, 2020 (Japanese Patent Application No. 2020-031170), the contents of which are incorporated herein by reference.

Claims (11)

  1. 　アルカリ可溶性樹脂（Ａ）、感光剤（Ｂ）、架橋剤（Ｃ）、界面活性剤（Ｄ）を含有し、前記架橋剤（Ｃ）が酸性基としてカルボキシル基、フェノール性水酸基、スルホ基及びリン酸基からなる群より選ばれる１以上を有する化合物を含有し、
    　前記酸性基を有する化合物の割合が、質量比で、（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）の合計に対して５～３５％の範囲にあり、
    　前記界面活性剤（Ｄ）がＦ原子を有さないポジ型感光性樹脂組成物。     It contains an alkali-soluble resin (A), a photosensitizer (B), a cross-linking agent (C), and a surfactant (D), and the cross-linking agent (C) contains a carboxyl group, a phenolic hydroxyl group, a sulfo group and phosphorus as acidic groups. Contains a compound having one or more selected from the group consisting of acid groups,
    The ratio of the compound having an acidic group is in the range of 5 to 35% with respect to the total of (A) + (B) + (C) + (D) in terms of mass ratio.
    A positive photosensitive resin composition in which the surfactant (D) does not have an F atom.
  2. 　前記感光剤（Ｂ）がキノンジアジド化合物を含有する請求項１に記載のポジ型感光性樹脂組成物。 The positive photosensitive resin composition according to claim 1, wherein the photosensitive agent (B) contains a quinonediazide compound.
  3. 　前記アルカリ可溶性樹脂（Ａ）の質量平均分子量が５００～１００００の範囲にある請求項１又は２に記載のポジ型感光性樹脂組成物。 The positive photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin (A) has a mass average molecular weight in the range of 500 to 10000.
  4. 　前記アルカリ可溶性樹脂（Ａ）がフェノール樹脂である請求項１～３のいずれか１項に記載のポジ型感光性樹脂組成物。 The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble resin (A) is a phenol resin.
  5. 　前記フェノール樹脂がオルトクレゾール樹脂である請求項４に記載のポジ型感光性樹脂組成物。 The positive photosensitive resin composition according to claim 4, wherein the phenol resin is an orthocresol resin.
  6. 　前記酸性基がカルボキシル基である請求項１～５のいずれか１項に記載のポジ型感光性樹脂組成物。 The positive photosensitive resin composition according to any one of claims 1 to 5, wherein the acidic group is a carboxyl group.
  7. 　前記架橋剤（Ｃ）が１分子中に前記カルボキシル基を１～３個有する化合物を含有する請求項６に記載のポジ型感光性樹脂組成物。 The positive photosensitive resin composition according to claim 6, wherein the cross-linking agent (C) contains a compound having 1 to 3 carboxyl groups in one molecule.
  8. 　前記架橋剤（Ｃ）中の前記酸性基を有する化合物の割合が、質量比で３０％以上である請求項１～７のいずれか１項に記載のポジ型感光性樹脂組成物。 The positive photosensitive resin composition according to any one of claims 1 to 7, wherein the ratio of the compound having an acidic group in the cross-linking agent (C) is 30% or more by mass ratio.
  9. 　更に溶媒（Ｅ）を含有し、前記溶媒における沸点が１７０℃以上の化合物の割合が１０～７０質量％の範囲にある請求項１～８のいずれか１項に記載のポジ型感光性樹脂組成物。 The positive photosensitive resin composition according to any one of claims 1 to 8, further containing the solvent (E) and having the proportion of the compound having a boiling point of 170 ° C. or higher in the solvent in the range of 10 to 70% by mass. thing.
  10. 　請求項１～９のいずれか１項に記載のポジ型感光性樹脂組成物を硬化した硬化物。 A cured product obtained by curing the positive photosensitive resin composition according to any one of claims 1 to 9.
  11. 　請求項１０に記載の硬化物を隔壁として含む光学素子。 An optical element containing the cured product according to claim 10 as a partition wall.
PCT/JP2021/007782 2020-03-04 2021-03-01 Positive-type photosensitive resin composition WO2021177250A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06118648A (en) * 1991-12-10 1994-04-28 Konica Corp Positive type photosensitive composition and image forming method
JP2010134422A (en) * 2008-10-28 2010-06-17 Jsr Corp Radiation-sensitive resin composition, interlayer insulation film and microlens, and method for producing them
JP2012252095A (en) * 2011-06-01 2012-12-20 Hitachi Chem Co Ltd Positive photosensitive resin composition and photosensitive film
JP2016042126A (en) * 2014-08-15 2016-03-31 Jsr株式会社 Radiation-sensitive resin composition, interlayer insulation film of display element, method of forming the same, and display element
JP2016166951A (en) * 2015-03-09 2016-09-15 Jnc株式会社 Photosensitive composition

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* Cited by examiner, † Cited by third party
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KR102229661B1 (en) 2013-10-21 2021-03-18 닛산 가가쿠 가부시키가이샤 Positive-type photosensitive resin composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06118648A (en) * 1991-12-10 1994-04-28 Konica Corp Positive type photosensitive composition and image forming method
JP2010134422A (en) * 2008-10-28 2010-06-17 Jsr Corp Radiation-sensitive resin composition, interlayer insulation film and microlens, and method for producing them
JP2012252095A (en) * 2011-06-01 2012-12-20 Hitachi Chem Co Ltd Positive photosensitive resin composition and photosensitive film
JP2016042126A (en) * 2014-08-15 2016-03-31 Jsr株式会社 Radiation-sensitive resin composition, interlayer insulation film of display element, method of forming the same, and display element
JP2016166951A (en) * 2015-03-09 2016-09-15 Jnc株式会社 Photosensitive composition

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