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

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• 2021
  • 2021-03-01 KR KR1020227030026A patent/KR20220149671A/ko unknown
  • 2021-03-01 CN CN202180018155.6A patent/CN115244462A/zh not_active Withdrawn
  • 2021-03-01 JP JP2022504364A patent/JPWO2021177250A1/ja not_active Withdrawn
  • 2021-03-01 WO PCT/JP2021/007782 patent/WO2021177250A1/ja active Application Filing
  • 2021-03-04 TW TW110107713A patent/TW202141186A/zh unknown

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