WO2023080254A1 - ポジ型感光性樹脂組成物 - Google Patents
ポジ型感光性樹脂組成物 Download PDFInfo
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- WO2023080254A1 WO2023080254A1 PCT/JP2022/041568 JP2022041568W WO2023080254A1 WO 2023080254 A1 WO2023080254 A1 WO 2023080254A1 JP 2022041568 W JP2022041568 W JP 2022041568W WO 2023080254 A1 WO2023080254 A1 WO 2023080254A1
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- resin composition
- photosensitive resin
- positive photosensitive
- acid
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- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- SVGQCVJXVAMCPM-UHFFFAOYSA-N triethyl(prop-2-enyl)silane Chemical compound CC[Si](CC)(CC)CC=C SVGQCVJXVAMCPM-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- ZFDUTAIOLLHHSG-UHFFFAOYSA-N trimethyl(2-methylprop-1-enylsilyloxy)silane Chemical compound C[Si](O[SiH2]C=C(C)C)(C)C ZFDUTAIOLLHHSG-UHFFFAOYSA-N 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000012989 trithiocarbonate Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Images
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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
-
- 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
- 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
-
- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
-
- 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
- H05B33/02—Details
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
Definitions
- the present invention relates to a positive photosensitive resin composition. More specifically, the present invention relates to a positive photosensitive resin composition containing a quinonediazide compound as a radiation-sensitive compound.
- the positive photosensitive resin composition is used as an interlayer insulating film, planarizing film, or protective film for semiconductor devices, or as an insulating film, planarizing film, or partition material for display devices such as organic EL displays (OLED) and liquid crystal displays. widely used as.
- a partition material is used in the gaps between the colored patterns in the display area or the edge of the peripheral portion of the display area.
- partition walls are first formed, and organic pixels are formed between the partition walls in order to prevent organic substance pixels from coming into contact with each other.
- This partition is generally formed by photolithography using a photosensitive resin composition and has insulating properties. Specifically, a photosensitive resin composition is applied onto a substrate using a coating device, volatile components are removed by means of heating or the like, and then exposed through a mask.
- the exposed portion is developed by removing it with a developing solution such as an alkaline aqueous solution, and the resulting pattern is heat-treated to form a partition wall (insulating film).
- a developing solution such as an alkaline aqueous solution
- the resulting pattern is heat-treated to form a partition wall (insulating film).
- an organic substance emitting three colors of red, green, and blue is deposited between the barrier ribs to form the pixels of the organic EL display device.
- Patent Document 1 Japanese Unexamined Patent Application Publication No. 2001-281440 discloses a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition exhibiting high light-shielding properties by heat treatment after exposure. describes a composition to which titanium black is added.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2002-116536 describes a radiation-sensitive resin composition containing [A] an alkali-soluble resin, [B] a 1,2-quinonediazide compound, and [C] a colorant, wherein carbon black describes a method of blackening a barrier rib material using
- Patent Document 3 Japanese Patent Application Laid-Open No. 2010-237310 describes a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition that exhibits light-shielding properties by heat treatment after exposure. Compositions with added thermal dyes are described.
- Patent Document 4 International Publication No. 2017/069172 discloses (A) a binder resin, (B) a quinonediazide compound, and (C) at least one black dye selected from solvent black color indexes 27 to 47. A positive-acting photosensitive resin composition containing a black dye is described.
- a chemically amplified photosensitive resin composition generally contains a resin in which an alkali-soluble functional group is protected with an acid-decomposable group, and a photoacid generator.
- the acid generated from the photoacid generator during exposure promotes decomposition (deprotection) of the acid-decomposable group to regenerate the alkali-soluble functional group. This promotes alkali dissolution of the resin in the exposed areas during development.
- the acid derived from the photoacid generator is regenerated after decomposing a certain acid-decomposable group and participates in the decomposition of another acid-decomposable group.
- the apparent quantum efficiency of the chemical amplification system based on the above reaction mechanism is expressed as the product of the quantum efficiency of acid generation and the reaction chain, so high sensitivity is achieved by using a photosensitive resin composition as a chemical amplification system. can do.
- Patent Document 5 International Publication No. 2015/087830 discloses a polybenzoxazole precursor containing a specific repeating unit, a photoacid generator, a solvent, a cross-linking agent, and a group in which the acid group is protected with an acid-decomposable group.
- a photosensitive resin composition is described containing a compound having in the molecule.
- Patent Document 6 International Publication No. 2020/246517 discloses a first resin (A) having a plurality of phenolic hydroxyl groups, at least a portion of which is protected with an acid-decomposable group, and epoxy a second resin (B) having a group and a phenolic hydroxyl group, at least one coloring agent (C) selected from the group consisting of black dyes and black pigments, and a photoacid generator (D).
- a type photosensitive resin composition is described.
- the partition wall material has a light-shielding property
- the sensitivity of the photosensitive resin composition tends to be low. Therefore, a photosensitive resin composition used for forming a partition wall material containing a colorant is required to have higher sensitivity.
- the photosensitive resin composition used to form a colored partition wall material it is necessary to use a considerable amount of a coloring agent in order to sufficiently enhance the light shielding properties of the cured film.
- a coloring agent in order to sufficiently enhance the light shielding properties of the cured film.
- the radiation irradiated to the film of the photosensitive resin composition is absorbed by the colorant, so that the effective intensity of the radiation in the film is reduced, and the photosensitive resin composition is not sufficiently exposed, resulting in poor patternability.
- a thick film for example, a film with a thickness of 2 to 3 ⁇ m is formed by blending a black colorant into a photosensitive resin composition for the purpose of improving the image quality of a display device, making it flexible, or saving power. is noticeable in
- a chemically amplified positive photosensitive resin composition has higher sensitivity than a positive photosensitive resin composition containing, for example, a quinonediazide compound as a radiation-sensitive compound.
- the photoacid generator used in the chemical amplification system is expensive, and the positive photosensitive resin composition of the chemical amplification system tends to cause coating unevenness in the coating, promoting decomposition of the acid-decomposable group. requires a post-exposure bake (PEB) for
- PEB post-exposure bake
- the acid generated from the photoacid generator during exposure diffuses in the film during the PEB process, so the pattern shape, dimension, sensitivity, etc. may change depending on the PEB conditions. Therefore, it is difficult to form a stepped pattern on a thick film with high accuracy using a chemically amplified positive photosensitive resin composition.
- An object of the present invention is to provide a positive photosensitive resin composition capable of forming a thick film pattern with high accuracy.
- the present inventors have found that in a positive photosensitive resin composition containing a quinonediazide compound as a radiation-sensitive compound, by combining a hydrophobic resin and an alkali-soluble resin as resin components with a fluorosurfactant, the alkalinity of the film surface is reduced. It has been found that the solubility can be relatively reduced, and as a result, a thick film pattern can be formed with high accuracy.
- the present invention includes the following aspects.
- the dissolution rate of the coating surface layer is lower than the dissolution rate of the entire coating, and the dissolution rate of the coating surface layer is the average dissolution rate at the time when the coating is dissolved until the thickness of the coating reaches 80%, and the dissolution rate of the entire coating.
- the positive photosensitive resin composition is the average dissolution rate at the time of dissolving until the film thickness of the film reaches 30%.
- the hydrophobic resin (A) has the formula (1) (In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 is represented by SiR 3 R 4 R 5 , and R 3 , R 4 and R 5 are each independently is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 5, s is an integer of 0 to 5, provided that r + s is an integer of 1 to 5 is an integer.)
- the positive photosensitive resin composition according to [3] which has at least one structural unit represented by formula (1), wherein s is an integer of 1 or more.
- the hydrophobic resin (A) has the formula (2) (In Formula (2), R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 8 is a hydrogen atom or a linear at least one selected from the group consisting of an alkyl group, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms; is a phenyl group substituted with
- the positive photosensitive resin composition according to any one of the above.
- the alkali-soluble resin (B) contains a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer, a resin having an epoxy group and a phenolic hydroxyl group, or a combination thereof. , the positive photosensitive resin composition according to any one of [1] to [6].
- [11] [1] An organic EL element partition comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [10].
- An organic EL element insulating film comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [10].
- An organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [10].
- FIG. 2 is a chart showing the sputtering time (horizontal axis) and silicon element concentration (vertical axis) of films of Examples 4, 6, and 7 obtained by XPS analysis.
- alkali-soluble means that the positive photosensitive resin composition or its components, or the film or cured film of the positive photosensitive resin composition is dissolved in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. It means possible.
- the "alkali-soluble resin” is a resin that can be dissolved in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide either alone or in a state of being contained in an unexposed or post-exposed positive photosensitive resin composition.
- Alkali-soluble resins include resins that are not alkali-soluble when the positive photosensitive resin composition is not exposed to light, but become alkali-soluble when exposed to light.
- alkali-soluble functional group means a group capable of imparting such alkali-solubility to a positive photosensitive resin composition or a component thereof, or a film or cured film of a positive photosensitive resin composition.
- Alkali-soluble functional groups include, for example, phenolic hydroxyl groups, carboxy groups, sulfo groups, phosphoric acid groups, acid anhydride groups, and mercapto groups.
- acid-decomposable group means a group that is decomposed (deprotected) by heating in the presence of an acid as necessary to generate an alkali-soluble functional group.
- radical polymerizable functional group means an ethylenically unsaturated group
- radical polymerizable compound means a compound having one or more ethylenically unsaturated groups.
- structural unit means an atomic group that constitutes part of the basic structure of a polymer, and this atomic group may have pendant atoms or pendant atomic groups.
- a radical (co)polymer it means a unit derived from a radically polymerizable compound used as a monomer, and in the case of a phenol novolac resin, one molecule of phenol (C 6 H 5 OH) and one means the following units formed from the condensation reaction of molecular formaldehyde (HCHO).
- Structural units with pendant groups include structural units with pendant groups used to form cross-linking sites or groups derived from them, and structural units with free pendant groups that are not involved in the formation of cross-linking sites. are considered to be different from each other.
- branched chain the structural unit containing the branch point (branching unit) and the structural unit contained in the linear molecular chain are considered different from each other.
- (meth)acrylic means acrylic or methacrylic
- (meth)acrylate means acrylate or methacrylate
- (meth)acryloyl means acryloyl or methacryloyl.
- the number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin, polymer, or copolymer are measured by gel permeation chromatography (GPC, gel permeation chromatography), standard polystyrene conversion values means
- Phenolic hydroxyl equivalent (epoxy equivalent of raw material + molecular weight of carboxylic acid to be added)/(number of phenolic hydroxyl groups of carboxylic acid) means a value calculated by
- resin component means hydrophobic resin (A) and alkali-soluble resin (B).
- a component corresponding to the fluorosurfactant (D) shall not be included in the hydrophobic resin (A) and the alkali-soluble resin (B).
- solid content includes optional components such as a resin component, a quinonediazide compound (C), a fluorosurfactant (D), a colorant (E), a dissolution accelerator (F), etc. means the total mass of the components excluding the solvent (G).
- a positive photosensitive resin composition of one embodiment includes a hydrophobic resin (A), an alkali-soluble resin (B), a quinonediazide compound (C), and a fluorosurfactant (D).
- a positive photosensitive resin composition is applied so that the film thickness after prebaking is 3 ⁇ 0.3 ⁇ m, prebaked at 125 ° C. for 120 seconds to form a film, and then exposed under the conditions of 30 mJ / cm 2 , When developed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution at a temperature of 23° C., the dissolution rate of the coating surface layer is lower than the dissolution rate of the entire coating.
- the dissolution rate of the coating surface layer is the average dissolution rate when the coating is dissolved until the thickness of the coating reaches 80%, and the dissolution rate of the entire coating is the dissolution rate until the thickness of the coating reaches 30%. It is the average dissolution rate at the time of exposure.
- Hydrophobic resin (A) is a resin that promotes its uneven distribution on the film surface by the fluorosurfactant (D) and makes the film surface of the positive photosensitive resin composition insoluble in an alkaline aqueous solution. .
- the hydrophobic resin (A) accompanies the fluorosurfactant (D) that migrates to the film surface in the process of forming the film of the positive photosensitive resin composition. Easy to migrate toward the film surface. Therefore, after forming the film, the hydrophobic resin (A) exists in a higher concentration on the surface of the film than inside the film, and lowers the alkali solubility of the surface of the film.
- the hydrophobic resin (A) suppresses the dissolution of the film surface in the unexposed areas as a resin component with low alkali solubility, while the exposed areas contain a carboxylic acid compound derived from the quinonediazide compound (C) and a highly alkali-soluble It is released from the coating into the developer along with the dissolution of the other resin components and any solubility enhancers.
- the dissolution of the inside of the film which has higher alkali solubility than the surface of the film, progresses quickly because the concentration of the hydrophobic resin (A) is relatively low. Thereby, the contrast between the exposed area and the unexposed area can be increased, and as a result, the pattern formability of the thick film of the positive photosensitive resin composition can be enhanced.
- a hydrophobic resin and a fluorosurfactant are used in combination to make the film surface insoluble in an alkaline aqueous solution, photoacid generation occurs during exposure. Since the acid generated from the agent diffuses in the coating during the PEB process, the acid concentration near the surface of the coating and inside the coating is more uniform than when the quinonediazide compound (C) is used as the radiation-sensitive compound. . Therefore, it is considered that the surface of the film in the exposed portion is difficult to dissolve during development, resulting in a decrease in sensitivity. Moreover, the photo-acid generator may have low thermal stability, and the use of such a photo-acid generator may accelerate the dissolution of the unexposed areas, resulting in deterioration of the pattern formability.
- the hydrophobic resin (A) is not particularly limited, but examples include acrylic resins, polystyrene resins, epoxy resins, polyamide resins, phenol resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polybenzoxazole resin precursors, and silicone resins. , cyclic olefin polymers, cardo resins, and derivatives of these resins. Derivatives of these resins preferably have hydrophobic groups. Hydrophobic groups include, for example, silicon-containing groups and fluorine-containing groups.
- hydrophobic resin (A) a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group is used as a base resin, and part or all of the alkali-soluble functional group is a group having the above-mentioned hydrophobic group. Transformed resins can also be used. Hydrophobic resin (A) can be used individually or in combination of 2 or more types.
- the hydrophobic resin (A) is a resin having at least one selected from the group consisting of silicon-containing groups and fluorine-containing groups.
- the silicon-containing groups and fluorine-containing groups may constitute the main chain of the hydrophobic resin (A) or may be pendant groups.
- Silicon-containing groups include, for example, a silyl group substituted with an aliphatic hydrocarbon group or an aryl group, a group having a cyclic siloxane structure, and a group having a silsesquioxane structure.
- a silyl group substituted with an aliphatic hydrocarbon group or an aryl group is mono-, di- or tri-substituted.
- the substituents of the silyl group substituted with an aliphatic hydrocarbon group or an aryl group may be the same or different.
- a silyl group substituted with an aliphatic hydrocarbon group or an aryl group is preferably trisubstituted.
- a silyl group substituted with an aliphatic hydrocarbon group or an aryl group may further have a substituent other than an alkyl group or an aryl group, such as a silyloxy group substituted with an aliphatic hydrocarbon group or an aryl group.
- the number of ring members of the cyclic siloxane moiety of the group having a cyclic siloxane structure is preferably 6-14. Some or all of the hydrogen atoms on the silicon atoms of the group having a cyclic siloxane structure may each independently be substituted with an aliphatic hydrocarbon group or an aryl group.
- a part or all of the hydrogen atoms on the silicon atoms of the group having a silsesquioxane structure may be independently substituted with an aliphatic hydrocarbon group or an aryl group.
- Aliphatic hydrocarbon groups or aliphatic hydrocarbon groups of silyl groups substituted with aryl groups, aliphatic hydrocarbon groups as substituents of groups having a cyclic siloxane structure, and substituents of groups having a silsesquioxane structure and the aliphatic hydrocarbon group as a substituent of the silyloxy group substituted with an aliphatic hydrocarbon group or an aryl group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms. , and more preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
- Examples of aliphatic hydrocarbon groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.
- saturated hydrocarbon group unsaturated hydrocarbon group such as ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl saturated monocyclic hydrocarbon groups such as cyclododecyl group; unsaturated monocyclic hydrocarbon groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group and cyclodecenyl group; bicyclo [2.2.
- the aryl group as a substituent of the silyloxy group substituted with a group hydrocarbon group or an aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms.
- Aryl groups having 6 to 20 carbon atoms include, for example, phenyl, naphthyl, fluorenyl, anthryl, and phenanthrenyl groups.
- silyl groups substituted with aliphatic hydrocarbon groups or aryl groups include trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, diphenylmethylsilyl, triphenylsilyl, and trimethylsilyl.
- An oxydimethylsilyl group is mentioned.
- Groups having a cyclic siloxane structure include, for example, a pentamethylcyclotrisilyloxy group, a heptamethylcyclotetrasilyloxy group, and a nonamethylcyclopentasilyloxy group.
- Groups having a silsesquioxane structure include, for example, a silsesquioxanyl group, a heptamethylsilsesquioxanyl group, a heptaethylsilsesquioxanyl group, a hepta(n-propyl)silsesquioxanyl group, and a hepta ( and n-butyl)silsesquioxanyl groups.
- fluorine-containing groups include fluorine-substituted alkyl groups, fluorine-substituted aryl groups, and fluoroacryloyl groups.
- the fluorine-substituted alkyl group may be a perfluoroalkyl group or a partially fluorinated alkyl group.
- the substituents of the fluorine-substituted alkyl group may be the same or different from each other.
- a fluorine-substituted alkyl group may further have a substituent other than a fluorine atom, such as a hydroxy group.
- the fluorine-substituted alkyl group is preferably a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group having 1 to 20 carbon atoms, more preferably a perfluoroalkyl group having 1 to 8 carbon atoms or It is a partially fluorinated alkyl group having 1 to 8 carbon atoms.
- perfluoroalkyl groups having 1 to 20 carbon atoms and partially fluorinated alkyl groups having 1 to 20 carbon atoms include trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, pentafluoropropyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro(2-methyl)isopropyl group, heptafluorobutyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluoro-tert-butyl group, perfluoroiso linear or branched fluorine-substituted alkyl groups such as pentyl group, nonafluorohexyl group, perfluoro(trimethyl)hexyl group, perfluorooctyl group, 2-perfluorohexylethyl group;
- fluorine-substituted alkyl groups having a hydroxy group as a substituent include -CH(CF 3 )OH, -C(CF 3 ) 2 OH, -C(CF 3 )(CH 3 )OH, and -C(C 2 F 5 ) 2 OH, with —C(CF 3 ) 2 OH being preferred.
- the fluorine-substituted aryl group may be a perfluoroaryl group or a partially fluorinated aryl group.
- the substituents of the fluorine-substituted aryl group may be the same or different from each other.
- a fluorine-substituted aryl group may further have a substituent other than a fluorine atom, such as a hydroxy group.
- the fluorine-substituted aryl group is preferably a perfluoroaryl group having 6 to 20 carbon atoms or a partially fluorinated aryl group having 6 to 20 carbon atoms.
- perfluoroaryl groups having 6 to 20 carbon atoms and partially fluorinated aryl groups having 6 to 20 carbon atoms include p-fluorophenyl group, pentafluorophenyl group, and 3,5-di(trifluoromethyl ) phenyl group.
- a fluorine-substituted aryl group is preferably a pentafluorophenyl group.
- the hydrophobic resin (A) is obtained by reacting a resin having functional groups such as hydroxy, carboxy, amino, and epoxy groups with a compound having a hydrophobic group to convert the functional group into a group containing a hydrophobic group. It can also be manufactured by
- the hydrophobic resin (A) is a copolymer of a polymerizable monomer having a hydrophobic group and another polymerizable monomer.
- Polymerizable monomers having a hydrophobic group include, for example, polymerizable monomers having a silicon-containing group and polymerizable monomers having a fluorine-containing group.
- Examples of the polymerizable monomer having a silicon-containing group include trimethylvinylsilane, trimethylallylsilane, trimethyl(3-butenyl)silane, tert-butyldimethylvinylsilane, (trimethylsilyloxy)dimethylvinylsilane, (trimethylsilyloxy)dimethylallylsilane, triethyl vinylsilane, triethylallylsilane, triethyl(3-butenyl)silane, (trimethylsilyl)methyl (meth)acrylate, 2-(trimethylsilyl)ethyl (meth)acrylate, 3-(trimethylsilyl)propyl (meth)acrylate, t-butyldimethylsilyl ( meth)acrylate, triisopropylsilylmethyl (meth)acrylate, bis(trimethylsilylmethyl)methyl (meth)acrylate, 4-(trimethylsilyl)cyclohe
- Examples of the polymerizable monomer having a fluorine-containing group include 2-perfluorohexylethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoro Propyl (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoropropyl) (meth)acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) Acrylate, 3,3,4,4,5,5,6,6,6-nonafluorohexyl (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoro-2-methylpropyl ) (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoro-2-phenylpropyl) (meth)acrylate, pentafluorophenyl (meth)acrylate, 3,5-bis(trifluoro methyl)phenyl (meth)acrylate, per
- polymerizable monomers include, for example, styrene; styrene derivatives such as ⁇ -methylstyrene, p-methylstyrene and p-ethylstyrene; acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert- Butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate,
- the other polymerizable monomer may be a polymerizable monomer having an alkali-soluble functional group.
- the polymerizable monomer having an alkali-soluble functional group include maleic acid derivatives such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; (meth)acrylic acid, ⁇ -bromo(meth)acrylic acid, ⁇ - (meth)acrylic acid derivatives such as chloro (meth)acrylic acid, ⁇ -furyl (meth)acrylic acid, ⁇ -styryl (meth)acrylic acid; maleic acid, fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, Unsaturated carboxylic acid compounds such as itaconic acid, crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, 6-maleimidohexanoic acid; 4-hydroxystyrene, 4-hydroxyphen
- R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R 2 is represented by SiR 3 R 4 R 5
- R 3 , R 4 and R 5 are each independently is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms
- r is an integer of 0 to 5
- s is an integer of 0 to 5
- r + s is an integer of 1 to 5 is an integer
- R 1 is preferably a hydrogen atom or a methyl group.
- R 3 , R 4 and R 5 are each independently methyl, ethyl, isopropyl, tert-butyl or phenyl.
- r is preferably an integer of 0 to 3, more preferably 0.
- s is preferably an integer of 1 to 3, more preferably 1.
- 4-triethylsilyloxyphenyl methacrylate and 4-tert-butyldimethylsilyloxyphenyl methacrylate are particularly preferred as such polymerizable monomers having a hydrophobic group.
- formula (2) after polymerization (In Formula (2), R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 8 is a hydrogen atom or a linear at least one selected from the group consisting of an alkyl group, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms; It is a phenyl group substituted with.) is preferred.
- R 6 and R 7 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
- R 8 is at least one selected from the group consisting of a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms; A phenyl group substituted with a species is preferable, and a cyclic alkyl group having 3 to 12 carbon atoms or a phenyl group is more preferable. Phenylmaleimide and N-cyclohexylmaleimide are particularly preferred as such other polymerizable monomers.
- R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.
- R9 is preferably a hydrogen atom or a methyl group.
- a is preferably an integer of 1 to 3, more preferably 1; 4-Hydroxyphenyl methacrylate is particularly preferred as another polymerizable monomer having such an alkali-soluble functional group.
- the hydrophobic resin (A) has formula (1) (In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 is represented by SiR 3 R 4 R 5 , and R 3 , R 4 and R 5 are each independently is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 5, s is an integer of 0 to 5, provided that r + s is an integer of 1 to 5 is an integer) and at least one structural unit represented by formula (1) in which s is an integer of 1 or more.
- R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- R 2 is represented by SiR 3 R 4 R 5
- R 3 , R 4 and R 5 are each independently is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms
- r is an integer of 0 to 5
- s is an integer
- the hydrophobic resin (A) has formula (2) (In Formula (2), R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 8 is a hydrogen atom or a linear at least one selected from the group consisting of an alkyl group, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms; It is a phenyl group substituted with.).
- the hydrophobic resin (A) has formula (3) (In Formula (3), R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.).
- a structural unit represented by formula (1) wherein s is an integer of 1 or more, a structural unit represented by formula (2), and a structural unit represented by formula (3)
- 4-triethylsilyloxyphenyl methacrylate or 4-tert-butyldimethylsilyloxyphenyl methacrylate is used as the polymerizable monomer having a hydrophobic group, and phenylmaleimide or N-cyclohexylmaleimide is used as the other polymerizable monomer. , 4-hydroxyphenyl methacrylate is particularly preferably used.
- Polymerization initiators for producing the hydrophobic resin (A) by radical polymerization include, but are not limited to, 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyro nitrile), dimethyl 2,2′-azobis(2-methylpropionate), 4,4′-azobis(4-cyanovaleric acid), 2,2′-azobis(2,4-dimethylvaleronitrile) (AVN ) and other azo polymerization initiators; dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1, A peroxide polymerization initiator having a 10-hour half-life temperature of 100 to 170° C.
- the amount of the polymerization initiator used is generally 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more and 40 parts by mass or less, or 20 parts by mass or more with respect to a total of 100 parts by mass of the polymerizable monomers. It is preferably 15 parts by mass or less or 15 parts by mass or less.
- a RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with the polymerization initiator.
- Thiocarbonylthio compounds such as, but not limited to, dithioesters, dithiocarbamates, trithiocarbonates, and xanthates can be used as RAFT agents.
- the RAFT agent can be used in the range of 0.005 to 20 parts by weight, preferably in the range of 0.01 to 10 parts by weight, per 100 parts by weight of the total polymerizable monomers.
- the silicon atom content is preferably 1% by mass to 10% by mass, more preferably 3% by mass or more, based on the mass of the hydrophobic resin (A). 8% by mass.
- the hydrophobic resin (A) having a silicon-containing group preferably contains structural units having a silicon-containing group in an amount of 3 mol% to 60 mol%, more preferably 5 mol% to 50 mol%, based on the total structural units of the hydrophobic resin (A). % amount.
- the content of fluorine atoms is preferably 1% by mass to 35% by mass, more preferably 5% by mass or more, based on the mass of the hydrophobic resin (A). 30% by mass.
- the hydrophobic resin (A) having a fluorine-containing group preferably contains structural units having a fluorine-containing group in an amount of 5 mol% to 55 mol%, more preferably 6 mol% to 50 mol%, based on the total structural units of the hydrophobic resin (A). % amount.
- the hydrophobic resin (A) may or may not have an alkali-soluble functional group.
- the hydrophobic resin (A) preferably contains 20 mol% to 90 mol%, more preferably 30 mol% to 85 mol%, more preferably 30 mol% to 85 mol% of structural units having an alkali-soluble functional group, based on the total structural units of the hydrophobic resin (A). is contained in an amount of 40 mol % to 80 mol %. In one embodiment, the hydrophobic resin (A) does not have alkali-soluble functional groups.
- the weight average molecular weight (Mw) of the hydrophobic resin (A) is preferably 3,000 to 80,000, more preferably 4,000 to 70,000, still more preferably 5,000 to 60,000.
- the number average molecular weight (Mn) of the hydrophobic resin (A) is preferably 1,000 to 30,000, more preferably 1,500 to 25,000, still more preferably 2,000 to 20,000.
- the polydispersity (Mw/Mn) of the hydrophobic resin (A) is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, still more preferably 1.2 to 2.8. .
- the positive photosensitive resin composition contains a hydrophobic resin (A) of 3% by mass to 50% by mass, preferably 4% by mass to 40% by mass, more preferably 4% by mass to 40% by mass, based on the solid content of 100% by mass. contains 5% by mass to 30% by mass. If the content of the hydrophobic resin (A) is 3% by mass or more based on the solid content of 100% by mass, the uneven distribution of the hydrophobic resin (A) on the coating surface due to the fluorosurfactant (D) is prevented. As a result, the concentration of the hydrophobic resin (A) becomes high on the surface of the film, and the surface of the film becomes poorly soluble in an alkaline aqueous solution, so that high sensitivity can be achieved.
- a hydrophobic resin (A) of 3% by mass to 50% by mass, preferably 4% by mass to 40% by mass, more preferably 4% by mass to 40% by mass, based on the solid content of 100% by mass. contains 5% by mass to 30% by mass.
- the content of the hydrophobic resin (A) is 50% by mass or less based on the solid content of 100% by mass, the carboxylic acid compound derived from the quinonediazide compound in the exposed area, other highly alkali-soluble resin components, and any Since the dissolution of the coating surface progresses rapidly with the dissolution of the dissolution accelerator, high sensitivity can be achieved.
- the hydrophobic resin (A) is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, still more preferably 15% by mass, based on the total mass of the resin components. Contains from mass % to 40 mass %. If the content of the hydrophobic resin (A) is 5% by mass or more based on the total mass of the resin components, the uneven distribution of the hydrophobic resin (A) on the coating surface due to the fluorosurfactant (D) can be prevented. As a result, the concentration of the hydrophobic resin (A) becomes high on the surface of the film, and the surface of the film becomes poorly soluble in an alkaline aqueous solution, so that high sensitivity can be achieved.
- the content of the hydrophobic resin (A) is 60% by mass or less based on the total mass of the resin components, the carboxylic acid compound derived from the quinonediazide compound in the exposed area, other highly alkali-soluble resin components, and any Since the dissolution of the coating surface progresses rapidly with the dissolution of the dissolution accelerator, high sensitivity can be achieved.
- Alkali-soluble resin (B) is not particularly limited, it is preferably a resin having an alkali-soluble functional group.
- Alkali-soluble functional groups include, but are not limited to, phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphoric acid groups, acid anhydride groups, and mercapto groups.
- An alkali-soluble resin (B) having two or more types of alkali-soluble functional groups may be used.
- the alkali-soluble resin (B) may have an alkali-soluble functional group protected with an acid-decomposable group.
- alkali-soluble resin (B) examples include homopolymers or copolymers of polymerizable monomers having alkali-soluble functional groups, and resins having epoxy groups and phenolic hydroxyl groups.
- Other alkali-soluble resins (B) include, for example, acrylic resins, polystyrene resins, epoxy resins, polyamide resins, phenol resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, and polybenzoxazoles having alkali-soluble functional groups. Included are resin precursors, silicone resins, cyclic olefin polymers, cardo resins, and derivatives of these resins.
- a derivative of a phenol resin is a polyalkenylphenol resin in which an alkenyl group is bonded to a benzene ring
- a derivative of a polystyrene resin is a hydroxypolystyrene resin derivative in which a phenolic hydroxyl group and a hydroxyalkyl group or an alkoxy group are bonded to a benzene ring.
- Alkali-soluble resin (B) can be used individually or in combination of 2 or more types.
- the alkali-soluble resin (B) may have a radically polymerizable functional group.
- the alkali-soluble resin (B) has a (meth)acryloyloxy group, allyl group or methallyl group as a radically polymerizable functional group.
- the positive photosensitive resin composition contains 5% by mass to 80% by mass, preferably 10% by mass to 75% by mass, more preferably 10% by mass to 75% by mass of the alkali-soluble resin (B) based on the solid content of 100% by mass. Contains 15% by mass to 70% by mass. If the content of the alkali-soluble resin (B) is 5% by mass or more based on the solid content of 100% by mass, the dissolution of the exposed area can be promoted to achieve high sensitivity, and the coating after heat curing can be improved. Stability and durability can be ensured. If the content of the alkali-soluble resin (B) is 80% by mass or less based on 100% by mass of the solid content, the solubility of the unexposed areas can be kept low and the residual film rate can be kept high.
- the alkali-soluble resin (B) is preferably 40% to 95% by mass, more preferably 50% to 90% by mass, still more preferably 60% by mass, based on the total mass of the resin components. Contains from mass % to 85 mass %. If the content of the alkali-soluble resin (B) is 40% by mass or more based on the total mass of the resin components, desired alkali solubility can be obtained. If the content of the alkali-soluble resin (B) is 95% by mass or less based on the total mass of the resin components, a highly sensitive positive photosensitive resin composition can be obtained.
- the alkali-soluble resin (B) is a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer, a resin having an epoxy group and a phenolic hydroxyl group, or including combinations of
- an alkali-soluble functional group possessed by a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer hereinafter also simply referred to as "a copolymer having an alkali-soluble functional group"
- a copolymer having an alkali-soluble functional group for example, phenolic hydroxyl groups, carboxy groups, sulfo groups, phosphate groups, acid anhydride groups, and mercapto groups.
- a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer may have two or more types of alkali-soluble functional groups.
- the copolymer having an alkali-soluble functional group has one or more selected from the group consisting of an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure. It is preferred to have a cyclic structure of
- a copolymer having an alkali-soluble functional group can be produced, for example, by radically polymerizing a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer. After synthesizing a copolymer by radical polymerization, an alkali-soluble functional group may be added to the copolymer.
- Examples of the polymerizable monomer having an alkali-soluble functional group include maleic acid derivatives such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; (meth)acrylic acid, ⁇ -bromo(meth)acrylic acid, ⁇ - (meth)acrylic acid derivatives such as chloro (meth)acrylic acid, ⁇ -furyl (meth)acrylic acid, ⁇ -styryl (meth)acrylic acid; maleic acid, fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, Unsaturated carboxylic acid compounds such as itaconic acid, crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, 6-maleimidohexanoic acid; 4-hydroxystyrene, 4-hydroxyphenyl (meth)acrylate, 3,5 -Polymerizable monomers having a phenolic hydroxyl
- the polymerizable monomer having an alkali-soluble functional group is preferably a (meth)acrylic acid derivative or a polymerizable monomer having a phenolic hydroxyl group, and a polymerizable monomer having a phenolic hydroxyl group. Body is more preferred.
- polymerizable monomers include, for example, styrene derivatives such as styrene, vinyl toluene, ⁇ -methylstyrene, p-methylstyrene and p-ethylstyrene; acrylamide; acrylonitrile; vinyl alcohols such as vinyl-n-butyl ether.
- Ether compounds methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate , tert-butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, (Meth)acrylic acid esters such as isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate and dicyclopentanyl (meth)acrylate; and N-substituted male
- R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.
- R9 is preferably a hydrogen atom or a methyl group.
- a is preferably an integer of 1 to 3, more preferably 1; 4-Hydroxyphenyl methacrylate is particularly preferred as such a polymerizable monomer having an alkali-soluble functional group.
- formula (2) after polymerization (In Formula (2), R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 8 is a hydrogen atom or a linear at least one selected from the group consisting of an alkyl group, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms; It is a phenyl group substituted with.) is preferred.
- R 6 and R 7 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
- R 8 is at least one selected from the group consisting of a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms; A phenyl group substituted with a species is preferable, and a cyclic alkyl group having 3 to 12 carbon atoms or a phenyl group is more preferable. Phenylmaleimide and N-cyclohexylmaleimide are particularly preferred as such other polymerizable monomers.
- the copolymer with alkali-soluble functional groups has formula (3) (In formula (3), R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.), and a structural unit represented by formula (2) (In Formula (2), R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 8 is a hydrogen atom or a linear at least one selected from the group consisting of an alkyl group, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms; is a phenyl group substituted with ).
- the polymerization initiator used in producing the hydrophobic resin (A) by radical polymerization was described. That's right.
- the type and amount of the RAFT agent that can be used together with the polymerization initiator are also as described for the RAFT agent used when producing the hydrophobic resin (A) by radical polymerization.
- the weight average molecular weight (Mw) of the copolymer having an alkali-soluble functional group is preferably 3,000 to 80,000, more preferably 4,000 to 70,000, still more preferably 5,000 to 60,000.
- the copolymer having an alkali-soluble functional group has a number average molecular weight (Mn) of preferably 1,000 to 30,000, more preferably 1,500 to 25,000, still more preferably 2,000 to 20,000.
- Polydispersity (Mw/Mn) of the copolymer having an alkali-soluble functional group is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, still more preferably 1.2 to 2.0. 8.
- a positive photosensitive resin composition excellent in coatability, pattern formability and alkali developability by adjusting the weight average molecular weight, number average molecular weight and polydispersity of the copolymer having an alkali-soluble functional group to the above ranges. can be obtained.
- the alkali-soluble functional group of the copolymer having an alkali-soluble functional group is a phenolic hydroxyl group
- the phenolic hydroxyl group equivalent of the copolymer having an alkali-soluble functional group is preferably 60 to 400, more preferably 80. ⁇ 350, more preferably 100-300.
- the thickness of the unexposed portion can be sufficiently maintained during alkali development. If the phenolic hydroxyl group equivalent of the copolymer having an alkali-soluble functional group is 400 or less, desired alkali solubility can be obtained.
- a copolymer having an alkali-soluble functional group corresponds to a resin having an epoxy group and a phenolic hydroxyl group, which will be described later, it is treated as a copolymer having an alkali-soluble functional group. That is, resins having epoxy groups and phenolic hydroxyl groups do not include copolymers having alkali-soluble functional groups.
- a resin having an epoxy group and a phenolic hydroxyl group is an alkaline aqueous solution-soluble resin.
- a resin having an epoxy group and a phenolic hydroxyl group may have an alkali-soluble functional group other than the phenolic hydroxyl group.
- a resin having an epoxy group and a phenolic hydroxyl group is, for example, a compound having at least two epoxy groups in one molecule (hereinafter sometimes referred to as an "epoxy compound”), a part of the epoxy group and a hydroxyl It can be obtained by reacting the carboxy group of a benzoic acid compound.
- Epoxy groups of resins containing epoxy groups and phenolic hydroxyl groups form crosslinks by reacting with phenolic hydroxyl groups during heat treatment (post-baking) after development, thereby improving the chemical resistance and heat resistance of the film. be able to. Since the phenolic hydroxyl group contributes to the solubility in an alkaline aqueous solution during development, a resin having an epoxy group and a phenolic hydroxyl group also functions as a dissolution accelerator for other resins when exposed at a low exposure dose.
- the photosensitive resin composition can be made highly sensitive.
- Reaction formula 1 shows an example of the reaction in which one of the epoxy groups of the epoxy compound reacts with the carboxyl group of the hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group.
- Compounds having at least two epoxy groups in one molecule include, for example, novolac epoxy resins such as phenol novolak epoxy resins and cresol novolac epoxy resins, bisphenol epoxy resins, biphenol epoxy resins, and naphthalene skeleton-containing epoxy resins. Mention may be made of resins, cycloaliphatic epoxy resins, and heterocyclic epoxy resins. These epoxy compounds may have two or more epoxy groups in one molecule, and may be used alone or in combination of two or more. Since these compounds are thermosetting compounds, it is common knowledge for those skilled in the art that their structures cannot be uniquely described due to differences in the presence or absence of epoxy groups, types of functional groups, degrees of polymerization, and the like.
- R 10 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and m is an integer of 1-50.
- phenolic novolak-type epoxy resins examples include EPICLON (registered trademark) N-770 (DIC Corporation) and jER (registered trademark)-152 (Mitsubishi Chemical Corporation).
- cresol novolac epoxy resins examples include EPICLON (registered trademark) N-695 (DIC Corporation) and EOCN (registered trademark)-102S (Nippon Kayaku Co., Ltd.).
- bisphenol-type epoxy resins include bisphenol A-type epoxies such as jER (registered trademark) 828, jER (registered trademark) 1001 (Mitsubishi Chemical Corporation), and YD-128 (trade name, Nippon Steel Chemical & Materials Co., Ltd.).
- Biphenol-type epoxy resins include, for example, jER (registered trademark) YX-4000 and jER (registered trademark) YL-6121H (Mitsubishi Chemical Corporation).
- naphthalene skeleton-containing epoxy resins include NC-7000 (trade name, Nippon Kayaku Co., Ltd.) and EXA-4750 (trade name, DIC Corporation).
- Alicyclic epoxy resins include, for example, EHPE (registered trademark)-3150 (Daicel Chemical Industries, Ltd.). Heterocyclic epoxy resins include, for example, TEPIC®, TEPIC-L, TEPIC-H, and TEPIC-S (Nissan Chemical Industries, Ltd.).
- the compound having at least two epoxy groups in one molecule is preferably a novolak type epoxy resin, more preferably at least one selected from the group consisting of phenol novolak type epoxy resins and cresol novolak type epoxy resins.
- it is a cresol novolac type epoxy resin.
- a positive photosensitive resin composition containing a novolak-type epoxy resin, particularly a resin having an epoxy group and a phenolic hydroxyl group derived from a cresol novolak-type epoxy resin has excellent pattern formability and is easy to control in alkali solubility. There is little outgassing.
- a hydroxybenzoic acid compound is a compound in which at least one of the 2-6 positions of benzoic acid is substituted with a hydroxyl group, and examples thereof include salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, and 2,4-dihydroxybenzoic acid. acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy-4- Examples include nitrobenzoic acid and 4-hydroxy-3-nitrobenzoic acid, and dihydroxybenzoic acid compounds are preferred from the viewpoint of enhancing alkali developability.
- a hydroxybenzoic acid compound can be used individually or in combination of 2 or more types.
- the resin having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, represented by formula (5) (In the formula (5), b is an integer of 1 to 5, and * represents the bonding portion of the compound having at least two epoxy groups in one molecule with the residue excluding the epoxy group involved in the reaction. ).
- a resin having an epoxy group and a phenolic hydroxyl group from an epoxy compound and a hydroxybenzoic acid compound it is possible to use 0.2 to 0.95 equivalents of the hydroxybenzoic acid compound with respect to 1 equivalent of the epoxy group of the epoxy compound. preferably 0.3 to 0.9 equivalents, more preferably 0.4 to 0.8 equivalents.
- the amount of the hydroxybenzoic acid compound is 0.2 equivalents or more, sufficient alkali solubility can be obtained, and when the amount is 0.95 equivalents or less, an increase in molecular weight due to side reactions can be suppressed.
- a catalyst may be used to promote the reaction between the epoxy compound and the hydroxybenzoic acid compound.
- the amount of the catalyst used can be 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture comprising the epoxy compound and the hydroxybenzoic acid compound.
- the reaction temperature can be 60-150° C., and the reaction time can be 3-30 hours.
- Catalysts used in this reaction include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, and zirconium octanoate.
- the number average molecular weight (Mn) of the resin having epoxy groups and phenolic hydroxyl groups is preferably 500-8000, more preferably 800-6000, still more preferably 1000-5000.
- the weight average molecular weight (Mw) of the resin having epoxy groups and phenolic hydroxyl groups is preferably 500 to 30,000, more preferably 2,000 to 25,000, still more preferably 3,000 to 20,000.
- the alkali development rate is appropriate and the dissolution rate difference between the exposed and unexposed areas is sufficient, resulting in good pattern resolution.
- the number average molecular weight is 8,000 or less, or the weight average molecular weight is 30,000 or less, the coatability and alkali developability are good.
- the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 300-7000, preferably 400-6000, more preferably 500-5000. If the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 300 or more, sufficient alkali solubility can be imparted to the resin having an epoxy group and a phenolic hydroxyl group. If the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 7000 or less, the strength and heat resistance of the cured film can be enhanced. Epoxy equivalent is determined by JIS K 7236:2009.
- the hydroxyl equivalent weight of the resin having an epoxy group and a phenolic hydroxyl group is 160-500, preferably 170-400, more preferably 180-300. If the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 160 or more, the strength and heat resistance of the cured film can be enhanced. If the hydroxyl equivalent of the resin having epoxy groups and phenolic hydroxyl groups is 500 or less, sufficient alkali solubility can be imparted to the resin having epoxy groups and phenolic hydroxyl groups. The hydroxyl equivalent is determined according to JIS K 0070:1992.
- the alkali-soluble resin (B) may contain a resin having an alkali-soluble functional group protected with an acid-decomposable group (hereinafter also simply referred to as "protected resin").
- the protective resin is not particularly limited as long as it has a plurality of alkali-soluble functional groups and at least part of the plurality of alkali-soluble functional groups are protected with an acid-decomposable group.
- Examples of protective resins include resins in which at least part of the alkali-soluble functional groups are protected with an acid-decomposable group, using the above-described alkali-soluble resin having a plurality of alkali-soluble functional groups as a base resin.
- Alkali-soluble functional groups include, for example, phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphoric acid groups, acid anhydride groups, and mercapto groups.
- the alkali-soluble functional group is preferably a phenolic hydroxyl group or a carboxyl group, more preferably a phenolic hydroxyl group.
- Post-exposure baking is optionally performed in the presence of an acid generated during exposure to promote decomposition (deprotection) of the acid-decomposable groups and regenerate the alkali-soluble functional groups. This promotes alkali dissolution of the protective resin in the exposed areas during development.
- Protective resin can be used individually or in combination of 2 or more types.
- the protective resin may be a combination of two or more resins differing in the structural units of polymers or copolymers, acid-decomposable groups, protection ratios of alkali-soluble functional groups, or combinations thereof.
- the protective resin can be obtained by protecting some of the alkali-soluble functional groups of a base resin having multiple alkali-soluble functional groups with acid-decomposable groups.
- a protective resin having a phenolic hydroxyl group protected with an acid-decomposable group has a partial structure of Ar—O—R 11 , where Ar is an aromatic ring derived from phenol. and R 11 represents an acid-decomposable group.
- the acid-decomposable group is a group that is decomposed (deprotected) by heating in the presence of an acid, if necessary, to generate an alkali-soluble functional group.
- an acid if necessary, to generate an alkali-soluble functional group.
- tert-butyl group 1,1-dimethyl-propyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-methyladamantyl group , 1-ethyladamantyl group, tert-butoxycarbonyl group, group having a tertiary alkyl group such as 1,1-dimethyl-propoxycarbonyl group; and formula (6) —CR 12 R 13 —OR 14 (6) (In formula (6), R 12 and R 13 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl
- the alkali-soluble functional group is a phenolic hydroxyl group
- the group represented by formula (6) forms an acetal structure or ketal structure together with an oxygen atom derived from the alkali-soluble functional group.
- the acid-decomposable group is preferably a group represented by formula (6), since a highly sensitive photosensitive resin composition can be obtained even with a low exposure dose.
- R 12 and R 13 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R 14 is selected from chlorine, bromine and iodine.
- a linear alkyl group having 1 to 12 carbon atoms a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, which may be substituted with a halogen atom selected from the group consisting of It is more preferable to have Examples of such acid-decomposable groups include 1-alkoxyalkyl groups.
- 1-alkoxyalkyl groups include, for example, methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1 -(2-chloroethoxy)ethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-cyclohexyloxyethyl group, and 1-(2-cyclohexylethoxy)ethyl group; - n-propoxyethyl groups are preferred.
- the acid-decomposable group a group represented by formula (6) in which one of R 12 or R 13 and R 14 are bonded to form a ring structure having 3 to 10 ring members is also preferably used. can do.
- R 12 or R 13 that does not participate in the formation of the ring structure is preferably a hydrogen atom.
- acid-decomposable groups include a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group, with a 2-tetrahydrofuranyl group being preferred.
- the protective reaction of the alkali-soluble functional group can be carried out under known conditions using a general protective agent.
- the protective resin can be obtained by reacting the base resin of the protective resin and the protective agent in no solvent or in a solvent such as toluene or hexane in the presence of an acid or base at a reaction temperature of -20 to 50°C. can.
- a known protective agent capable of protecting an alkali-soluble functional group can be used.
- protective agents that can be used include isobutene when the acid-decomposable group is a tert-butyl group and di-tert-butyl dicarbonate when the acid-decomposable group is a tert-butoxycarbonyl group.
- Chloromethyl methyl ether when the acid-decomposable group is a methoxymethyl group
- 2-tetrahydrofuranyl group when it is a 2-tetrahydrofuranyl group.
- 2,3-dihydrofuran and 2-tetrahydropyranyl groups 3,4-dihydro-2H-pyran and the like can be used.
- acids examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid.
- organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid.
- Salts of organic acids such as the pyridinium salt of p-toluenesulfonic acid, can also be used as acid sources.
- the base examples include inorganic hydroxides such as sodium hydroxide and potassium hydroxide; inorganic carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and cesium carbonate; metal hydrides such as sodium hydride; Amine compounds such as N,N-dimethyl-4-aminopyridine, imidazole, triethylamine and diisopropylethylamine are included.
- inorganic hydroxides such as sodium hydroxide and potassium hydroxide
- inorganic carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and cesium carbonate
- metal hydrides such as sodium hydride
- Amine compounds such as N,N-dimethyl-4-aminopyridine, imidazole, triethylamine and diisopropylethylamine are included.
- the polymerizable monomer having an alkali-soluble functional group protected with an acid-decomposable group can also be obtained by polymerizing or copolymerizing the polymer and optionally other polymerizable monomers. Protection of the alkali-soluble functional group of the polymerizable monomer having an alkali-soluble functional group can be carried out in the same manner as protection of the alkali-soluble functional group of the base resin.
- the protective resin is represented by formula (7) (In formula (7), R 15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 16 is an acid-decomposable group, p is an integer of 0 to 5, q is 0 to 5 where p + q is an integer of 1 to 5.) and has at least one structural unit represented by formula (7), wherein q is an integer of 1 or more is preferred.
- the acid-labile group for R 16 is represented by formula (6) —CR 12 R 13 —OR 14 (6) (In formula (6), R 12 , R 13 and R 14 are as defined above.) is preferred.
- R 12 and R 13 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms
- R 14 is a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a branched alkyl group having 3 to 12 carbon atoms, which may be substituted with a halogen atom selected from the group consisting of chlorine, bromine and iodine; 12 cyclic alkyl groups are more preferred.
- acid-decomposable groups include 1-alkoxyalkyl groups.
- 1-alkoxyalkyl groups include, for example, methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1 -(2-chloroethoxy)ethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-cyclohexyloxyethyl group, and 1-(2-cyclohexylethoxy)ethyl group; - n-propoxyethyl groups are preferred.
- Examples of the acid-decomposable group in which one of R 12 or R 13 and R 14 are bonded to form a ring structure having 3 to 10 ring members include 2-tetrahydrofuranyl group and 2-tetrahydropyranyl group. and the 2-tetrahydrofuranyl group is preferred.
- the protective resin is represented by the formula (2) (In Formula (2), R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 8 is a hydrogen atom or a linear at least one selected from the group consisting of an alkyl group, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms; It is a phenyl group substituted with.).
- R 6 and R 7 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
- R 8 is at least one selected from the group consisting of a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms; A phenyl group substituted with a species is preferable, and a cyclic alkyl group having 3 to 12 carbon atoms or a phenyl group is more preferable.
- a structural unit represented by formula (7) and q is an integer of 1 or more, i.e., represented by formula (7) in which at least one alkali-soluble functional group is protected with an acid-decomposable group is 5% to 95%, preferably 15% to 90%, more preferably 25% to 85% of the total number of structural units in the protective resin.
- the positive photosensitive resin composition contains 0.5% to 50% by mass, preferably 1% to 40% by mass, more preferably 2% by mass of the protective resin based on 100% by mass of solid content. Contains from mass % to 30 mass %. If the content of the protective resin is 0.5% by mass or more based on the solid content of 100% by mass, the dissolution of the exposed area can be promoted and the solubility of the unexposed area and the exposed area can be differentiated. , high sensitivity can be achieved, and the stability and durability of the film after thermosetting can be ensured.
- the content of the protective resin is 50% by mass or less based on 100% by mass of the solid content, the residual amount of unreacted acid-decomposable groups is reduced, the solubility of the exposed area is increased, and high sensitivity is achieved. be able to.
- quinonediazide compound (C) produces an alkali-soluble carboxylic acid compound through the reaction shown in Reaction Formula 2 below when irradiated with radiation such as visible light, ultraviolet light, ⁇ -rays, and electron beams.
- the quinonediazide compound (C) interacts (e.g., forms hydrogen bonds) with an alkali-soluble functional group, such as a phenolic hydroxyl group, of the alkali-soluble resin (B) before exposure to light, and converts the alkali-soluble resin (B) into an alkaline aqueous solution.
- an alkali-soluble functional group such as a phenolic hydroxyl group
- the presence of the alkali-soluble carboxylic acid compound in the irradiated portion makes it easier for the resin in that portion to dissolve in the alkaline aqueous solution together with the carboxylic acid compound.
- the produced carboxylic acid compound accelerates the decomposition of the acid-decomposable group of the protective resin optionally contained in the positive photosensitive resin composition, regenerates the alkali-soluble functional group, and improves the alkali-soluble property of the protective resin.
- the carboxylic acid compound has a relatively larger molecular structure than acids generated from photoacid generators commonly used in chemically amplified resists, such as p-toluenesulfonic acid and 1-propanesulfonic acid, and diffuses in the film. hard to do.
- a quinonediazide compound (C) can be used individually or in combination of 2 or more types.
- the positive photosensitive resin composition preferably does not substantially contain a photoacid generator generally used in chemically amplified resists, and contains only the quinonediazide compound (C) as a photosensitive agent without containing the photoacid generator. It is more preferable to include "Substantially free of photoacid generators generally used in chemically amplified resists" means that the amount of the photoacid generator contained in the positive photosensitive resin composition is 100 parts by mass in total of the resin components. As a standard, it means 0.2 parts by mass or less, 0.1 parts by mass or less, or 0.05 parts by mass or less. When the positive photosensitive resin composition does not substantially contain a photoacid generator commonly used in chemically amplified resists, it is preferable because the stability of the process is good and high sensitivity can be achieved.
- high-resolution patterns can be formed without the post-exposure bake (PEB) required for typical chemically amplified resists.
- PEB post-exposure bake
- the quinonediazide compound (C) has a relatively high quantum yield, and a carboxylic acid compound is efficiently produced in the exposed area.
- the alkali-soluble resin (B) contains a resin having an epoxy group and a phenolic hydroxyl group
- the ring-opening polymerization of the epoxy group of the resin having an epoxy group and a phenolic hydroxyl group does not proceed. Alkali solubility of resins having groups and phenolic hydroxyl groups can be maintained.
- the quinonediazide compound (C) includes a polyhydroxy compound in which sulfonic acid of quinonediazide is ester-bonded, a polyamino compound in which sulfonic acid of quinonediazide is sulfonamide-bonded, a polyhydroxypolyamino compound in which sulfonic acid of quinonediazide is ester-bonded or Those having sulfonamide bonds and the like can be mentioned. From the viewpoint of the contrast between the exposed and unexposed areas, it is preferable that 20 mol % or more of all the functional groups of the polyhydroxy compound or polyamino compound are substituted with quinonediazide.
- polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC , DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ , TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPH
- Polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diamino Examples include, but are not limited to, diphenyl sulfide and the like.
- polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.
- the quinonediazide compound (C) is preferably 1,2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinonediazide-5-sulfonate of a polyhydroxy compound.
- the positive photosensitive resin composition contains quinone diazide compound (C) of 5 parts by mass to 60 parts by mass, preferably 10 parts by mass to 50 parts by mass, based on a total of 100 parts by mass of the resin components. It preferably contains 15 to 42 parts by mass. If the content of the quinonediazide compound (C) is 5 parts by mass or more based on the above total of 100 parts by mass, high sensitivity can be achieved. If the content of the quinonediazide compound (C) is 60 parts by mass or less based on the above total of 100 parts by mass, the alkali developability is good.
- fluorosurfactant (D) is not particularly limited, a surfactant having at least one fluorinated hydrocarbon group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group and a hydrophilic group is used. be able to.
- fluorosurfactants (D) include perfluoroalkylsulfonic acids, partially fluorinated alkylsulfonic acids, perfluoroalkylcarboxylic acids, partially fluorinated alkylcarboxylic acids, perfluoroalkyl phosphates, partially Fluorinated alkyl phosphates, perfluoroalkyltrimethylammonium salts, partially fluorinated alkyltrimethylammonium salts, perfluoroalkylbetaines, partially fluorinated alkylbetaines, perfluoroalkylEO adducts, and fluorotelomer alcohols.
- a perfluoroalkyl group a perfluoroalkyl group, a partially fluorinated alkyl group, a perfluoroalkylene group or a partially fluorinated alkylene group, a sulfo group, a carboxyl group, a phosphoric acid group, an ammonium group, and an oxyalkylene group
- a homopolymer or copolymer having a hydrophilic group such as a polyoxyalkylene group in the molecule can also be used.
- the fluorosurfactants (D) can be used alone or in combination of two or more.
- the fluorosurfactant (D) preferably contains an acrylic copolymer having at least one fluorinated hydrocarbon group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group.
- the acrylic copolymer can promote migration of the hydrophobic resin (A) to the film surface of the positive photosensitive resin composition to make the film surface more insoluble in alkali.
- the acrylic copolymer has formula (8) (In formula (8), R 17 is a hydrogen atom or a methyl group, L 1 is a divalent group having 1 to 30 carbon atoms, and Rf 1 may contain one or more ether bonds in the chain.
- R 18 is a hydrogen atom or a methyl group
- R 19 is each independently a linear or branched alkylene group having 2 to 4 carbon atoms, a linear per a fluoroalkylene group or a linear partially fluorinated alkylene group, or a branched perfluoroalkylene group or a branched partially fluorinated alkylene group having 2 to 4 carbon atoms
- each R 20 is independently a hydrogen atom and 1 to 6 alkyl group, or a perfluoroalkyl group or partially fluorinated alkyl group having 1 to 6 carbon atoms
- c is an integer of 2 to 50.
- It is a copolymer (D1) with a polymerizable monomer having a group represented by.
- the divalent group having 1 to 30 carbon atoms represented by L 1 may contain at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, and carbon It may contain a perfluoroalkyl group or a partially fluorinated alkyl group having 4 to 6 atoms.
- Rf 1 is preferably -C 4 F 9 or -C 6 F 13 .
- the fluorine-containing polymerizable monomer represented by formula (8) can be used alone or in combination of two or more.
- examples of linear or branched alkylene groups having 2 to 4 carbon atoms represented by R 19 include ethylene group, propylene group, tetramethylene group, 1-methylethylene group, 2-methyl Examples include ethylene, 1-ethylethylene, 2-ethylethylene, and isobutylene groups.
- the linear perfluoroalkylene group or linear partially fluorinated alkylene group having 1 to 4 carbon atoms represented by R 19 includes, for example, -CF 2 -, -CF 2 CF 2 -, -CF 2 CF 2 CF 2- , -CF 2 CF 2 CF 2 CF 2 -, -CHF-, CF 2 CH 2 -, and -CF 2 CHF-.
- the branched perfluoroalkylene group or branched partially fluorinated alkylene group having 2 to 4 carbon atoms represented by R 19 includes -CF(CF 3 )-, -CF(CF 3 )CF 2 -, -CF 2 CF (CF 3 )-, -CF(CF 2 CF 3 )CF 2 -, -CF 2 CF(CF 2 CF 3 )-, -CF(CHF 2 )CF 2 -, -CF 2 CF(CHF 2 )-, -CF(CF 2 CHF 2 )CF 2 - and -CF 2 CF(CF 2 CHF 2 )-.
- R 19 may be the same or different from each other.
- R 19 is preferably a propylene group, a tetramethylene group, a 1-methylethylene group, a 2-methylethylene group, a 1-ethylethylene group, a 2-ethylethylene group, or an isobutylene group, More preferably, the same groups are linked together via adjacent oxygen atoms to form a polyoxypropylene chain, polyoxytetramethylene chain, polyoxymethylethylene chain, polyoxyethylethylene chain, or polyoxyisobutylene chain.
- examples of alkyl groups having 1 to 6 carbon atoms represented by R 20 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and n-hexyl group. is mentioned.
- Examples of the C 1-6 perfluoroalkyl group or partially fluorinated alkyl group represented by R 20 include -CF 3 , -C 2 F 5 , -C 3 F 7 , -C 4 F 9 , -C5F11 , -C6F13 , -CH2F , -CHF2 , -C2HF4 , -C3H2F5 , -C3HF6 , -C4HF8 , -C5 HF 10 , and —C 6 HF 12 .
- the polymerizable monomer having a polyoxyalkylene group represented by formula (9) can be used alone or in combination of two or more.
- the copolymer (D1) is a fluorine-containing polymerizable monomer represented by formula (8), in addition to a polymerizable monomer having a polyoxyalkylene group represented by formula (9), other polymerization It may be a copolymer with a polar monomer.
- polymerizable monomers include, for example, formula (10) (In formula (10), R 21 is a hydrogen atom or a methyl group, and R 22 is each independently a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a group containing a silyl group. .) A polymerizable monomer represented by is mentioned.
- linear, branched or cyclic alkyl groups having 1 to 18 carbon atoms represented by R 22 include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n -hexyl group, n-octyl group, n-decyl group, n-dodecyl group, stearyl group, isopropyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, isobornyl group, adamantyl group, and dicyclo A pentanyl group can be mentioned.
- Groups containing a silyl group include, for example, a trimethoxysilylpropyl group, a (trimethylsilyloxy)dimethylsilylpropyl group, and a tris(trimethylsilyloxy)silylpropyl group.
- polymerizable monomers include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-methoxystyrene; and maleimide, methylmaleimide, ethylmaleimide, n-propylmaleimide, isopropylmaleimide, Maleimide compounds such as n-butylmaleimide, n-hexylmaleimide, n-octylmaleimide, n-dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide are also included.
- aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-methoxystyrene
- maleimide methylmaleimide, ethylmaleimide, n-propylmaleimide, isopropylmaleimi
- polymerizable monomers can be used alone or in combination of two or more.
- the mass ratio (mass of fluorine-containing polymerizable monomer represented by formula (8)/mass of polymerizable monomer having a polyoxyalkylene group represented by formula (9)) is preferably 10/90. to 70/30, more preferably 15/85 to 60/40, still more preferably 25/75 to 50/50.
- it is preferably used in an amount such that the other polymerizable monomer is 50% by mass or less based on the mass of the copolymer (D1).
- the copolymer (D1) is, for example, a fluorine-containing polymerizable monomer represented by formula (8), a polymerizable monomer having a polyoxyalkylene group represented by formula (9), and optionally Other polymerizable monomers can be obtained by radical polymerization using a polymerization initiator in an organic solvent.
- organic solvents examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfoxides such as sulfoxide; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane; and aromatic hydrocarbons such as toluene and xylene.
- ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
- esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate
- amides such as dimethylformamide, di
- polymerization initiators examples include peroxide polymerization initiators such as benzoyl peroxide, and azo polymerization initiators such as 2,2'-azobisisobutyronitrile. Chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid, and the like may be used if desired.
- the number average molecular weight (Mn) of the copolymer (D1) is preferably from 2,000 to 100,000, more preferably from 2,500 to 50000.
- the fluorine atom content of the copolymer (D1) is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.
- the fluorine atom content of the copolymer (D1) is a value calculated from the mass ratio of fluorine atoms based on the total mass of the polymerizable monomers used.
- the acrylic copolymer has formula (11) (In formula (11), R 23 is a radically polymerizable functional group, L 2 is a divalent group having 1 to 8 carbon atoms, L 3 is a divalent group having 1 to 8 carbon atoms, Each Rf 2 is independently a fluorinated alkylene group having 1 to 3 carbon atoms, and d is an integer of 1 to 100.) and a fluorine-containing polymerizable monomer represented by the formula (12) (In formula (12), R 24 is a hydrogen atom or a methyl group, R 25 is each independently a linear or branched alkylene group having 2 to 4 carbon atoms, and R 26 is a hydrogen atom or a carbon atom. is an alkyl group of numbers 1 to 6, and e is an integer of 1 to 80.) It is a copolymer (D2) with a polymerizable monomer having an oxyalkylene group represented by.
- the radically polymerizable functional group represented by R 23 includes, for example, CH 2 ⁇ CHCO—, CH 2 ⁇ C(CH 3 )CO—, and CH 2 ⁇ CH—C 6 H 4 —. is mentioned. R 23 may be the same or different from each other. R 23 is preferably CH 2 ⁇ CHCO— or CH 2 ⁇ C(CH 3 )CO— from the viewpoint of availability and radical polymerizability. It is more preferable to have
- the divalent group having 1 to 8 carbon atoms represented by L 2 may contain at least one heteroatom selected from the group consisting of an oxygen atom and a nitrogen atom.
- the C 1-8 divalent group represented by L 3 may contain at least one heteroatom selected from the group consisting of an oxygen atom and a nitrogen atom.
- the fluorinated alkylene group having 1 to 3 carbon atoms represented by Rf 2 is specifically —CF 2 — (perfluoromethylene group), —CF 2 CF 2 — (perfluoro ethylene group), -CF 2 CF 2 CF 2 -, -CF 2 CF(CF 3 )-, and -CF(CF 3 )CF 2 -.
- the moiety represented by -(Rf 2 O) d Rf 2 - in formula (11) preferably contains a combination of a perfluoromethylene group and a perfluoroethylene group.
- the molar ratio of perfluoromethylene groups to perfluoroethylene groups is preferably 1/10 to 10/1.
- d is preferably 3-100, more preferably 6-70.
- the fluorine-containing polymerizable monomer represented by formula (11) preferably has 18 to 200 fluorine atoms, more preferably 25 to 150 fluorine atoms.
- the fluorine-containing polymerizable monomer represented by formula (11) can be used alone or in combination of two or more.
- straight or branched alkylene groups having 2 to 4 carbon atoms represented by R 25 include ethylene group, propylene group, tetramethylene group and isobutylene group.
- R 25 may be the same or different from each other.
- R 25 is preferably an ethylene group or a propylene group, and the same groups are linked via adjacent oxygen atoms to form a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxyethylene chain. More preferably, ethylene chains and polyoxypropylene chains form linked chains.
- examples of alkyl groups having 1 to 6 carbon atoms represented by R 26 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and n-hexyl group. is mentioned.
- e is preferably 3-50.
- the polymerizable monomer having an oxyalkylene group represented by formula (12) can be used alone or in combination of two or more.
- the copolymer (D2) is a fluorine-containing polymerizable monomer represented by formula (11), a polymerizable monomer having an oxyalkylene group represented by formula (12), and other polymerizable It may be a copolymer with a monomer.
- Other polymerizable monomers include, for example, those described for the copolymer (D1).
- the copolymer (D2) can be obtained by radical polymerization as described for the copolymer (D1).
- the number average molecular weight (Mn) of the copolymer (D2) is preferably 500 to 20000, more preferably 1500 to 10,000, and the weight average molecular weight (Mw) of the copolymer (D2) is preferably 2,000 to 100,000, more preferably 3,000 to 50,000.
- the fluorine atom content of the copolymer (D2) is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass.
- the fluorine atom content of the copolymer (D2) is a value calculated from the mass ratio of fluorine atoms based on the total mass of the polymerizable monomers used.
- fluorosurfactant (D) examples include Megafac (registered trademark) F-251, F-281, F-430, F-444, R-40, F-553, F-554, F- 555, F-556, F-557, F-558, F-559, F-562, and F-563 (trade name, DIC Corporation), and Surflon (registered trademark) S-242, S-243, S -386, S-420, and S-611 (trade name, AGC Seimi Chemical Co., Ltd.).
- the fluorosurfactant (D) is preferably Megafac (registered trademark) F-563, F-559, F-554, R-40, or F-562, more preferably Megafac (registered trademark) F-563, F-554, or R-40.
- the content of the fluorosurfactant (D) in the positive photosensitive resin composition is preferably 0.01 to 5 parts by mass, more preferably 0.01 part by mass, based on 100 parts by mass of the total resin components. 03 parts by mass to 3 parts by mass, more preferably 0.05 parts by mass to 2 parts by mass. If the content of the fluorine-based surfactant (D) is 0.01 parts by mass or more based on the above total of 100 parts by mass, the leveling property of the positive photosensitive resin composition is improved, so that the positive photosensitive
- the hydrophobic resin composition can be uniformly applied to the substrate, thereby promoting uneven distribution of the hydrophobic resin (A).
- the content of the fluorine-based surfactant (D) is 5 parts by mass or less based on the above total of 100 parts by mass, the cured film after post-baking is not adversely affected.
- the leveling property can be enhanced and the uneven distribution of the hydrophobic resin (A) can be promoted.
- the positive photosensitive resin composition may further contain at least one colorant (E) selected from the group consisting of black dyes and black pigments.
- the visibility of a display device such as an organic EL display can be improved by forming black partition walls in the organic EL element using the photosensitive resin composition containing the coloring agent (E).
- the colorant (E) due to the presence of the colorant (E), the amount of transmitted radiation during exposure drops sharply from the surface to the inside of the film. Therefore, the quinonediazide compound (C)-derived carboxylic acid compound is generated in a relatively large amount in the vicinity of the film surface, but is less likely to be generated inside the film.
- the quinonediazide compound (C)-derived carboxylic acid compound Since the quinonediazide compound (C)-derived carboxylic acid compound has low diffusivity in the film, it stays in the vicinity of the film surface and contributes to the promotion of dissolution of the exposed portion of the film surface. Since the concentration of the hydrophobic resin (A) is relatively low inside the film, the alkali solubility is relatively high. Therefore, even if the radiation does not sufficiently penetrate into the inside of the film, a highly sensitive and highly accurate thick film pattern can be formed by using the positive photosensitive resin composition of this embodiment.
- black dyes include dyes defined by the color index (C.I.) of Solvent Black 27-47.
- the black dye is preferably Solvent Black 27, 29 or 34 C.I. I. It is defined by Solvent Black 27-47 C.I. I.
- the light-shielding property of the cured positive photosensitive resin composition film can be maintained.
- a positive photosensitive resin composition containing a black dye leaves less residue of a coloring agent during development and can form a high-definition pattern, as compared with a positive photosensitive resin composition containing a black pigment.
- black pigments include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigments, and lactam pigments. Surface-treated black pigments may also be used. Examples of commercially available perylene-based pigments include K0084, K0086, Pigment Black 21, 30, 31, 32, 33, and 34 from BASF. Examples of commercially available lactam pigments include Irgaphor® Black S0100CF from BASF. The black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene-based pigments, and lactam-based pigments because of its high light-shielding properties.
- the content of the colorant (E) in the positive photosensitive resin composition is preferably 10 to 150 parts by mass, more preferably 15 to 100 parts by mass, based on the total 100 parts by mass of the resin components. , more preferably 20 to 80 parts by mass. If the content of the colorant (E) is 10 parts by mass or more based on the above total of 100 parts by mass, sufficient light shielding properties can be obtained. The opacity of the subsequent coating can be maintained. If the content of the colorant (E) is 150 parts by mass or less based on the above total of 100 parts by mass, the film retention rate and sensitivity are appropriate. high heat resistance.
- the positive photosensitive resin composition contains, as optional components, a dissolution accelerator (F), a thermosetting agent, a second surfactant other than the fluorosurfactant (D), and a second colorant other than the colorant (E). etc.
- optional ingredients are defined as none of (A)-(E).
- the positive photosensitive resin composition may further contain a dissolution accelerator (F) for improving the solubility of the alkali-soluble portion in the developer during development.
- a dissolution accelerator (F) for improving the solubility of the alkali-soluble portion in the developer during development.
- the dissolution accelerator (F) include organic low-molecular-weight compounds selected from the group consisting of compounds having a carboxyl group and compounds having a phenolic hydroxyl group.
- the dissolution accelerator (F) can be used alone or in combination of two or more.
- low-molecular-weight compounds refer to compounds with a molecular weight of 1000 or less.
- the organic low-molecular compound has a carboxyl group or a plurality of phenolic hydroxyl groups and is alkali-soluble.
- organic low-molecular-weight compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, etc.
- aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid
- succinic acid glutaric acid, adipic acid, pimel
- Aliphatic dicarboxylic acids such as aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid and mesitylene acid; Aromatic polycarboxylic acids such as mellitic acid, trimesic acid, melophanic acid, pyromellitic acid and hemimellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid and gallic acid; phenylacetic acid, hydroatropic acid, hydrosilicone Other carboxylic acids such as mic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, umberic acid; catechol, resorcinol, hydroquinone, 1,
- the content of the dissolution accelerator (F) in the positive photosensitive resin composition can be 0.1 parts by mass to 50 parts by mass, preferably 1 part by mass, based on the total of 100 parts by mass of the resin components. parts to 35 parts by mass, more preferably 2 parts to 20 parts by mass. If the content of the dissolution accelerator (F) is 0.1 parts by mass or more based on the above total of 100 parts by mass, the dissolution of the resin component can be effectively promoted, and if it is 50 parts by mass or less Excessive dissolution of the resin component can be suppressed, and the pattern formability and surface quality of the film can be improved.
- thermosetting agent A thermal radical generator can be used as the thermosetting agent.
- Preferred thermal radical generators include organic peroxides, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl Examples of organic peroxides having a 10-hour half-life temperature of 100 to 170° C., such as cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide. be able to.
- the content of the heat curing agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less, based on the total 100 parts by mass of solid content excluding the heat curing agent. .
- the positive photosensitive resin composition contains a second A surfactant can be included.
- the second surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene aryl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and organosiloxane polymers KP323, KP326, KP341 (trade name, Shin-Etsu Chemical Co., Ltd. ).
- a 2nd surfactant can be used individually or in combination of 2 or more types.
- the content of the second surfactant is preferably 2 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.1 part by mass, based on the total 100 parts by mass of the solid content excluding the second surfactant. It is 5 parts by mass or less.
- the positive photosensitive resin composition does not contain a second surfactant.
- the positive photosensitive resin composition can contain a second coloring agent other than the coloring agent (E).
- the second colorant include dyes, organic pigments, and inorganic pigments.
- the second coloring agent can be used in a content that does not impair the effects of the present invention according to the purpose.
- dyes examples include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diphenylmethane dyes, and triphenylmethane dyes.
- pigments for example, C.I. I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Blue 15, 15:1, 15:4, 22, 60, 64, C.I. I. Pigment Green 7, and C.I. I. Pigment Brown 23, 25, 26 can be mentioned.
- the positive photosensitive resin composition can be dissolved or dispersed in the solvent (G) and used as a coating composition in the form of a solution or dispersion.
- a solution obtained by dissolving a hydrophobic resin (A) and an alkali-soluble resin (B) in a solvent (G) is added with a quinonediazide compound (C), a fluorosurfactant (D), and, if necessary,
- a coating composition containing a positive photosensitive resin composition is prepared by mixing optional components such as a coloring agent (E), a dissolution accelerator (F), a thermosetting agent, and other surfactants in a predetermined ratio. can do.
- the coating composition can be adjusted to a viscosity suitable for the coating method used by varying the amount of solvent (G).
- Examples of the solvent (G) include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol.
- glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether
- ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate
- diethylene glycol diethylene glycol.
- Diethylene glycol compounds such as monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether;
- Propylene glycol monoalkyl ether acetate compounds such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate
- aromatic hydrocarbons such as toluene and xylene
- ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and cyclohexanone;
- the solid content concentration of the coating composition can be appropriately determined depending on the purpose of use.
- the coating composition may have a solids concentration of 1 to 60% by weight, 3 to 50% by weight, or 5 to 40% by weight.
- a known method can be used for the method of dispersing and mixing when using a pigment.
- ball mills such as ball mills, sand mills, bead mills, paint shakers and rocking mills; blade types such as kneaders, paddle mixers, planetary mixers and Henschel mixers; roll types such as three-roll mixers; An ultrasonic wave, a homogenizer, a rotation/revolution mixer, etc. may be used. It is preferable to use a bead mill from the viewpoint of dispersion efficiency and fine dispersion.
- the prepared coating composition is usually filtered before use.
- Filtration means include, for example, a Millipore filter with a pore size of 0.05 to 1.0 ⁇ m.
- the coating composition prepared in this way also has excellent long-term storage stability.
- a coating composition is prepared by dissolving or dispersing the positive photosensitive resin composition in a solvent.
- the coating composition can then be applied to the substrate surface and the solvent removed by means such as heating to form a coating.
- the method of applying the coating composition to the substrate surface is not particularly limited, and for example, a spray method, a roll coating method, a slit method, or a spin coating method can be used.
- the solvent is usually removed by heating to form a film (pre-bake).
- the heating conditions vary depending on the type and blending ratio of each component, but usually at 70 to 130° C., for example, 30 seconds to 20 minutes on a hot plate and 1 to 60 minutes in an oven to obtain a coating. can be done.
- the thickness of the coating formed is 2-3 ⁇ m.
- the pre-baked film is irradiated with radiation (for example, visible light, ultraviolet light, deep ultraviolet light, X-rays, electron beams, gamma rays, or synchrotron radiation) through a photomask having a predetermined pattern (exposure step).
- radiation for example, visible light, ultraviolet light, deep ultraviolet light, X-rays, electron beams, gamma rays, or synchrotron radiation
- Preferred radiation is ultraviolet to visible light having a wavelength of 250-450 nm.
- the radiation is i-line.
- the radiation is ghi rays.
- the positive photosensitive resin composition contains a protective resin as the alkali-soluble resin (B)
- heat treatment can be performed after the exposure step to promote decomposition of the acid-decomposable groups.
- PEB promotes deprotection of the protected alkali-soluble functional groups in the protective resin in the exposed area, and can further increase the alkali-solubility of the exposed area.
- Heating conditions vary depending on the type and blending ratio of each component, but usually PEB is performed by heating at 70 to 140° C., for example, 30 seconds to 20 minutes on a hot plate and 1 to 60 minutes in an oven. can be done.
- no PEB process is included after the exposure process. As a result, it is possible to prevent flow, deformation, etc. of the film due to heating, to form a thick film pattern with high accuracy, and to reduce the number of processes involved in forming partition walls or insulating films.
- the coating is developed by contacting it with a developer, and unnecessary portions are removed to form a pattern on the coating (development process).
- the developer include inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline.
- inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia
- primary amines such as ethylamine and n-propyl
- ammonium salts pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, cyclic amines such as 1,5-diazabicyclo[4.3.0]-5-nonane, etc.
- Aqueous solutions can be used.
- An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like to an alkaline aqueous solution can also be used as a developer.
- Development time is usually 30 to 180 seconds.
- the developing method may be any one of a liquid swell method, a shower method, a dipping method, and the like.
- the coating can be patterned by washing with running water for 30 to 90 seconds, removing unnecessary portions, and air-drying with compressed air or compressed nitrogen.
- the film having the pattern formed thereon is subjected to heat treatment at 100 to 350° C. for 20 to 200 minutes using a heating device such as a hot plate or oven to obtain a cured film (post-baking, heat treatment process).
- a heating device such as a hot plate or oven to obtain a cured film
- the temperature may be maintained constant, may be increased continuously, or may be increased stepwise.
- the heat treatment is preferably performed in a nitrogen gas atmosphere.
- a positive photosensitive resin composition can form a film in which the alkali solubility of the surface of the film is lower than that of the entire film.
- the positive photosensitive resin composition was applied so that the film thickness after prebaking was 3 ⁇ 0.3 ⁇ m, prebaked at 125 ° C. for 120 seconds to form a film, and then applied at 30 mJ / cm 2 .
- the dissolution rate of the coating surface layer is lower than the dissolution rate of the entire coating when the coating is exposed under these conditions and developed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution at a temperature of 23°C.
- the dissolution rate of the coating surface layer is the average dissolution rate at the time when the coating is dissolved until the thickness of the coating reaches 80%, and the dissolution rate of the entire coating is the coating thickness of 30%. It is the average dissolution rate at the time of dissolving up to The surface and overall average dissolution rate of the coating is determined by the procedure described in the Examples.
- the difference between the dissolution rate of the coating surface layer and the dissolution rate of the entire coating is preferably 3 nm/sec or more, more preferably 5 nm/sec or more, and still more preferably 8 nm/sec or more.
- the positive photosensitive resin composition is applied so that the film thickness after prebaking is 3 ⁇ 0.3 ⁇ m, prebaked at 125 ° C. for 120 seconds to form a film, and then at a temperature of 23 ° C.
- Remaining film ratio (%) film thickness after development ( ⁇ m)/film thickness before development ( ⁇ m) is 90% or more, preferably 95% or more, more preferably 99% or more.
- the residual film ratio is an index of the solubility of the unexposed area, and the higher the residual film ratio, the greater the difference in solubility between the exposed and unexposed areas. can.
- the optical density (OD value) of the cured film of the positive photosensitive resin composition is 0.5 or more per 1 ⁇ m of film thickness. It is preferably 0.7 or more, and even more preferably 1.0 or more. If the cured film has an OD value of 0.5 or more per 1 ⁇ m of film thickness, sufficient light shielding properties can be obtained.
- a method for producing an organic EL element partition wall or an organic EL element insulating film of one embodiment includes dissolving or dispersing a positive photosensitive resin composition in a solvent to prepare a coating composition, and applying the coating composition to a substrate. to form a coating, remove the solvent contained in the coating and dry the coating, irradiate the dried coating with radiation through a photomask to expose the coating, and expose the exposed coating to the developer Forming a pattern on the film by contact development, and heat-treating the patterned film at a temperature of 100° C. to 350° C. to form an organic EL element partition wall or an organic EL element insulating film.
- the above PEB can also be performed after exposure and before development.
- the positive photosensitive resin composition of the present disclosure can form a highly sensitive and highly accurate thick film pattern even in an embodiment in which the positive photosensitive resin composition contains the colorant (E).
- Organic EL element partition wall One embodiment is an organic EL element partition containing a cured product of a positive photosensitive resin composition.
- the positive photosensitive resin composition preferably contains a coloring agent (E).
- Organic EL element insulating film containing a cured product of a positive photosensitive resin composition.
- the positive photosensitive resin composition preferably contains a coloring agent (E).
- Organic EL element One embodiment is an organic EL device containing a cured product of a positive photosensitive resin composition.
- the positive photosensitive resin composition preferably contains a coloring agent (E).
- the weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were calculated under the following measurement conditions using a calibration curve prepared using polystyrene standard substances.
- Alkali-soluble resin (B) production of a copolymer (PCX-01) of a polymerizable monomer having an alkali-soluble functional group (phenolic hydroxyl group) and another polymerizable monomer 4- 28.0 g of hydroxyphenyl methacrylate (“PQMA” by Showa Denko Co., Ltd.) and 7.89 g of N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) were mixed with 7.7 g of 1-methoxy-2-propyl acetate (Daicel Co., Ltd.) as a solvent.
- PCX-01 hydroxyphenyl methacrylate
- PQMA hydroxyphenyl methacrylate
- N-cyclohexylmaleimide Nippon Shokubai Co., Ltd.
- the precipitated copolymer was recovered by filtration and vacuum-dried at 90° C. for 4 hours to recover 33.4 g of white powder.
- the obtained PCX-01 had a number average molecular weight of 6,600 and a weight average molecular weight of 11,600.
- Alkali-soluble resin (B) Production of a copolymer (PCX-02e) of a polymerizable monomer having an alkali-soluble functional group (phenolic hydroxyl group) and another polymerizable monomer 4- 25.5 g of hydroxyphenyl methacrylate (“PQMA” by Showa Denko Co., Ltd.) and 4.50 g of N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) were mixed with 1-methoxy-2-propyl acetate (Daicel Co., Ltd.) as a solvent.
- PCX-02e a copolymer having an alkali-soluble functional group (phenolic hydroxyl group) and another polymerizable monomer 4- 25.5 g of hydroxyphenyl methacrylate (“PQMA” by Showa Denko Co., Ltd.) and 4.50 g of N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) were mixed with 1-me
- the precipitated copolymer was collected by filtration and vacuum-dried at 90° C. for 4 hours to collect 32.4 g of white powder.
- the obtained PCX-02e had a number average molecular weight of 3,100, a weight average molecular weight of 6,700, and a phenolic hydroxyl group equivalent of 210.
- Hydrophobic resin (A) Production of resin having silicon-containing group (PCX-02e-TBDMS34) 4-hydroxyphenyl methacrylate (Showa Denko Co., Ltd. “PQMA”) 15.9 g, 4-tert-butyl 16.6 g of dimethylsilyloxyphenyl methacrylate (PQMA-TBDMS) and 4.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were added to 55.8 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) as a solvent.
- PCX-02e-TBDMS34 4-hydroxyphenyl methacrylate
- PQMA-TBDMS 4-tert-butyl 16.6 g of dimethylsilyloxyphenyl methacrylate
- N-cyclohexylmaleimide Tokyo Chemical Industry Co., Ltd.
- PCX-02e-TBDMS34 had a number average molecular weight of 3,753 and a weight average molecular weight of 7,581.
- Hydrophobic resin (A) Production of resin (PCX-02e-TES34) having silicon-containing group 4-hydroxyphenyl methacrylate (Showa Denko Co., Ltd. "PQMA") 15.9 g, 4-triethylsilyloxy 16.6 g of phenyl methacrylate (PQMA-TES) and 4.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were completely dissolved in 55.8 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) as a solvent. rice field.
- PCX-02e-TES34 silicon-containing group 4-hydroxyphenyl methacrylate
- PQMA-TES 4-triethylsilyloxy 16.6 g of phenyl methacrylate
- N-cyclohexylmaleimide Tokyo Chemical Industry Co., Ltd.
- PCX-02e-TES34 had a number average molecular weight of 3,847 and a weight average molecular weight of 7,534.
- the content of silicon atoms was 4.0% by mass based on the mass of PCX-02e-TES34.
- Hydrophobic resin (A) production of resin having fluorine-containing group (PCX-02e-C6SFMA36) 4-hydroxyphenyl methacrylate (Showa Denko Co., Ltd. “PQMA”) 12.1 g, 2-perfluorohexyl 20.5 g of ethyl methacrylate (Tokyo Chemical Industry Co., Ltd.) and 3.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were completely dissolved in 84.5 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) as a solvent. Dissolved.
- PCX-02e-C6SFMA36 4-hydroxyphenyl methacrylate
- PQMA Showa Denko Co., Ltd.
- 2-perfluorohexyl 20.5 g of ethyl methacrylate Tokyo Chemical Industry Co., Ltd.
- 3.62 g of N-cyclohexylmaleimide
- PCX-02e-C6SFMA36 The precipitated copolymer was recovered by filtration and vacuum dried at 80° C. for 5 hours to recover 5.58 g of white powder (PCX-02e-C6SFMA36).
- the obtained PCX-02e-C6SFMA36 had a number average molecular weight of 2,869 and a weight average molecular weight of 5,743.
- the molar ratio of the structural unit derived from 2-perfluorohexylethyl methacrylate, the structural unit represented by formula (2), and the structural unit represented by formula (3) was 36:6:58. and the structural unit having an alkali-soluble functional group was 58 mol % based on all structural units.
- the content of fluorine atoms was 24% by mass based on the mass of PCX-02e-C6SFMA36.
- Alkali-soluble resin (B) Production of resin (PCX-02e-THF28) in which the alkali-soluble functional group (phenolic hydroxyl group) is protected with a 2-tetrahydrofuranyl group In a 100 mL three-necked flask , PCX-02e 10.0 g of Production Example 2, and pyridinium salt of p-toluenesulfonic acid (Tokyo Chemical Industry Co., Ltd.) 0.60 g as an acid catalyst, tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.) 50.0 g Dissolved.
- PCX-02e-THF28 a resin in which the alkali-soluble functional group (phenolic hydroxyl group) was protected with a 2-tetrahydrofuranyl group was prepared. Obtained.
- PCX-02e-THF28 thus obtained had a number average molecular weight of 3700, a weight average molecular weight of 6800, a proportion of phenolic hydroxyl groups protected with acid-decomposable groups of 28 mol%, and at least one phenolic hydroxyl group being acid-decomposable.
- the number of structural units represented by formula (7) protected by groups was 25% of the total number of structural units of PCX-02e-THF28.
- the proportion of phenolic hydroxyl groups protected by acid-decomposable groups was determined using a thermogravimetric differential thermal analyzer (TG/DTA6200, Hitachi High-Tech Science Co., Ltd.) in a nitrogen gas stream at a heating rate of 10°C/min. It was calculated from the weight loss rate (%) of the resin at 260°C when the temperature was raised from room temperature to 250°C under the following conditions, held for 10 minutes, and further heated to 400°C at a temperature increase rate of 10°C/min. .
- Alkali-soluble resin (B) Production of resin (N695OH70) having epoxy group and phenolic hydroxyl group 75.2 g of ⁇ -butyrolactone (Mitsubishi Chemical Co., Ltd.) as a solvent in a 300 mL three-necked flask, 1 As a compound having at least two epoxy groups in the molecule, 37.8 g of EPICLON (registered trademark) N-695 (DIC Corporation, cresol novolak type epoxy resin, epoxy equivalent: 214) was charged and heated at 60°C in a nitrogen gas atmosphere. Dissolved.
- EPICLON registered trademark
- N-695 DIC Corporation, cresol novolak type epoxy resin, epoxy equivalent: 214
- Hydrophobic resin (A) As the hydrophobic resin (A), PCX-02e-TBDMS34 of Production Example 3, PCX-02e-TES34 of Production Example 4 (resin having a silicon-containing group), and PCX-02e-C6SFMA36 of Production Example 5 (fluorine-containing group) was used.
- Alkali-soluble resin (B) As the alkali-soluble resin (B), PCX-02e-THF28 of Production Example 6, PCX-01 of Production Example 1, PCX-02e of Production Example 2, N695OH70 of Production Example 7, and EPICLON (registered trademark) N-695 ( DIC Corporation, cresol novolak type epoxy resin, epoxy equivalent 214) was used.
- TS-150A has a quinonediazide structure in an average of 1.5 R out of 3 R per molecule.
- TS-200A has a quinonediazide structure for an average of 2.0 R out of 3 R per molecule.
- Fluorine-based surfactant (D) As the fluorosurfactant (D), Megafac (registered trademark) F-562, Megafac (registered trademark) F-554, Megafac (registered trademark) R-40, Megafac (registered trademark) F-563, and Megafac (registered trademark) F-559 (all manufactured by DIC Corporation).
- KF2201 silicone-based surfactant, Shin-Etsu Chemical Co., Ltd.
- a glass substrate (size 100 mm ⁇ 100 mm ⁇ 1 mm) is bar-coated with a positive photosensitive resin composition so that the dry film thickness is 3 ⁇ 0.3 ⁇ m, and after vacuum drying at room temperature for 60 seconds, it is placed on a hot plate with a lid. The solvent was dried by heating at 125° C. for 120 seconds (pre-baking). After measuring the dry film thickness using an optical film thickness measuring device (F20-NIR, Filmetrics Co., Ltd.), an exposure device incorporating an ultra-high pressure mercury lamp (trade name Multilight ML-251A / B, Ushio Inc. company) under the condition of 30 mJ/cm 2 .
- an optical film thickness measuring device F20-NIR, Filmetrics Co., Ltd.
- an exposure device incorporating an ultra-high pressure mercury lamp (trade name Multilight ML-251A / B, Ushio Inc. company) under the condition of 30 mJ/cm 2 .
- the amount of exposure was measured using an ultraviolet integrating photometer (trade name: UIT-150, light receiving unit: UVD-S365, USHIO INC.). After that, using a spin developing device (AD-1200, Takizawa Sangyo Co., Ltd.), development is performed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution at a temperature of 23 ° C., and the film thickness of the developed film is determined by optical film thickness. Measured using a measuring device. By changing the development time and performing alkali development, the development time was obtained until the film thickness of the exposed portion reached 80% or 30%, respectively.
- an ultraviolet integrating photometer trade name: UIT-150, light receiving unit: UVD-S365, USHIO INC.
- An alkali dissolution rate (nm/sec) was obtained by dividing the amount of film loss (nm) after development by the development time (sec).
- the above-mentioned alkali dissolution rate at the time when the film thickness of the film in the exposed portion is 80% is taken as the average dissolution speed of the coating surface layer, and the time when the film thickness in the exposed portion is dissolved until the film thickness is 30%. was taken as the average dissolution rate of the entire coating.
- a glass substrate (size 100 mm ⁇ 100 mm ⁇ 1 mm) was bar-coated with a positive photosensitive resin composition so that the dry film thickness was 3.0 ⁇ m, dried in vacuum at room temperature for 60 seconds, and placed on a hot plate with a lid at 125 °C. was heated for 120 seconds for pre-baking.
- the film was exposed through a quartz photomask (having an opening pattern of ⁇ 10 ⁇ m) with an exposure apparatus (trade name: Multilight ML-251A/B, USHIO INC.) incorporating an ultra-high pressure mercury lamp.
- the amount of exposure was measured using an ultraviolet integrating photometer (trade name: UIT-150, light receiving unit: UVD-S365, USHIO INC.).
- a glass substrate (size 100 mm ⁇ 100 mm ⁇ 1 mm) was bar-coated with a positive photosensitive resin composition so that the dry film thickness was 3.0 ⁇ m, dried in vacuum at room temperature for 60 seconds, and placed on a hot plate with a lid at 125 °C. was heated for 120 seconds for pre-baking.
- a spin developing device (AD-1200, Takizawa Sangyo Co., Ltd.) was used to add 2.38% by mass of tetramethylammonium. Alkali development was carried out with an aqueous hydroxide solution for 60 seconds.
- the film thickness after alkali development was measured again using an optical film thickness measuring device (F20-NIR, Filmetrics Co., Ltd.), and the dissolved film thickness ( ⁇ m) before and after development was used as an index of the unexposed area solubility. .
- [OD value of cured film] A glass substrate (size 100 mm ⁇ 100 mm ⁇ 1 mm) was spin-coated with a positive photosensitive resin composition to a dry film thickness of about 1.5 ⁇ m, and prebaked by heating on a hot plate at 125°C for 120 seconds. rice field. After that, the coating was obtained by curing at 250° C. for 60 minutes in a nitrogen gas atmosphere. The OD value of the film after curing was measured with a transmission densitometer (BMT-1, Sakata Inx Engineering Co., Ltd.), corrected with the OD value of the glass alone, and converted to an OD value per 1 ⁇ m of film thickness. The thickness of the coating was measured using an optical film thickness measuring device (F20-NIR, Filmetrics Co., Ltd.).
- the positive photosensitive resin compositions of Examples 1 to 14 have an unexposed area solubility of 0 ⁇ m, so that the contrast between the exposed area and the unexposed area can be increased. It was determined that a thick film pattern could be formed with high accuracy. Furthermore, it was also confirmed that the exposure amount capable of forming a pattern with a hole diameter of 10 ⁇ m after development was 300 mJ/cm 2 or less, indicating high sensitivity.
- FIG. 1 shows a chart showing the sputtering time (horizontal axis) and silicon element concentration (vertical axis) of the films of Examples 4, 6 and 7 obtained by XPS analysis.
- the equipment and measurement conditions used for the XPS analysis were as follows.
- the positive photosensitive resin composition according to the present disclosure can be suitably used for radiation lithography for forming partition walls or insulating films of organic EL elements.
- an organic EL device provided with a partition or an insulating film formed from the positive photosensitive resin composition of the embodiment containing the colorant (E) is suitably used as an electronic component of a display device exhibiting good contrast. be.
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Abstract
Description
[1]
疎水性樹脂(A)と、
アルカリ可溶性樹脂(B)と、
キノンジアジド化合物(C)と、
フッ素系界面活性剤(D)と
を含むポジ型感光性樹脂組成物であって、前記ポジ型感光性樹脂組成物をプリベーク後の膜厚が3±0.3μmになるように塗布し、125℃で120秒プリベークして被膜を形成した後、30mJ/cm2の条件で露光し、温度23℃にて2.38質量%テトラメチルアンモニウムヒドロキシド水溶液で現像したときに、被膜表面層の溶解速度が被膜全体の溶解速度よりも低く、前記被膜表面層の溶解速度とは、前記被膜の膜厚が80%となるまで溶解させた時点での平均溶解速度であり、前記被膜全体の溶解速度とは、前記被膜の膜厚が30%となるまで溶解させた時点での平均溶解速度である、ポジ型感光性樹脂組成物。
[2]
前記被膜表面層の溶解速度と前記被膜全体の溶解速度の差が3nm/秒以上である、[1]に記載のポジ型感光性樹脂組成物。
[3]
前記疎水性樹脂(A)が、ケイ素含有基及びフッ素含有基からなる群より選ばれる少なくとも1つを有する樹脂である、[1]又は[2]に記載のポジ型感光性樹脂組成物。
[4]
前記疎水性樹脂(A)が、式(1)
で表される構造単位を有し、sが1以上の整数である式(1)で表される構造単位を少なくとも1つ有する、[3]に記載のポジ型感光性樹脂組成物。
[5]
前記疎水性樹脂(A)が、式(2)
で表される構造単位を更に有する、[4]に記載のポジ型感光性樹脂組成物。
[6]
前記フッ素系界面活性剤(D)が、フッ素化アルキル基及びフッ素化アルキレン基からなる群より選ばれる少なくとも1つのフッ素化炭化水素基を有するアクリル系共重合体を含む、[1]~[5]のいずれかに記載のポジ型感光性樹脂組成物。
[7]
前記アルカリ可溶性樹脂(B)が、アルカリ可溶性官能基を有する重合性単量体とその他の重合性単量体との共重合体、エポキシ基及びフェノール性水酸基を有する樹脂、又はそれらの組合せを含む、[1]~[6]のいずれかに記載のポジ型感光性樹脂組成物。
[8]
黒色染料及び黒色顔料からなる群より選ばれる少なくとも1種の着色剤(E)を更に含む、[1]~[7]のいずれかに記載のポジ型感光性樹脂組成物。
[9]
前記着色剤(E)を、樹脂成分の合計100質量部を基準として10質量部~150質量部含む、[8]に記載のポジ型感光性樹脂組成物。
[10]
前記ポジ型感光性樹脂組成物の硬化被膜の光学濃度(OD値)が膜厚1μmあたり0.5以上である、[8]又は[9]に記載のポジ型感光性樹脂組成物。
[11]
[1]~[10]のいずれかに記載のポジ型感光性樹脂組成物の硬化物を含む有機EL素子隔壁。
[12]
[1]~[10]のいずれかに記載のポジ型感光性樹脂組成物の硬化物を含む有機EL素子絶縁膜。
[13]
[1]~[10]のいずれかに記載のポジ型感光性樹脂組成物の硬化物を含む有機EL素子。
フェノール性水酸基当量=
(原料のエポキシ当量+付加させるカルボン酸の分子量)/(カルボン酸のフェノール性水酸基数)
によって算出される値を意味する。
一実施態様のポジ型感光性樹脂組成物は、疎水性樹脂(A)と、アルカリ可溶性樹脂(B)と、キノンジアジド化合物(C)と、フッ素系界面活性剤(D)とを含む。ポジ型感光性樹脂組成物をプリベーク後の膜厚が3±0.3μmになるように塗布し、125℃で120秒プリベークして被膜を形成した後、30mJ/cm2の条件で露光し、温度23℃にて2.38質量%テトラメチルアンモニウムヒドロキシド水溶液で現像したときに、被膜表面層の溶解速度が被膜全体の溶解速度よりも低い。被膜表面層の溶解速度とは、被膜の膜厚が80%となるまで溶解させた時点での平均溶解速度であり、被膜全体の溶解速度とは、被膜の膜厚が30%となるまで溶解させた時点での平均溶解速度である。
疎水性樹脂(A)は、フッ素系界面活性剤(D)によって被膜表面へのその偏在化が促進され、ポジ型感光性樹脂組成物の被膜表面をアルカリ水溶液に対して難溶化する樹脂である。いかなる理論に拘束される訳ではないが、疎水性樹脂(A)は、ポジ型感光性樹脂組成物の被膜の形成過程で、被膜表面に移動するフッ素系界面活性剤(D)に随伴して被膜表面に向かって移動しやすい。そのため、被膜形成後に、疎水性樹脂(A)は、被膜内部と比べて被膜表面により高濃度で存在し、被膜表面のアルカリ溶解性を低下させる。現像時には、疎水性樹脂(A)は、アルカリ低溶解性の樹脂成分として未露光部の被膜表面の溶解を抑制しつつ、露光部ではキノンジアジド化合物(C)由来のカルボン酸化合物、アルカリ可溶性の高い他の樹脂成分、及び任意の溶解促進剤の溶解に伴い、被膜から現像液中に放出される。露光部において被膜表面が一旦溶解すると、疎水性樹脂(A)の濃度が相対的に低いために被膜表面に比べアルカリ溶解性の高い被膜内部の溶解は速やかに進行する。これにより、露光部と未露光部のコントラストを増加させることができ、その結果、ポジ型感光性樹脂組成物の厚膜におけるパターン形成性を高めることができる。
アルカリ可溶性樹脂(B)は特に限定されないが、アルカリ可溶性官能基を有する樹脂であることが好ましい。アルカリ可溶性官能基としては、特に限定されないが、フェノール性水酸基、カルボキシ基、スルホ基、リン酸基、酸無水物基、及びメルカプト基が挙げられる。2種類以上のアルカリ可溶性官能基を有するアルカリ可溶性樹脂(B)を使用してもよい。アルカリ可溶性樹脂(B)は、酸分解性基で保護されたアルカリ可溶性官能基を有していてもよい。
アルカリ可溶性官能基を有する重合性単量体とその他の重合性単量体の共重合体(以下、単に「アルカリ可溶性官能基を有する共重合体」ともいう。)の有するアルカリ可溶性官能基としては、例えば、フェノール性水酸基、カルボキシ基、スルホ基、リン酸基、酸無水物基、及びメルカプト基が挙げられる。アルカリ可溶性官能基を有する重合性単量体とその他の重合性単量体の共重合体は、2種類以上のアルカリ可溶性官能基を有してもよい。アルカリ可溶性官能基を有する重合性単量体及びその他の重合性単量体が有する重合性官能基としては、例えば、CH2=CH-、CH2=C(CH3)-、CH2=CHCO-、CH2=C(CH3)CO-、-OC-CH=CH-CO-等のラジカル重合性官能基が挙げられる。
エポキシ基及びフェノール性水酸基を有する樹脂はアルカリ水溶液可溶性樹脂である。エポキシ基及びフェノール性水酸基を有する樹脂はフェノール性水酸基以外のアルカリ可溶性官能基を有していてもよい。エポキシ基及びフェノール性水酸基を有する樹脂は、例えば、1分子中に少なくとも2個のエポキシ基を有する化合物(以下、「エポキシ化合物」と表記することがある。)のエポキシ基の一部と、ヒドロキシ安息香酸化合物のカルボキシ基を反応させることで得ることができる。エポキシ基及びフェノール性水酸基を有する樹脂のエポキシ基は、現像後の加熱処理(ポストベーク)時にフェノール性水酸基との反応により架橋を形成し、これにより被膜の耐薬品性、耐熱性などを向上させることができる。フェノール性水酸基は現像時のアルカリ水溶液に対する可溶性に寄与することから、エポキシ基及びフェノール性水酸基を有する樹脂は、低露光量で露光したときに他の樹脂の溶解促進剤としても機能し、これにより感光性樹脂組成物を高感度にすることができる。
アルカリ可溶性樹脂(B)は、酸分解性基で保護されたアルカリ可溶性官能基を有する樹脂(以下、単に「保護樹脂」ともいう。)を含んでもよい。保護樹脂は、複数のアルカリ可溶性官能基を有し、複数のアルカリ可溶性官能基の少なくとも一部が酸分解性基で保護されたものであれば特に限定されない。保護樹脂としては、例えば、複数のアルカリ可溶性官能基を有する上記のアルカリ可溶性樹脂をベース樹脂として、そのアルカリ可溶性官能基の少なくとも一部が酸分解性基で保護された樹脂が挙げられる。アルカリ可溶性官能基としては、例えば、フェノール性水酸基、カルボキシ基、スルホ基、リン酸基、酸無水物基、及びメルカプト基を挙げることができる。アルカリ可溶性官能基はフェノール性水酸基又はカルボキシ基であることが好ましく、フェノール性水酸基であることがより好ましい。アルカリ可溶性官能基の一部が酸分解性基で保護されていることにより、保護樹脂の露光前のアルカリ溶解性は抑制されている。保護樹脂は、酸分解性基で保護されたアルカリ可溶性官能基以外のアルカリ可溶性官能基を有していてもよい。露光時に発生した酸の存在下、必要に応じて露光後ベーク(PEB、post exposure bake)を行うことにより、酸分解性基の分解(脱保護)が促進され、アルカリ可溶性官能基が再生する。これにより現像時に露光部で保護樹脂のアルカリ溶解が促進される。保護樹脂は、単独で、又は2種類以上を組み合わせて使用することができる。例えば、保護樹脂は、重合体又は共重合体の構造単位、酸分解性基、アルカリ可溶性官能基の保護率、又はこれらの組合せが異なる2種類以上の樹脂の組合せであってよい。
保護樹脂は、複数のアルカリ可溶性官能基を有するベース樹脂のアルカリ可溶性官能基の一部を酸分解性基で保護することによって得ることができる。例えば、アルカリ可溶性官能基がフェノール性水酸基の場合、酸分解性基で保護されたフェノール性水酸基を有する保護樹脂は、Ar-O-R11の部分構造を有し、Arはフェノール由来の芳香環を表し、R11は酸分解性基を表す。
-CR12R13-O-R14 (6)
(式(6)中、R12及びR13は、それぞれ独立して水素原子、炭素原子数1~4の直鎖アルキル基、又は炭素原子数3~4の分岐アルキル基であり、R14は、炭素原子数1~12の直鎖アルキル基、炭素原子数3~12の分岐アルキル基、炭素原子数3~12の環状アルキル基、炭素原子数7~12のアラルキル基、又は炭素原子数2~12のアルケニル基であり、R12又はR13の一方とR14とが結合して環員数3~10の環構造を形成してもよく、R12、R13及びR14は、塩素、臭素及びヨウ素からなる群より選ばれるハロゲン原子で置換されていてもよい。)で表される基が挙げられる。式(6)で表される基は、アルカリ可溶性官能基がフェノール性水酸基の場合、アルカリ可溶性官能基由来の酸素原子と一緒にアセタール構造又はケタール構造を形成する。これらの酸分解性基は、単独で、又は2種類以上を組み合わせて用いることができる。
-CR12R13-O-R14 (6)
(式(6)中、R12、R13及びR14は、前記のとおりである。)で表される基であることが好ましい。式(6)中、R12及びR13は、それぞれ独立して水素原子、炭素原子数1~4の直鎖アルキル基、又は炭素原子数3~4の分岐アルキル基であり、R14は、塩素、臭素及びヨウ素からなる群より選ばれるハロゲン原子で置換されていてもよい、炭素原子数1~12の直鎖アルキル基、炭素原子数3~12の分岐アルキル基、又は炭素原子数3~12の環状アルキル基であることがより好ましい。そのような酸分解性基としては、例えば、1-アルコキシアルキル基が挙げられる。1-アルコキシアルキル基としては、例えば、メトキシメチル基、1-メトキシエチル基、1-エトキシエチル基、1-n-プロポキシエチル基、1-n-ブトキシエチル基、1-イソブトキシエチル基、1-(2-クロロエトキシ)エチル基、1-(2-エチルヘキシルオキシ)エチル基、1-シクロヘキシルオキシエチル基、及び1-(2-シクロヘキシルエトキシ)エチル基が挙げられ、1-エトキシエチル基及び1-n-プロポキシエチル基が好ましい。R12又はR13の一方とR14とが結合して環員数3~10の環構造を形成した酸分解性基としては、例えば、2-テトラヒドロフラニル基、及び2-テトラヒドロピラニル基が挙げられ、2-テトラヒドロフラニル基が好ましい。
キノンジアジド化合物(C)は、可視光、紫外光、γ線、電子線等の放射線が照射されると下記反応式2に示す反応を経てアルカリ可溶性のカルボン酸化合物を生成する。キノンジアジド化合物(C)は、感光前にはアルカリ可溶性樹脂(B)のアルカリ可溶性官能基、例えばフェノール性水酸基と相互作用(例えば水素結合形成)して、そのアルカリ可溶性樹脂(B)をアルカリ水溶液に対して不溶化させる。その一方で、放射線が照射された部分にアルカリ可溶性のカルボン酸化合物が存在することで、その部分にある樹脂がカルボン酸化合物と一緒にアルカリ水溶液に溶解し易くなる。また、生成したカルボン酸化合物は、ポジ型感光性樹脂組成物に任意で含まれる保護樹脂の酸分解性基の分解を促進して、そのアルカリ可溶性官能基を再生させ、保護樹脂のアルカリ溶解性を増大させる。更に、カルボン酸化合物は、化学増幅レジストに一般に使用される光酸発生剤から生じる酸、例えばp-トルエンスルホン酸、1-プロパンスルホン酸などよりも分子構造が相対的に大きく、被膜中で拡散しにくい。これらが相乗的に作用する結果、未露光部と露光部のアルカリ溶解性の差を大きくすることができ、それにより低露光量でも高感度で高解像度のパターンを形成することができる。キノンジアジド化合物(C)は、単独で、又は2種類以上を組み合わせて使用することができる。ポジ型感光性樹脂組成物は、化学増幅レジストに一般に使用される光酸発生剤を実質的に含まないことが好ましく、当該光酸発生剤を含まずに感光剤としてキノンジアジド化合物(C)のみを含むことがより好ましい。「化学増幅レジストに一般に使用される光酸発生剤を実質的に含まない」とは、ポジ型感光性樹脂組成物に含まれる上記光酸発生剤の量が、樹脂成分の合計100質量部を基準として、0.2質量部以下、0.1質量部以下、又は0.05質量部以下であることを意味する。ポジ型感光性樹脂組成物が化学増幅レジストに一般に使用される光酸発生剤を実質的に含まない場合、プロセスの安定性が良好であるとともに、高感度を実現することができるため好ましい。
フッ素系界面活性剤(D)は特に限定されないが、フッ素化アルキル基及びフッ素化アルキレン基からなる群より選ばれる少なくとも1つのフッ素化炭化水素基と親水性基とを有する界面活性剤を使用することができる。そのようなフッ素系界面活性剤(D)としては、例えば、パーフルオロアルキルスルホン酸、部分フッ素化アルキルスルホン酸、パーフルオロアルキルカルボン酸、部分フッ素化アルキルカルボン酸、パーフルオロアルキルリン酸エステル、部分フッ素化アルキルリン酸エステル、パーフルオロアルキルトリメチルアンモニウム塩、部分フッ素化アルキルトリメチルアンモニウム塩、パーフルオロアルキルベタイン、部分フッ素化アルキルベタイン、パーフルオロアルキルEO付加物、及びフッ素テロマーアルコールが挙げられる。フッ素系界面活性剤(D)としては、パーフルオロアルキル基、部分フッ素化アルキル基、パーフルオロアルキレン基又は部分フッ素化アルキレン基と、スルホ基、カルボキシ基、リン酸基、アンモニウム基、オキシアルキレン基、ポリオキシアルキレン基等の親水性基とを分子内に有する単独重合体又は共重合体も使用することができる。フッ素系界面活性剤(D)は、単独で、又は2種類以上を組み合わせて使用することができる。
で表される含フッ素重合性単量体と、式(9)
で表される基を有する重合性単量体との共重合体(D1)である。
で表される重合性単量体が挙げられる。
で表される含フッ素重合性単量体と、式(12)
で表されるオキシアルキレン基を有する重合性単量体との共重合体(D2)である。
ポジ型感光性樹脂組成物は、黒色染料及び黒色顔料からなる群より選ばれる少なくとも1種の着色剤(E)を更に含んでもよい。着色剤(E)を含む感光性樹脂組成物を用いて有機EL素子に黒色の隔壁を形成することにより、有機ELディスプレイ等の表示装置の視認性を向上させることができる。この実施態様では、着色剤(E)が存在するために露光時の放射線の透過量が被膜の表面から内部にかけて急激に低下する。そのため、キノンジアジド化合物(C)由来のカルボン酸化合物は、被膜表面の近傍では比較的多く発生するが、被膜内部では発生しにくい。キノンジアジド化合物(C)由来のカルボン酸化合物は被膜中での拡散性が低いため、被膜表面の近傍に留まって露光部の被膜表面の溶解促進に寄与する。被膜内部は疎水性樹脂(A)の濃度が相対的に低いためにアルカリ可溶性が相対的に高い。そのため、被膜内部まで十分に放射線が透過しない場合であっても、この実施態様のポジ型感光性樹脂組成物を用いることにより、高感度で高精度の厚膜パターンを形成することができる。
ポジ型感光性樹脂組成物は任意成分として、溶解促進剤(F)、熱硬化剤、フッ素系界面活性剤(D)以外の第2界面活性剤、着色剤(E)以外の第2着色剤等を含むことができる。本開示において、任意成分は(A)~(E)のいずれにも当てはまらないものと定義する。
ポジ型感光性樹脂組成物は、現像時にアルカリ可溶性部分の現像液への溶解性を向上させるための溶解促進剤(F)をさらに含んでもよい。溶解促進剤(F)として、カルボキシ基を有する化合物及びフェノール性水酸基を有する化合物からなる群より選択される有機低分子化合物が挙げられる。溶解促進剤(F)は、単独で、又は2種類以上を組み合わせて使用することができる。
熱硬化剤として、熱ラジカル発生剤を使用することができる。好ましい熱ラジカル発生剤としては、有機過酸化物を挙げることができ、具体的にはジクミルパーオキサイド、2,5-ジメチル-2,5-ジ(tert-ブチルパーオキシ)ヘキサン、tert-ブチルクミルパーオキサイド、ジ-tert-ブチルパーオキサイド、1,1,3,3-テトラメチルブチルハイドロパーオキサイド、クメンハイドロパーオキサイド等の10時間半減期温度が100~170℃の有機過酸化物を挙げることができる。
ポジ型感光性樹脂組成物は、例えば塗工性を向上させるため、被膜の平滑性を向上させるため、又は被膜の現像性を向上させるために、フッ素系界面活性剤(D)以外の第2界面活性剤を含有することができる。第2界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル;ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアリールエーテル;ポリオキシエチレンジラウレート、ポリオキシエチレンジステアレート等のポリオキシエチレンジアルキルエステル等のノニオン系界面活性剤;及びオルガノシロキサンポリマーKP323、KP326、KP341(商品名、信越化学工業株式会社)が挙げられる。第2界面活性剤は、単独で、又は2種類以上を組み合わせて使用することができる。
ポジ型感光性樹脂組成物は、着色剤(E)以外の第2着色剤を含有することができる。第2着色剤としては、例えば、染料、有機顔料、及び無機顔料が挙げられる。第2着色剤は、目的に合わせて、本発明の効果を損なわない含有量で使用することができる。
〈溶媒(G)〉
ポジ型感光性樹脂組成物は、溶媒(G)に溶解又は分散させて溶液状態又は分散液状態のコーティング組成物として用いることができる。例えば、疎水性樹脂(A)及びアルカリ可溶性樹脂(B)を溶媒(G)に溶解して得られた溶液に、キノンジアジド化合物(C)、及びフッ素系界面活性剤(D)、並びに必要に応じて着色剤(E)、溶解促進剤(F)、熱硬化剤、その他界面活性剤等の任意成分を所定の割合で混合することにより、ポジ型感光性樹脂組成物を含むコーティング組成物を調製することができる。コーティング組成物は、溶媒(G)の量を変化させることにより、使用する塗布方法に適した粘度に調整することができる。
ポジ型感光性樹脂組成物を放射線リソグラフィーに使用する場合、まず、ポジ型感光性樹脂組成物を溶媒に溶解又は分散してコーティング組成物を調製する。次に、コーティング組成物を基板表面に塗布し、加熱等の手段により溶媒を除去して、被膜を形成することができる。基板表面へのコーティング組成物の塗布方法は特に限定されず、例えば、スプレー法、ロールコート法、スリット法、又はスピンコート法を使用することができる。
ポジ型感光性樹脂組成物は、被膜表面のアルカリ溶解性が被膜全体のアルカリ溶解性と比較して低い被膜を形成することができる。具体的には、ポジ型感光性樹脂組成物をプリベーク後の膜厚が3±0.3μmになるように塗布し、125℃で120秒プリベークして被膜を形成した後、30mJ/cm2の条件で露光し、温度23℃にて2.38質量%テトラメチルアンモニウムヒドロキシド水溶液で現像したときに、被膜表面層の溶解速度が被膜全体の溶解速度よりも低い。被膜表面層の溶解速度とは、上記被膜の膜厚が80%となるまで溶解させた時点での平均溶解速度であり、被膜全体の溶解速度とは、上記被膜の膜厚が30%となるまで溶解させた時点での平均溶解速度である。被膜の表面及び全体の平均溶解速度は、実施例に記載した手順により決定される。被膜表面層の溶解速度と被膜全体の溶解速度の差は、好ましくは3nm/秒以上、より好ましくは5nm/秒以上、更に好ましくは8nm/秒以上である。
一実施態様では、ポジ型感光性樹脂組成物をプリベーク後の膜厚が3±0.3μmになるように塗布し、125℃で120秒プリベークして被膜を形成した後、温度23℃にて2.38質量%テトラメチルアンモニウムヒドロキシド水溶液で60秒間アルカリ現像したときに、下式:
残膜率(%)=現像後の膜厚(μm)/現像前の膜厚(μm)
で定義される残膜率が90%以上、好ましくは95%以上、より好ましくは99%以上である。残膜率は未露光部の溶解性の指標であり、残膜率が高いほど露光部と未露光部の溶解性の差が大きく、高低差の大きい厚膜パターンを高精度で形成することができる。
ポジ型感光性樹脂組成物が着色剤(E)を含む実施態様において、ポジ型感光性樹脂組成物の硬化被膜の光学濃度(OD値)は、膜厚1μmあたり0.5以上であることが好ましく、0.7以上であることがより好ましく、1.0以上であることが更に好ましい。硬化被膜のOD値が膜厚1μmあたり0.5以上であれば、十分な遮光性を得ることができる。
一実施態様は、ポジ型感光性樹脂組成物の硬化物を含む有機EL素子隔壁である。ポジ型感光性樹脂組成物は着色剤(E)を含むことが好ましい。
一実施態様は、ポジ型感光性樹脂組成物の硬化物を含む有機EL素子絶縁膜である。ポジ型感光性樹脂組成物は着色剤(E)を含むことが好ましい。
一実施態様は、ポジ型感光性樹脂組成物の硬化物を含む有機EL素子である。ポジ型感光性樹脂組成物は着色剤(E)を含むことが好ましい。
実施例及び比較例で使用した原料を以下のとおり製造又は入手した。
装置名:Shodex(登録商標)GPC-101
カラム:Shodex(登録商標)LF-804
移動相:テトラヒドロフラン
流速:1.0mL/分
検出器:Shodex(登録商標)RI-71
温度:40℃
4-ヒドロキシフェニルメタクリレート(昭和電工株式会社「PQMA」)28.0g、及びN-シクロヘキシルマレイミド(株式会社日本触媒)7.89gを、溶媒である1-メトキシ-2-プロピルアセテート(株式会社ダイセル)77.1gに、重合開始剤としてV-601(富士フイルム和光純薬株式会社)3.66gを、1-メトキシ-2-プロピルアセテート(株式会社ダイセル)14.6gにそれぞれ完全に溶解させた。得られた2つの溶液を、300mLの3つ口型フラスコ中、窒素ガス雰囲気下で85℃に加熱した1-メトキシ-2-プロピルアセテート(株式会社ダイセル)61.2gに同時に2時間かけて滴下し、その後85℃で3時間反応させた。室温まで冷却した反応溶液を815gのトルエン中に滴下し、共重合体を沈殿させた。沈殿した共重合体をろ過により回収し、90℃で4時間真空乾燥し白色の粉体を33.4g回収した。得られたPCX-01の数平均分子量は6600、重量平均分子量は11600であった。
4-ヒドロキシフェニルメタクリレート(昭和電工株式会社「PQMA」)25.5g、及びN-シクロヘキシルマレイミド(株式会社日本触媒)4.50gを、溶媒である1-メトキシ-2-プロピルアセテート(株式会社ダイセル)77.1gに、重合開始剤としてV-601(富士フイルム和光純薬株式会社)3.66gを、1-メトキシ-2-プロピルアセテート(株式会社ダイセル)14.6gにそれぞれ完全に溶解させた。得られた2つの溶液を、300mLの3つ口型フラスコ中、窒素ガス雰囲気下で85℃に加熱した1-メトキシ-2-プロピルアセテート(株式会社ダイセル)61.2gに同時に2時間かけて滴下し、その後85℃で3時間反応させた。室温まで冷却した反応溶液を815gのトルエン中に滴下し、共重合体を沈殿させた。沈殿した共重合体をろ過により回収し、90℃で4時間真空乾燥し白色の粉体を32.4g回収した。得られたPCX-02eの数平均分子量は3100、重量平均分子量は6700、フェノール性水酸基当量は210であった。
4-ヒドロキシフェニルメタクリレート(昭和電工株式会社「PQMA」)15.9g、4-tert-ブチルジメチルシリルオキシフェニルメタクリレート(PQMA-TBDMS)16.6g、及びN-シクロヘキシルマレイミド(東京化成工業株式会社)4.62gを、溶媒であるイソプロピルアセテート(神港有機化学工業株式会社)55.8gに完全に溶解させた。重合開始剤としてV-601(富士フイルム和光純薬株式会社)2.86gを、イソプロピルアセテート(神港有機化学工業株式会社)4.29gに完全に溶解させた。得られた2つの溶液を、還流管が付いた300mLの3つ口型フラスコ中、窒素ガス雰囲気下で89℃に加熱したイソプロピルアセテート(神港有機化学工業株式会社)90.5gに、同時に2時間かけて滴下し、その後、89℃で4時間反応させた。室温まで冷却した反応溶液50gを、250gのヘキサンに滴下し、共重合体を沈殿させた。沈殿した共重合体をろ過により回収し、80℃で5時間真空乾燥し、白色の粉体(PCX-02e-TBDMS34)を9.73g回収した。得られたPCX-02e-TBDMS34の数平均分子量は3753、重量平均分子量は7581であった。PCX-02e-TBDMS34において、sが1以上の整数である式(1)で表される構造単位と式(2)で表される構造単位と式(3)で表される構造単位のモル比は、式(1):式(2):式(3)=32:7:61であり、全構造単位を基準として、アルカリ可溶性官能基を有する構造単位は61モル%であった。ケイ素原子の含有量は、PCX-02e-TBDMS34の質量を基準として、4.0質量%であった。
4-ヒドロキシフェニルメタクリレート(昭和電工株式会社「PQMA」)15.9g、4-トリエチルシリルオキシフェニルメタクリレート(PQMA-TES)16.6g、及びN-シクロヘキシルマレイミド(東京化成工業株式会社)4.62gを、溶媒であるイソプロピルアセテート(神港有機化学工業株式会社)55.8gに完全に溶解させた。重合開始剤としてV-601(富士フイルム和光純薬株式会社)2.86gを、イソプロピルアセテート(神港有機化学工業株式会社)4.29gに完全に溶解させた。得られた2つの溶液を、還流管が付いた300mLの3つ口型フラスコ中、窒素ガス雰囲気下で89℃に加熱したイソプロピルアセテート(神港有機化学工業株式会社)90.4gに、同時に2時間かけて滴下し、その後、89℃で4時間反応させた。室温まで冷却した反応溶液50gを、200gのヘキサンと50gのトルエンの混合溶媒に滴下し、共重合体を沈殿させた。沈殿した共重合体をろ過により回収し、80℃で5時間真空乾燥し、白色の粉体(PCX-02e-TES34)を9.49g回収した。得られたPCX-02e-TES34の数平均分子量は3847、重量平均分子量は7534であった。PCX-02e-TES34において、sが1以上の整数である式(1)で表される構造単位と式(2)で表される構造単位と式(3)で表される構造単位のモル比は、式(1):式(2):式(3)=32:7:61であり、全構造単位を基準として、アルカリ可溶性官能基を有する構造単位は61モル%であった。ケイ素原子の含有量は、PCX-02e-TES34の質量を基準として、4.0質量%であった。
4-ヒドロキシフェニルメタクリレート(昭和電工株式会社「PQMA」)12.1g、2-パーフルオロヘキシルエチルメタクリレート(東京化成工業株式会社)20.5g、及びN-シクロヘキシルマレイミド(東京化成工業株式会社)3.62gを、溶媒であるイソプロピルアセテート(神港有機化学工業株式会社)84.5gに完全に溶解させた。重合開始剤としてV-601(富士フイルム和光純薬株式会社)3.74gを、イソプロピルアセテート(神港有機化学工業株式会社)14.9gに完全に溶解させた。得られた2つの溶液を、還流管が付いた300mLの3つ口型フラスコ中、窒素ガス雰囲気下で89℃に加熱したイソプロピルアセテート(神港有機化学工業株式会社)51.0gに、同時に2時間かけて滴下し、その後、89℃で4時間反応させた。室温まで冷却した反応溶液50gを、250gのヘキサンに滴下し、共重合体を沈殿させた。沈殿した共重合体をろ過により回収し、80℃で5時間真空乾燥し、白色の粉体(PCX-02e-C6SFMA36)を5.58g回収した。得られたPCX-02e-C6SFMA36の数平均分子量は2869、重量平均分子量は5743であった。PCX-02e-C6SFMA36において、2-パーフルオロヘキシルエチルメタクリレートに由来する構造単位と式(2)で表される構造単位と式(3)で表される構造単位のモル比は36:6:58であり、全構造単位を基準として、アルカリ可溶性官能基を有する構造単位は58モル%であった。フッ素原子の含有量は、PCX-02e-C6SFMA36の質量を基準として、24質量%であった。
100mLの3つ口型フラスコ中で、製造例2のPCX-02e 10.0g、及び酸触媒としてp-トルエンスルホン酸のピリジニウム塩(東京化成工業株式会社)0.60gを、テトラヒドロフラン(富士フイルム和光純薬株式会社)50.0gに溶解させた。その後窒素ガス雰囲気下で氷冷し、2,3-ジヒドロフラン(東京化成工業株式会社)2.34gを1時間かけて滴下した。その後室温で4時間撹拌した。飽和炭酸水素ナトリウム水溶液で酸触媒を中和した後、水層を除去した。さらに有機層を水で2回洗浄した。その後、テトラヒドロフランを留去した。得られた固体を酢酸エチル50.0gに溶解させ、200gのトルエン中に滴下し、生成物を沈殿させた。沈殿物をろ過により回収し、80℃で4時間真空乾燥して白色の粉体10.0gを回収した。得られた粉体をプロピレングリコールモノメチルエーテルアセテートに溶解し、アルカリ可溶性官能基(フェノール性水酸基)が2-テトラヒドロフラニル基で保護された樹脂(PCX-02e-THF28)の固形分20質量%溶液を得た。得られたPCX-02e-THF28の数平均分子量は3700、重量平均分子量は6800、酸分解性基で保護されているフェノール性水酸基の割合は28モル%、少なくとも1つのフェノール性水酸基が酸分解性基で保護されている式(7)で表される構造単位の数は、PCX-02e-THF28の全構造単位数の25%であった。酸分解性基で保護されているフェノール性水酸基の割合は、熱重量示差熱分析装置(TG/DTA6200、株式会社日立ハイテクサイエンス)を用い、窒素ガス気流中、昇温速度10℃/分の条件下で室温から250℃まで昇温し、10分保持し、さらに昇温速度10℃/分の条件で400℃まで昇温したときの、260℃における樹脂の重量減少率(%)より算出した。
300mLの3つ口型フラスコに溶媒としてγ-ブチロラクトン(三菱ケミカル株式会社)75.2g、1分子中に少なくとも2個のエポキシ基を有する化合物としてEPICLON(登録商標)N-695(DIC株式会社、クレゾールノボラック型エポキシ樹脂、エポキシ当量214)37.8gを仕込み、窒素ガス雰囲気下、60℃で溶解させた。そこへヒドロキシ安息香酸化合物として3,5-ジヒドロキシ安息香酸(富士フイルム和光純薬株式会社)20.1g(エポキシ1当量に対して0.65当量)、及び反応触媒としてトリフェニルホスフィン(東京化成工業株式会社)0.166g(0.660mmol)を追加し、110℃で21時間反応させた。反応溶液を室温に戻し、γ-ブチロラクトンで固形分20質量%に希釈し、溶液をろ過して274.2gのエポキシ基及びフェノール性水酸基を有する樹脂(N695OH70)の溶液を得た。得られた反応物の数平均分子量は3000、重量平均分子量は5100、エポキシ当量は2200、フェノール性水酸基当量は161であった。
疎水性樹脂(A)として、製造例3のPCX-02e-TBDMS34、及び製造例4のPCX-02e-TES34(ケイ素含有基を有する樹脂)、並びに製造例5のPCX-02e-C6SFMA36(フッ素含有基を有する樹脂)を使用した。
アルカリ可溶性樹脂(B)として、製造例6のPCX-02e-THF28、製造例1のPCX-01、製造例2のPCX-02e、製造例7のN695OH70、及びEPICLON(登録商標)N-695(DIC株式会社、クレゾールノボラック型エポキシ樹脂、エポキシ当量214)を使用した。
キノンジアジド化合物(C)として、TS-150A及びTS-200A(4,4’-[1-[4-[1-(4-ヒドロキシフェニル)-1-メチルエチル]フェニル]エチリデン]ビスフェノール(TrisP-PA)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(1,2-ナフトキノンジアジド-5-スルホン酸)とのエステル、東洋合成工業株式会社);TPPA(4)-150DF(4,4’-[1-[4-[1-(4-ヒドロキシフェニル)-1-メチルエチル]フェニル]エチリデン]ビスフェノール(TrisP-PA)の1,2-ナフトキノンジアジド-4-スルホン酸エステル、東洋合成工業株式会社);並びにTHDPP-280(2-(4-ヒドロキシフェニル)-2-(2’,4’-ジヒドロキシフェニル)プロパンの1,2-ナフトキノンジアジド-5-スルホン酸エステル、東洋合成工業株式会社)を使用した。
フッ素系界面活性剤(D)として、メガファック(登録商標)F-562、メガファック(登録商標)F-554、メガファック(登録商標)R-40、メガファック(登録商標)F-563、及びメガファック(登録商標)F-559(全てDIC株式会社)を使用した。
着色剤として、黒色染料であるVALIFAST(登録商標)BLACK 3820(ソルベントブラック27のC.I.で規定される黒色染料、オリエント化学工業株式会社、表1における「VB3820」)、及びVALIFAST(登録商標)BLACK 3804(ソルベントブラック34のC.I.で規定される黒色染料、オリエント化学工業株式会社、表1における「VB3804」)を使用した。
溶解促進剤(F)としてフロログルシノールを使用した。
溶媒(G)としてγ-ブチロラクトン(GBL)及びプロピレングリコールモノメチルエーテルアセテート(PGMEA)の混合溶媒(GBL:PGMEA=40:60(質量比))を使用した。
実施例及び比較例で使用した評価方法は以下のとおりである。
ガラス基板(大きさ100mm×100mm×1mm)にポジ型感光性樹脂組成物を乾燥膜厚が3±0.3μmになるようにバーコートし、常温真空乾燥60秒間の後、蓋つきホットプレート上125℃で120秒加熱し溶媒を乾燥した(プリベーク)。乾燥膜厚を光学式膜厚測定装置(F20-NIR、フィルメトリクス株式会社)を用いて測定した後、超高圧水銀ランプを組み込んだ露光装置(商品名マルチライトML-251A/B、ウシオ電機株式会社)で30mJ/cm2の条件で露光した。露光量は紫外線積算光量計(商品名UIT-150 受光部 UVD-S365、ウシオ電機株式会社)を用いて測定した。その後、スピン現像装置(AD-1200、滝沢産業株式会社)を用い、温度23℃にて2.38質量%テトラメチルアンモニウムヒドロキシド水溶液で現像し、現像後の被膜の膜厚を光学式膜厚測定装置を用いて測定した。現像時間を変えてアルカリ現像を行うことにより、露光部の被膜の膜厚が80%となるまで又は30%となるまでの現像時間をそれぞれ得た。現像後の被膜の減少量(nm)を現像時間(秒)で割ってアルカリ溶解速度(nm/秒)を得た。露光部の被膜の膜厚が80%となるまで溶解させた時点の上記アルカリ溶解速度を、被膜表面層の平均溶解速度とし、露光部の被膜の膜厚が30%となるまで溶解させた時点の上記アルカリ溶解速度を、被膜全体の平均溶解速度とした。
ガラス基板(大きさ100mm×100mm×1mm)にポジ型感光性樹脂組成物を乾燥膜厚が3.0μmになるようにバーコートし、常温真空乾燥60秒間の後、蓋つきホットプレート上125℃で120秒加熱してプリベークを行った。超高圧水銀ランプを組み込んだ露光装置(商品名マルチライトML-251A/B、ウシオ電機株式会社)で石英製のフォトマスク(φ10μmの開口パターンを有するもの)を介して被膜を露光した。露光量は紫外線積算光量計(商品名UIT-150 受光部 UVD-S365、ウシオ電機株式会社)を用いて測定した。露光後、スピン現像装置(AD-1200、滝沢産業株式会社)を用い2.38質量%テトラメチルアンモニウムヒドロキシド水溶液で60秒間アルカリ現像を行なった。露光量を変えながら上記手順を繰り返して、現像後にガラス基板に完全に達するホール径10μmのパターンが形成できる最小露光量(mJ/cm2)を感度とした。
ガラス基板(大きさ100mm×100mm×1mm)にポジ型感光性樹脂組成物を乾燥膜厚が3.0μmになるようにバーコートし、常温真空乾燥60秒間の後、蓋つきホットプレート上125℃で120秒加熱してプリベークを行った。乾燥膜厚を光学式膜厚測定装置(F20-NIR、フィルメトリクス株式会社)を用いて測定した後、スピン現像装置(AD-1200、滝沢産業株式会社)を用い2.38質量%テトラメチルアンモニウムヒドロキシド水溶液で60秒間アルカリ現像を行なった。アルカリ現像後の膜厚を再び光学式膜厚測定装置(F20-NIR、フィルメトリクス株式会社)を用いて測定し、現像前後で溶解した膜厚(μm)を未露光部溶解性の指標とした。未露光部溶解性が0μmであることは、下式:
残膜率(%)=現像後の膜厚(μm)/現像前の膜厚(μm)
で定義される残膜率が100%であることと等価である。
ガラス基板(大きさ100mm×100mm×1mm)にポジ型感光性樹脂組成物を乾燥膜厚が約1.5μmになるようにスピンコートし、ホットプレート上125℃で120秒加熱してプリベークを行った。その後、窒素ガス雰囲気下250℃で60分硬化させることにより被膜を得た。硬化後の被膜のOD値を透過濃度計(BMT-1、サカタインクスエンジニアリング株式会社)で測定し、ガラスのみのOD値で補正を行って、被膜の厚さ1μm当たりのOD値に換算した。被膜の厚みは光学式膜厚測定装置(F20-NIR、フィルメトリクス株式会社)を用いて測定した。
[実施例1~14、比較例1~2]
表1に記載の組成で樹脂成分を溶媒(G)中で混合して溶解して得られた溶液に、表1に記載のキノンジアジド化合物(C)、フッ素系界面活性剤(D)又はその他の界面活性剤、着色剤(E)、及び溶解促進剤(F)を加えて、更に混合した。成分が溶解したことを目視で確認した後、孔径0.22μmのミリポアフィルターで濾過し、固形分濃度12質量%のポジ型感光性樹脂組成物を調製した。表1における組成の質量部は固形分換算値である。実施例1~14、及び比較例1~2のポジ型感光性樹脂組成物の評価結果を表1に示す。比較例2のポジ型感光性樹脂組成物は、塗工時にはじきが発生してパターンを形成することができなかったため評価していない。
[装置]
装置:Quantera II(アルバック・ファイ株式会社)
X線:Alモノクロ 100μm,25W,15kV
分析面積:100μm(Spot)
電子・イオン中和銃:ON
光電子取出し角:45度
[測定条件]
Depth profile
Ar2500+(アルゴンガスクラスタービーム:GCIB)加速電圧及びクラスター面積:5kV,17nA,2×2mm
Pass Energy:224eV
Step:0.1eV
Dwell:20ms
Sweep time:C,O(2);F(4);Si,Cr,N,S(10)
スパッタインターバル:0.25分×4サイクル/1分×5サイクル/3分×8サイクル
試料固定:銅クリップ
結合エネルギー補正については、C1sスペクトルのC-C,C-Hピークを284.6eVとした。
Claims (13)
- 疎水性樹脂(A)と、
アルカリ可溶性樹脂(B)と、
キノンジアジド化合物(C)と、
フッ素系界面活性剤(D)と
を含むポジ型感光性樹脂組成物であって、前記ポジ型感光性樹脂組成物をプリベーク後の膜厚が3±0.3μmになるように塗布し、125℃で120秒プリベークして被膜を形成した後、30mJ/cm2の条件で露光し、温度23℃にて2.38質量%テトラメチルアンモニウムヒドロキシド水溶液で現像したときに、被膜表面層の溶解速度が被膜全体の溶解速度よりも低く、前記被膜表面層の溶解速度とは、前記被膜の膜厚が80%となるまで溶解させた時点での平均溶解速度であり、前記被膜全体の溶解速度とは、前記被膜の膜厚が30%となるまで溶解させた時点での平均溶解速度である、ポジ型感光性樹脂組成物。 - 前記被膜表面層の溶解速度と前記被膜全体の溶解速度の差が3nm/秒以上である、請求項1に記載のポジ型感光性樹脂組成物。
- 前記疎水性樹脂(A)が、ケイ素含有基及びフッ素含有基からなる群より選ばれる少なくとも1つを有する樹脂である、請求項1又は2に記載のポジ型感光性樹脂組成物。
- 前記フッ素系界面活性剤(D)が、フッ素化アルキル基及びフッ素化アルキレン基からなる群より選ばれる少なくとも1つのフッ素化炭化水素基を有するアクリル系共重合体を含む、請求項1又は2に記載のポジ型感光性樹脂組成物。
- 前記アルカリ可溶性樹脂(B)が、アルカリ可溶性官能基を有する重合性単量体とその他の重合性単量体との共重合体、エポキシ基及びフェノール性水酸基を有する樹脂、又はそれらの組合せを含む、請求項1又は2に記載のポジ型感光性樹脂組成物。
- 黒色染料及び黒色顔料からなる群より選ばれる少なくとも1種の着色剤(E)を更に含む、請求項1又は2に記載のポジ型感光性樹脂組成物。
- 前記着色剤(E)を、樹脂成分の合計100質量部を基準として10質量部~150質量部含む、請求項8に記載のポジ型感光性樹脂組成物。
- 前記ポジ型感光性樹脂組成物の硬化被膜の光学濃度(OD値)が膜厚1μmあたり0.5以上である、請求項8に記載のポジ型感光性樹脂組成物。
- 請求項1又は2に記載のポジ型感光性樹脂組成物の硬化物を含む有機EL素子隔壁。
- 請求項1又は2に記載のポジ型感光性樹脂組成物の硬化物を含む有機EL素子絶縁膜。
- 請求項1又は2に記載のポジ型感光性樹脂組成物の硬化物を含む有機EL素子。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012220855A (ja) * | 2011-04-13 | 2012-11-12 | Nagase Chemtex Corp | 感放射線性樹脂組成物 |
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JP2016177027A (ja) * | 2015-03-19 | 2016-10-06 | 日立化成株式会社 | 感光性樹脂組成物、該感光性樹脂組成物を用いた形成したパターン硬化膜、及び該パターン硬化膜を撥インク性バンク膜として備える有機el用表示装置 |
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Publication number | Priority date | Publication date | Assignee | Title |
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