WO2015046295A1 - 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置及び有機ｅｌ表示装置 - Google Patents

感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置及び有機ｅｌ表示装置 Download PDF

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WO2015046295A1
WO2015046295A1 PCT/JP2014/075366 JP2014075366W WO2015046295A1 WO 2015046295 A1 WO2015046295 A1 WO 2015046295A1 JP 2014075366 W JP2014075366 W JP 2014075366W WO 2015046295 A1 WO2015046295 A1 WO 2015046295A1
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group
structural unit
resin composition
photosensitive resin
polymer
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PCT/JP2014/075366
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English (en)
French (fr)
Japanese (ja)
Inventor
知樹 松田
山田　悟
健太 山▲ざき▼
達也 霜山
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富士フイルム株式会社
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Priority to JP2015539293A priority Critical patent/JP6272338B2/ja
Priority to KR1020167007212A priority patent/KR101819625B1/ko
Priority to CN201480052174.0A priority patent/CN105917274B/zh
Publication of WO2015046295A1 publication Critical patent/WO2015046295A1/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133345—Insulating layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations

Definitions

  • the present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening
  • the present invention relates to a product and a method for producing a cured film using the product.
  • an interlayer insulating film is generally used to insulate between wirings arranged in layers. Is provided.
  • a material for forming the interlayer insulating film a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and a material having sufficient flatness is preferable (for example, , See Patent Document 1).
  • Patent Document 2 discloses a radiation-sensitive material including a copolymer having a repeating unit having a tertiary ester group and a repeating unit having an acid anhydride structure.
  • JP 2011-209681 A Japanese Patent Laid-Open No. 7-234511
  • the present invention is intended to solve such problems, and is a photosensitive resin composition capable of improving chemical resistance, lowering a relative dielectric constant, and further improving pattern dimension stability.
  • the purpose is to provide.
  • the polymer component in the photosensitive resin composition has a structural unit having a group in which an acid group is protected by an acid-decomposable group, and a crosslinkable group.
  • ⁇ 1> (A) a polymer component, (B) a photoacid generator, and (C) a solvent, (A) the polymer component includes at least one of the following (1) and (2), and Satisfy at least one of the following (3) and (4); (1) (a1) a polymer (A1) comprising a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a structural unit having a crosslinkable group, (2) a polymer (A2) containing the structural unit (a1) and a polymer (A3) containing the structural unit (a2); (3) At least one of the polymers (A1) to (A3) is a polymer containing (a4) a structural unit having a group that generates a carboxyl group by alkaline hydrolysis.
  • a polymer (A4) containing the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2) is included;
  • the photosensitive resin composition according to ⁇ 2>, wherein the carboxylic anhydride structure is a 5-membered or 6-membered cyclic carboxylic anhydride structure.
  • R A1a represents a substituent
  • n 1a R A1a s are independent and may be the same or different
  • Z 1a may be —C ( ⁇ O) —O—C ( Represents a monocyclic or polycyclic structure containing ⁇ O) —
  • n 1a represents an integer of 0 or more.
  • ⁇ 5> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the structural unit (a4) is represented by the following formula (1A) and / or (1B).
  • ⁇ 6> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the structural unit (a4) is represented by the formula (1A).
  • ⁇ 7> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein (A) the polymer component includes (a3) a structural unit having an acid group.
  • ⁇ 8> The photosensitive resin composition according to ⁇ 7>, wherein the proportion of the structural unit (a3) in the polymer component (A) is 5 to 20 mol%.
  • ⁇ 9> Any one of ⁇ 1> to ⁇ 8>, wherein the crosslinkable group contained in the structural unit (a2) is at least one selected from an epoxy group, an oxetanyl group, and —NH—CH 2 —OR 2 Wherein R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • the photoacid generator is an oxime sulfonate compound.
  • ⁇ 12> (1) A step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 11> on a substrate, (2) a step of removing the solvent from the applied photosensitive resin composition; (3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays, (4) developing the exposed photosensitive resin composition with an aqueous developer, and (5) a post-baking step of thermosetting the developed photosensitive resin composition; The manufacturing method of the cured film containing this.
  • ⁇ 13> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 11>, or a cured film formed by the method for producing a cured film according to ⁇ 12>.
  • ⁇ 14> The cured film according to ⁇ 13>, which is an interlayer insulating film.
  • ⁇ 15> A liquid crystal display device or an organic EL display device having the cured film according to ⁇ 13> or ⁇ 14>.
  • the present invention it is possible to provide a photosensitive resin composition that can improve chemical resistance, reduce the relative dielectric constant, and improve the dimensional stability of the pattern.
  • 1 shows a conceptual diagram of a configuration of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
  • the schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.
  • 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
  • 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
  • the photosensitive resin composition of the present invention is (A) a polymer component, (B) a photoacid generator, and (C) a solvent, wherein the (A) polymer component includes at least one of the following (1) and (2), and Satisfy at least one of 3) and (4); (1) (a1) a polymer (A1) comprising a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a structural unit having a crosslinkable group, (2) The polymer (A2) containing the structural unit (a1) and the polymer (A3) containing the structural unit (a2); (3) At least one of the polymers (A1) to (A3) is a polymer containing (a4) a structural unit having a group that generates a carboxyl group by alkaline hydrolysis.
  • the polymer (A4) containing the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2) is included;
  • the proportion of the structural unit (a2) is 10 to 40 mol% and the proportion of the structural unit (a4) is 1 to 20 mol% with respect to all the structural units constituting the polymer component (A). It is characterized by that.
  • ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can make chemical-resistance favorable, can make a dielectric constant low, and can make pattern dimension stability favorable can be provided.
  • pattern dimension stability refers to development conditions (for example, when developing with a developer (typically an alkaline aqueous solution) after performing an exposure process on a film obtained using a photosensitive resin composition. It means the variability of the pattern dimension with respect to the fluctuation of the development time, the alkali concentration of the developer, etc., and the smaller the fluctuation of the pattern dimension, the better.
  • High pattern dimensional stability is one of the important performance issues in practical use. In the present invention, the reason why high pattern dimensional stability can be obtained is presumed, but it is considered that the reason is that the (A) polymer component has the structural unit (a4) at a ratio of a specific ratio or more. It is done.
  • the structural unit (a4) is gradually changed to a hydrophilic structural unit under the action of hydrolysis with an alkaline developer, and the affinity of the polymer component (A) for the developer is gradually increased. Therefore, it is estimated that the development speed is controlled to a desired speed and stable development is realized.
  • the (A) polymer component is the structural unit (a2). ) And (a4) at a specific ratio. That is, the structural unit (a2) is a structural unit necessary for improving chemical resistance, but if it is too much, it is considered that the relative dielectric constant tends to increase and the dimensional stability tends to decrease. Moreover, although the said structural unit (a4) is a structural unit required in order to obtain favorable pattern dimensional stability, when too large, there exists a tendency to reduce chemical resistance and / or to raise a dielectric constant. Conceivable.
  • the polymer means a compound obtained by polymerizing 5 or more of one or more monomers (that is, having 5 or more repeating units) and having a molecular weight of 1,000 or more.
  • the polymer component (A) in the present invention refers to a collection of all the polymers contained in the composition. Therefore, the surfactant described later may correspond to the polymer component (A) in the present invention.
  • the weight average molecular weight of the polymer component is preferably 1,000 to 200,000, and more preferably 2,000 to 50,000.
  • the ratio of the polymer obtained by addition polymerization of the compound having a polymerizable unsaturated bond in the total mass of the polymer component (A) is preferably 60 to 100% by mass, and preferably 90 to 100% by mass. More preferred is 98 to 100% by mass.
  • a polymer obtained by addition polymerization of the compound having a polymerizable unsaturated bond is an ⁇ , ⁇ -unsaturated carboxylic acid (for example, (meth) acrylic acid, maleic acid, itaconic acid, etc.), an ester thereof, and an anhydride thereof. It is preferable that it is a polymer containing the structural unit derived from at least 1 sort (s).
  • a polymer component becomes a main component of the component except the solvent of the composition of this invention, and it is preferable to occupy 60 mass% or more of a total solid.
  • Examples of the polymer constituting the (A) polymer component in the present invention include the following (A1) to (A6).
  • any of the polymers (A1) to (A6) is preferably a polymer obtained by addition polymerization of a compound having a polymerizable unsaturated bond. Further, the total ratio of the polymers (A1) to (A5) in the total mass of the polymer component (A) is preferably 60 to 100% by mass, and more preferably 90 to 100% by mass. 98 to 100% by mass is particularly preferable.
  • the polymer component is (a1) a structural unit having an acid group protected by an acid-decomposable group, (a2) a structural unit having a crosslinkable group, and (a4) a carboxyl group by alkali hydrolysis. 1 type or more of polymers (henceforth a polymer (A1a)) which has the structural unit which has group are included.
  • the polymer (A1a) may contain (a3) a structural unit having an acid group.
  • the polymer component (A) may have at least one of the polymers (A2) to (A6). In this embodiment, it is preferable that content of polymers other than a polymer (A1a) is 10 mass% or less in (A) polymer component.
  • a polymer component includes (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group (hereinafter referred to as polymer (A1b)). And (a4) a structural unit having a group having a carboxyl group by alkali hydrolysis, and (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a cross-linking A polymer containing no structural unit having a functional group (hereinafter also referred to as polymer (A4)) is included.
  • the polymer (A1b) usually does not contain the structural unit (a4).
  • the polymer (A1b) and / or the polymer (A4) may further contain (a3) a structural unit having an acid group.
  • the polymer component (A) may have at least one of the polymers (A2), (A3), (A5), and (A6).
  • content of polymers other than a polymer (A1b) and a polymer (A4) is 10 mass% or less in (A) polymer component.
  • the polymer (A2a) usually does not contain the structural unit (a2).
  • the polymer (A3b) usually does not contain the structural unit (a1) and the structural unit (a4).
  • the polymer (A2a) and / or the polymer (A3b) may further contain the structural unit (a3).
  • the polymer component (A) may have at least one of the polymers (A4) to (A6).
  • content of polymers other than a polymer (A2a) and a polymer (A3b) is 10 mass% or less in (A) polymer component.
  • a polymer component includes (a1) a polymer containing a structural unit having an acid group protected by an acid-decomposable group (hereinafter also referred to as polymer (A2b)), and (a2) a crosslinkable group And (a4) a polymer (hereinafter, also referred to as polymer (A3a)) containing a structural unit having a group that generates a carboxyl group by alkali hydrolysis.
  • the polymer (A2b) usually does not contain the structural unit (a2) and the structural unit (a4). Further, the polymer (A3a) usually does not contain the structural unit (a1).
  • the polymer (A2b) and / or the polymer (A3a) may further contain the structural unit (a3).
  • the polymer component (A) may have at least one of the polymers (A4) to (A6).
  • content of polymers other than a polymer (A2b) and a polymer (A3a) is 10 mass% or less in (A) polymer component.
  • a polymer component includes (a1) a polymer containing a structural unit having an acid group protected by an acid-decomposable group (hereinafter also referred to as polymer (A2b)), and (a2) a crosslinkable group A polymer containing a structural unit (hereinafter also referred to as polymer (A3b)), (a4) a structural unit having a group that generates a carboxyl group by alkali hydrolysis, and (a1) an acid group is acid-decomposed. And a polymer having no structural unit having a group protected by a functional group and (a2) a crosslinkable group (hereinafter also referred to as polymer (A4)).
  • the polymer (A2b) usually does not contain the structural unit (a2) and the structural unit (a4).
  • the polymer (A3b) usually does not contain the structural unit (a1) and the structural unit (a4). At least one of the polymer (A2b), the polymer (A3b) and the polymer (A4) may further contain the structural unit (a3).
  • composition ratio of the polymer (A2b) to the polymer (A3b) is (mass ratio (polymer (A2b) / polymer)).
  • (A3b)) is preferably 0.2 to 5, and more preferably 0.25 to 5.
  • the (A) polymer component may have the said polymer (A5) and / or (A6).
  • content of polymers other than a polymer (A2b), a polymer (A3b), and a polymer (A4) is 10 mass% or less in (A) polymer component.
  • the content of the structural unit (a1) is preferably 3 to 80 mol%, preferably 8 to 75 mol% in the total structural units of the polymer component (A) from the viewpoint of improving sensitivity. Is more preferable, and 15 to 65 mol% is more preferable.
  • the content of the structural unit (a2) is from 10 to 40 mol%, more preferably from 10 to 35 mol%, further preferably from 15 to 35 mol%, based on all the structural units of the polymer component (A). 35 mol% is still more preferable.
  • the content of the structural unit (a4) is 1.0 to 20 mol%, more preferably 1.0 to 15 mol%, and more preferably 1.0 to 10 mol% in all the structural units of the polymer component (A).
  • the content of the structural unit (a3) is preferably from 5 to 20 mol%, more preferably from 5 to 15 mol%, more preferably from 8 to 15 mol% is more preferable.
  • the total content of the structural units (a1), (a2) and (a4) is preferably 20 to 100 mol%, more preferably 30 to 90 mol%, based on the total structural units of the polymer component (A).
  • the total content of the structural units (a1), (a2), (a3), and (a4) is preferably 20 to 100 mol%, and preferably 30 to 100 mol%, based on the total structural units of the polymer component (A). Is more preferable.
  • the molecular weight of the polymer contained in the polymer component is a weight average molecular weight in terms of polystyrene, preferably in the range of 1,000 to 200,000, more preferably in the range of 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value.
  • the ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
  • the weight average molecular weight of the compound used in the present invention is defined as a polystyrene converted value by GPC measurement.
  • the weight average molecular weight and number average molecular weight are, for example, HLC-8220 (manufactured by Tosoh Corporation), TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6.0 mm ID ⁇ 15.0 cm) as a column, and eluent. It can be determined by using tetrahydrofuran (THF).
  • HLC-8220 manufactured by Tosoh Corporation
  • TSKgel Super AWM-H manufactured by Tosoh Corporation, 6.0 mm ID ⁇ 15.0 cm
  • THF tetrahydrofuran
  • (A) Production Method of Polymer Component >> also, various methods are known for the synthesis method of the polymer component (A). For example, in order to form at least the structural units represented by the above (a1) and (a2), It can be synthesized by polymerizing a radical polymerizable monomer mixture containing the radical polymerizable monomer used in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
  • the polymer component (A) preferably contains 50 mol% or more, more preferably 80 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units. preferable.
  • the polymer component has at least one structural unit (a1) having a group in which an acid group is protected by an acid-decomposable group.
  • a polymer component has a structural unit (a1), it can be set as the photosensitive resin composition in which pattern formation by an exposure and image development process is possible.
  • the “group in which the acid group is protected with an acid-decomposable group” in the present invention those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
  • Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
  • Specific acid-decomposable groups include groups that are relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group described later) or an acid.
  • a group that is relatively difficult to decompose for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group
  • a tertiary alkyl group such as a tert-butyl ester group
  • a tertiary alkyl carbonate group such as a tert-butyl carbonate group
  • the structural unit (a1) is preferably a structural unit having a protected carboxyl group protected with an acid-decomposable group or a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.
  • the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order. To do.
  • the structural unit (a1-1) is a structural unit having a protected carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
  • the structural unit having a carboxyl group that can be used for the structural unit (a1-1) is not particularly limited, and a known structural unit can be used.
  • Examples thereof include a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid. It is done.
  • the structural unit (a1-1-1) used as the structural unit having a carboxyl group will be described.
  • ⁇ (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>>>>>
  • the unsaturated carboxylic acid used in the present invention include those listed below. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid. And leuoxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, and the like.
  • the unsaturated dicarboxylic acid examples include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
  • the unsaturated carboxylic acid may be a mono (2- (meth) acryloyloxyalkyl) ester of a polyvalent carboxylic acid.
  • succinic acid mono (2-acryloyloxyethyl)
  • succinic acid mono 2-methacryloyloxyethyl
  • mono (2-acryloyloxyethyl) phthalate mono (2-methacryloyloxyethyl) phthalate and the like.
  • the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends thereof.
  • unsaturated carboxylic acid acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
  • acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyl Roxyethyl hexahydrophthalic acid or 2- (meth) acryloyloxyethyl phthalic acid is preferably used, and acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid is preferably used. More preferred.
  • the structural unit (a1-1-1) may be composed of one type alone, or may be composed of two or more types.
  • acid-decomposable group that can be used for the structural unit (a1-1) >>>>>
  • the acid-decomposable group that can be used for the structural unit (a1-1) the acid-decomposable groups described above can be used.
  • the acid-decomposable group is preferably a group having a structure protected in the form of an acetal.
  • the carboxyl group is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, the basic physical properties of the photosensitive resin composition, particularly the sensitivity and pattern shape, the formation of contact holes, the storage stability of the photosensitive resin composition
  • the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10).
  • the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10)
  • the entire protected carboxyl group is — (C ⁇ O) —O—CR 101
  • the structure is R 102 (OR 103 ).
  • R 101 and R 102 each independently represents a hydrogen atom, an alkyl group or an aryl group
  • R 103 represents an alkyl group or an aryl group
  • R 101 or R 102 and R 103 may be linked to form a cyclic ether.
  • R 101 and R 102 each independently represent a hydrogen atom, an alkyl group, or an aryl group.
  • R 103 represents an alkyl group or an aryl group.
  • R 101 or R 102 may form a cyclic ether linked and the R 103.
  • the alkyl group may be linear, branched or cyclic.
  • R 101 and R 102 are preferably a hydrogen atom or an alkyl group, and at least one of R 101 and R 102 preferably represents an alkyl group. It is preferable that one of R 101 and R 102 is a hydrogen atom or a methyl group, and particularly preferably one of which is the other is a methyl group with a hydrogen atom.
  • R 103 is preferably an alkyl group or an aryl group, and particularly preferably an alkyl group.
  • the linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
  • the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms.
  • Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
  • the alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group.
  • R 101 , R 102 and R 103 When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group, and a naphthyl group.
  • the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
  • the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is straight.
  • the alkyl group is a chain or branched chain, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent. These substituents may be further substituted with the above substituents.
  • R 101 , R 102 and R 103 represent an aryl group
  • the aryl group preferably has 6 to 12 carbon atoms, and preferably 6 to 10 carbon atoms. More preferred.
  • the aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
  • R 101 , R 102 and R 103 can be bonded together to form a ring together with the carbon atom to which they are bonded.
  • Examples of the ring structure when R 101 and R 102 , R 101 and R 103 or R 102 and R 103 are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
  • radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-10) a commercially available one may be used, or it may be synthesized by a known method. Things can also be used. For example, it can be synthesized by the synthesis method described in paragraph Nos. 0037 to 0040 of JP2011-212494A, the contents of which are incorporated herein.
  • a first preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (1-11).
  • R 1 and R 2 each represent a hydrogen atom, an alkyl group or an aryl group, at least either one of R 1 and R 2 represent an alkyl group or an aryl group, R 3 Represents an alkyl group or an aryl group, and R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or Represents an arylene group.
  • R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred.
  • R 1 and R 2 are aryl groups, a phenyl group is preferred.
  • R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
  • X represents a single bond or an arylene group, and a single bond is preferable.
  • a second preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (1-12).
  • Formula (1-12) (In the formula (1-12), R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenylene group, and R 122 to R 128 each independently represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms.) R 121 is preferably a hydrogen atom or a methyl group. L 1 is preferably a carbonyl group. R 122 to R 128 are preferably hydrogen atoms.
  • R represents a hydrogen atom or a methyl group.
  • the structural unit (a1-2) is a structural unit (a1-2-1) having a protected phenolic hydroxyl group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below.
  • ⁇ (a1-2-1) Structural Unit Having Phenolic Hydroxyl Group examples include a hydroxystyrene structural unit and a structural unit in a novolac resin.
  • a structural unit derived from hydroxystyrene or ⁇ -methylhydroxystyrene includes: It is preferable from the viewpoint of sensitivity.
  • a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.
  • R 220 represents a hydrogen atom or a methyl group
  • R 221 represents a single bond or a divalent linking group
  • R 222 represents a halogen atom or a straight chain having 1 to 5 carbon atoms or Represents a branched alkyl group
  • a represents an integer of 1 to 5
  • b represents an integer of 0 to 4
  • a + b is 5 or less
  • R 222 is 2 or more, these R 222 may be different from each other or the same.
  • R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
  • R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved.
  • the divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like.
  • R 221 is a single bond, a methylene group, or an ethylene group.
  • the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.
  • A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production.
  • the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
  • R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
  • B represents 0 or an integer of 1 to 4;
  • acid-decomposable group that can be used for the structural unit (a1-2) >>>>>
  • the acid-decomposable group that can be used for the structural unit (a1-2) as with the acid-decomposable group that can be used for the structural unit (a1-1), known ones can be used. It is not limited.
  • a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability.
  • the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above general formula (a1-10).
  • the protected phenolic hydroxyl group as a whole is —Ar—O—CR 101 R
  • the structure is 102 (OR 103 ).
  • Ar represents an arylene group.
  • Examples of the radical polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include paragraph number 0042 of JP2011-215590A. And the like.
  • a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
  • acetal protecting group for the phenolic hydroxyl group examples include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group.
  • 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually or in combination of 2 or more types.
  • the radical polymerizable monomer used for forming the structural unit (a1-2) a commercially available one may be used, or one synthesized by a known method may be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.
  • the structural unit (a1-1) is characterized by faster development than the structural unit (a1-2). Therefore, when it is desired to develop quickly, the structural unit (a1-1) is preferable. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2).
  • the polymer component has a structural unit (a2) having a crosslinkable group, and the structural unit (a2) is 10 to 40 with respect to all the structural units constituting the (A) polymer component. Contains mol%.
  • the crosslinkable group is defined as a group that can react with each other by a heat treatment to form a covalent bond, or a functional group that can react with an acid group to form a covalent bond.
  • the heat treatment is preferably a step (post-bake step) of thermosetting after development.
  • the temperature at which the structural unit having a crosslinkable group starts thermal crosslinking is preferably, for example, 70 to 200 ° C., more preferably 90 to 180 ° C.
  • the crosslinking initiation temperature of a structural unit derived from glycidyl methacrylate is 115 ° C.
  • the crosslinking initiation temperature of a structural unit derived from 3-ethyl-3-oxetanylmethyl methacrylate described later is 151 ° C.
  • These crosslinking initiation temperatures can be measured using, for example, real-time infrared spectroscopy (RT-IR). For example, it can be measured using FTS60A / 896 or FTS7000 manufactured by Digilab. For example, the following measuring methods are mentioned.
  • Each photosensitive resin composition is slit-coated on an aluminum plate (mirror finish, thickness: 100 ⁇ m), then pre-baked on a hot plate at 95 ° C. for 140 seconds to volatilize the solvent, and the photosensitive resin composition layer is formed into a film thickness It was formed to 4.0 ⁇ m, a Digilab FTS7000 was equipped with a Digilab Spectra Mono and a reflective heating stage with a temperature controller made by Systems Engineering, and time-resolved FT-IR measurement (integration: 10 Scan / spectra, Time resolution: 10 sec / spectra, detector: TGS).
  • Preferred embodiments of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene.
  • the (A-1) polymer component preferably contains a structural unit containing at least one of an epoxy group and an oxetanyl group, and a structural unit containing an epoxy group It is more preferable to contain. In more detail, the following are mentioned.
  • the (A) polymer component preferably contains a structural unit having an epoxy group and / or an oxetanyl group (hereinafter also referred to as a structural unit (a2-1)).
  • the structural unit (a2-1) may have at least one epoxy group or oxetanyl group in one structural unit, and includes one or more epoxy groups, one or more oxetanyl groups, and two or more epoxy groups.
  • Group may have two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and a total of epoxy groups and / or oxetanyl groups It is more preferable to have one or two, and it is even more preferable to have one epoxy group or one oxetanyl group.
  • radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, and glycidyl ⁇ -n-propyl acrylate.
  • radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Examples thereof include acrylate esters and compounds described in paragraph No. 0027 of JP2012-088459A, the contents of which are incorporated herein.
  • radical polymerizable monomer used for forming the structural unit (a1-2-1) having an epoxy group and / or oxetanyl group include a monomer having a methacrylate structure and an acrylate ester. A monomer containing a structure is preferred.
  • glycidyl methacrylate 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl.
  • Benzyl glycidyl ether, acrylic acid (3-ethyloxetane-3-yl) methyl, and methacrylic acid (3-ethyloxetane-3-yl) methyl are from the viewpoint of improving the copolymerization reactivity and various properties of the cured film. preferable.
  • These structural units can be used individually by 1 type or in combination of 2 or more types.
  • R represents a hydrogen atom or a methyl group.
  • (a2-2) Structural unit having an ethylenically unsaturated group >>>
  • the structural unit (a2) having a crosslinkable group there may be mentioned the structural unit (a2-2) having an ethylenically unsaturated group.
  • the structural unit (a2-2) is preferably a structural unit having an ethylenically unsaturated group in the side chain, and a structural unit having an ethylenically unsaturated group at the terminal and having a side chain having 3 to 16 carbon atoms. More preferred.
  • the polymer component (A) used in the present invention is a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Is also preferable.
  • R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • the structural unit (a2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).
  • Formula (a2-30) (In general formula (a2-30), R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) R 2 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • R 2 include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.
  • the polymer component has (a4) one or more structural units having a group that generates a carboxyl group by alkaline hydrolysis, and the structural unit (a4) comprises (A) all of the constituents of the polymer component. It is contained in an amount of 1.0 to 20 mol% based on the structural unit.
  • the structural unit (a4) is converted into a structural unit having a carboxyl group by the action of alkali hydrolysis.
  • a standard solution JIS standard, aqueous solution containing K0022
  • a structural unit having a monomer change rate of 80% or more is defined as a structural unit that satisfies the conditions of the present invention.
  • the analytical instrument for example, liquid chromatography can be used, and the reaction rate can be calculated from the measured peak integrated value (area) of the monomer.
  • the structural unit represented by the following structural formula (a4-1) has a rate of change of 80% or more when the alkali hydrolyzability of the corresponding monomer (a4-1m) is measured by the above measuring method.
  • the structural unit is determined to be a structural unit corresponding to the structural unit (a4).
  • the group that generates a carboxyl group by alkali hydrolysis is not limited to a specific structure as long as the above hydrolyzable conditions are satisfied.
  • Specific examples include carboxylic anhydrides, cyclic or acyclic esters, and acid halides. , Groups having a structure such as carbamate, sulfonic anhydride, cyclic or acyclic sulfonate, cyclic or acyclic sulfinate, alkoxysilyl, and the like.
  • the group that generates a carboxyl group by alkaline hydrolysis is preferably a group having a carboxylic acid anhydride structure or a group having a lactone structure (that is, a cyclic ester structure), and preferably a group having a carboxylic acid anhydride structure. More preferred is a group having a 5-membered or 6-membered cyclic carboxylic acid anhydride structure.
  • the carboxylic acid anhydride structure may be either chain or cyclic, but is a cyclic carboxylic acid anhydride structure. It is preferable.
  • the number of ring members is preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and particularly preferably a 5-membered ring.
  • other ring structures may be condensed to the cyclic carboxylic acid anhydride structure to form a polycyclic structure, but it is preferable that no polycyclic structure is formed.
  • the other ring structures are condensed in a form that forms a bicyclo structure or a spiro structure, and the number of other ring structures that are condensed. Is preferably 1 to 5, and more preferably 1 to 3.
  • examples of other ring structures include a cyclic hydrocarbon group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, and the like.
  • the heterocyclic group is not particularly limited, and examples thereof include those having one or more heteroatoms out of the atoms constituting the ring or aromatic heterocyclic groups.
  • heterocyclic group a 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring is especially preferable.
  • the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include an oxolane ring, an oxane ring, and a dioxane ring.
  • the carboxylic anhydride structure used in the present invention may or may not have a substituent, but preferably does not have a substituent.
  • substituents include, but are not limited to, for example, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, Examples include a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferred are an alkyl group having 1 to 4 carbon atoms and a cyano group.
  • the alkyl group a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms is preferable. More preferred are ⁇ 3 alkyl groups.
  • the number of substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2.
  • the carboxylic anhydride structure used in the present invention has a plurality of substituents, the plurality of substituents may be the same as or different from each other. Further, when another ring structure is condensed to the carboxylic acid anhydride structure, the other ring structure may have a substituent.
  • the structural unit having a carboxylic acid anhydride structure used in the present invention preferably includes a partial structure represented by the following general formula (1).
  • General formula (1) (In the general formula (1), R A1a represents a substituent, and n 1a R A1a s are independent and may be the same or different.
  • Z 1a is —C ( ⁇ O) —O—C Represents a monocyclic or polycyclic structure containing ( ⁇ O) —, and n 1a represents an integer of 0 or more.)
  • R A1a represents a substituent, and n 1a R A1a s are independent and may be the same or different.
  • R A1a has the same meaning as the substituent that the carboxylic anhydride structure described above may have, and the preferred range is also the same.
  • Z 1a represents a monocyclic or polycyclic structure containing —C ( ⁇ O) —O—C ( ⁇ O) —, and preferably represents a monocyclic structure.
  • Z 1a represents a monocyclic structure, it preferably forms a 5- to 7-membered ring, more preferably forms a 5- or 6-membered ring, and particularly preferably forms a 5-membered ring.
  • n 1a represents an integer of 0 or more, preferably an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
  • a plurality of substituents may be the same as or different from each other. A plurality of substituents may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
  • Rx represents a hydrogen atom, a methyl group, a CH 2 OH group, or a CF 3 group.
  • the structural unit (a4) is preferably represented by the following formula (1A) or (1B), and particularly preferably represented by the formula (1A).
  • composition of the present invention structural units having two or more carboxylic anhydride structures may be used in combination.
  • the lactone structure is not particularly limited as long as the hydrolyzability condition is satisfied.
  • the lactone structure used in the present invention is preferably a lactone structure that forms a 5- to 7-membered ring, and more preferably a lactone structure that forms a 5-membered or 6-membered ring.
  • a lactone structure forming a 5- to 7-membered ring may be condensed with another ring structure on the lactone structure to form a polycyclic structure.
  • other ring structures are not condensed to the lactone structure.
  • the lactone structure forming a 5- to 7-membered ring is condensed with another ring structure
  • the other ring structure is preferably condensed so as to form a bicyclo structure or a spiro structure.
  • examples of other ring structures include a cyclic hydrocarbon group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, and the like.
  • the heterocyclic group is not particularly limited, and examples thereof include those having one or more heteroatoms out of the atoms constituting the ring or aromatic heterocyclic groups.
  • heterocyclic group a 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring is especially preferable.
  • the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include an oxolane ring, an oxane ring, and a dioxane ring.
  • the number of the other ring structures condensed to the lactone structure is preferably 1 to 5 1 to 3 are more preferable.
  • the lactone structure used in the present invention may or may not have a substituent, but preferably does not have a substituent.
  • substituents include, but are not limited to, for example, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, Examples include a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferred are an alkyl group having 1 to 4 carbon atoms and a cyano group.
  • the alkyl group a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms is preferable. More preferred are ⁇ 3 alkyl groups.
  • the number of substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2.
  • the lactone structure used in the present invention has a plurality of substituents, the plurality of substituents may be the same as or different from each other. Further, when another ring structure is condensed to the lactone structure, this other ring structure may have a substituent.
  • the structural unit having a lactone structure used in the present invention preferably contains a partial structure represented by the following general formula (2-1).
  • Formula (2-1) (In General Formula (2-1), R A1 represents a substituent, and n1 R A1 s are independent and may be the same or different. Z 1 is —O—C ( ⁇ O) — And n1 represents an integer of 0 or more.)
  • R A1 represents a substituent, and n1 R A1 s are independent and may be the same or different.
  • R A1 has the same meaning as the substituent that the above-mentioned lactone structure may have, and the preferred range is also the same.
  • Z 1 represents a monocyclic or polycyclic structure containing —O—C ( ⁇ O) —, and preferably represents a monocyclic structure.
  • the monocyclic structure is preferably a lactone structure that forms a 5- to 7-membered ring, and more preferably a lactone structure that forms a 5-membered or 6-membered ring.
  • the polycyclic structure preferably has a condensed lactone structure with another cyclic structure forming a bicyclo structure or a spiro structure.
  • the other ring structures are synonymous with the other ring structures described above, and the preferred ranges are also the same.
  • n1 represents an integer of 0 or more, preferably an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
  • a plurality of substituents may be the same as or different from each other.
  • a plurality of substituents may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.
  • the structural unit (a4) is a structural unit containing a lactone structure, it is preferably represented by the following general formula (2-2).
  • Formula (2-2) (In the general formula (2-2), R X1 represents a hydrogen atom or an alkyl group. R A2 represents a substituent, and n2 R A2 s are independent and may be the same or different. 1 represents a single bond or a divalent linking group, Z 2 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —, and n2 represents an integer of 0 or more. ) In general formula (2-2), R X1 represents a hydrogen atom or an alkyl group.
  • alkyl group a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
  • the alkyl group may have a substituent.
  • a hydroxyl group or a halogen atom is preferable.
  • R A2 represents a substituent, and n2 R A2 s are independent and may be the same or different.
  • R A2 has the same meaning as the substituent that the lactone structure described above may have, and the preferred range is also the same.
  • a 1 represents a single bond or a divalent linking group.
  • Examples of the divalent linking group include a linear, branched or cyclic alkylene group, an arylene group, —O—, —COO—, —S—, —NR ′′ —, —CO—, and —NR ′′ CO—. , —SO 2 — and the like, or a combination of these groups.
  • R ′′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom.
  • Examples of the divalent linking group include —O—, —COO—, —S—, —NH— and At least one of —CO— or a group thereof and — (CH 2 ) m — (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4) Groups consisting of combinations are preferred.
  • Z 2 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —, and has the same meaning as Z 1 in general formula (2-1). The preferred range is also the same.
  • n2 represents an integer of 0 or more, and is synonymous with n1 in general formula (1), and the preferred range is also the same.
  • the structural unit (a4) is a structural unit containing a lactone structure, it is preferably represented by the following general formula (2-3).
  • General formula (2-3) (In the general formula (2-3), R X2 represents a hydrogen atom or an alkyl group. R A3 represents a substituent, and n3 R A3 s are independent and may be the same or different. 2 represents a single bond or a divalent linking group, Z 3 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —, and n3 represents an integer of 0 or more.
  • X 1 represents an oxygen atom or —NR ′′ —.
  • R ′′ represents a hydrogen atom or an alkyl group.
  • R A3 represents a substituent, and n3 R A3 s are independent and may be the same or different.
  • R A3 has the same meaning as the substituent that the lactone structure described above may have, and the preferred range is also the same.
  • a 2 represents a single bond or a divalent linking group.
  • the divalent linking group is synonymous with the case where A 1 in the general formula (2-2) represents a divalent linking group.
  • a preferred divalent linking group is at least one of —COO— and —CO—, or these groups, and — (CH 2 ) m — (m is an integer of 1 to 10, preferably 1 to 6.
  • a 2 in the general formula (2-3) is preferably a single bond.
  • Z 3 represents a monocyclic or polycyclic structure containing a group represented by —O—C ( ⁇ O) —, and has the same meaning as Z 1 in general formula (2-1). The preferred range is also the same.
  • n3 represents an integer of 0 or more, and is synonymous with n1 in general formula (2-1), and the preferred range is also the same.
  • X 1 represents an oxygen atom or —NR ′′ —, preferably an oxygen atom.
  • R ′′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferable.
  • the structure represented by the general formula (2-1) preferably includes a structure represented by any one of the following general formulas (LC1-1) to (LC1-21). More preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), Particularly preferred structures are (LC1-1), (LC1-4), and (LC1-17).
  • the structural unit (a4) includes such a structure, the relative dielectric constant can be further lowered while improving the chemical resistance of the composition of the present invention.
  • (Rb 2 ) represents a substituent, which may or may not have ( That is, in the general formulas (LC1-1) to (LC1-21), n4 is 0).
  • the preferred substituent (Rb 2 ) is synonymous with the substituent that the above-mentioned lactone structure may have, and the preferred range is also the same.
  • n4 has the same meaning as n1 in the general formula (2-1), and the preferred range is also the same.
  • the structural unit having a lactone structure usually has an optical isomer, but any optical isomer may be used.
  • One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
  • the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.
  • the structural unit (a4) when it has a lactone structure, it is preferably represented by the following formula (2A), (2B), (2C) or (2D), and represented by the formula (2A). More preferably.
  • the composition of the present invention may have two or more structural units as the structural unit (a4).
  • a structural unit having an acid anhydride structure and a structural unit having a lactone structure may be used in combination. it can.
  • the total amount is a numerical range of the structural unit (a4) mentioned later.
  • the polymer component preferably contains (a3) a structural unit having an acid group.
  • the acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
  • Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Examples include amide groups, sulfonylimide groups, and the like, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
  • the structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. .
  • the polymer component contains (a3) a structural unit having an acid group
  • at least one of the polymers (A1) to (A4) has the above structural unit (a3).
  • a polymer having none of the structural units (a1), (a2) and (a4) and having the structural unit (a3) (hereinafter, also referred to as polymer (A5)) can be used as (A ) It may be contained in the polymer component.
  • the polymer (A5) is preferably a resin having a carboxyl group in the side chain.
  • a resin having a carboxyl group in the side chain For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048
  • methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.
  • benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / Benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzine Methacrylate / methacrylic acid copolymer and the like.
  • Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein. These polymers may contain only 1 type and may contain 2 or more types.
  • ARUFON UC-3000 commercially available ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.) Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586, Joncryl 67 (above, manufactured by BASF) and the like can also be used.
  • a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.
  • a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group for example, compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.
  • the polymer component (A) may have other structural units (a5) in addition to the structural units (a1), (a2), (a4) and (a3). Good.
  • the polymer component (A) has the structural unit (a5), at least one of the polymers (A1) to (A5) may have the structural unit (a5).
  • a polymer having no structural unit (a1) to (a4) and having the structural unit (a5) also referred to as polymer (A6)
  • it is contained in the polymer component (A). Also good.
  • the raw material monomer for forming the structural unit (a5) is not particularly limited, and examples thereof include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, and unsaturated compounds. Examples thereof include dicarboxylic acid diesters, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, and other unsaturated compounds.
  • the monomer which becomes a structural unit (a5) can be used individually or in combination of 2 or more types.
  • the structural unit (a5) is styrene, methyl styrene, ⁇ -methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, or methyl (meth) acrylate.
  • styrenes and groups having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics.
  • Specific examples include styrene, methylstyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.
  • (meth) acrylic acid alkyl ester is preferable as the other structural unit (a5) from the viewpoint of adhesion.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
  • the photosensitive resin composition of the present invention contains (B) a photoacid generator.
  • the photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • the photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.
  • photoacid generator examples include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation.
  • photoacid generators can be used singly or in combination of two or more.
  • trichloromethyl-s-triazines diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-212494A. These can be illustrated and their contents are incorporated herein.
  • Preferred examples of the oxime sulfonate compound that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1-1).
  • General formula (B1-1) (In the general formula (B1-1), R 21 represents an alkyl group or an aryl group. The wavy line represents a bond with another group.)
  • any group may be substituted, and the alkyl group in R 21 may be linear, branched or cyclic. Acceptable substituents are described below.
  • the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group represented by R 21 has a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group, etc.). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
  • aryl group for R 21 an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.
  • the aryl group of R 21 may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.
  • the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is preferably an oxime sulfonate compound represented by the following general formula (B1-2).
  • General formula (B1-2) (In the formula (B1-2), R 42 represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents 0-3. Represents an integer, and when m4 is 2 or 3, a plurality of Xs may be the same or different.
  • the alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • the halogen atom as X is preferably a chlorine atom or a fluorine atom.
  • m4 is preferably 0 or 1.
  • m4 is 1
  • X is a methyl group
  • substitution position of X is the ortho position
  • R 42 is a linear alkyl group having 1 to 10 carbon atoms
  • 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
  • the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-3).
  • General formula (B1-3) (In Formula (B1-3), R 43 has the same meaning as R 42 in Formula (B1-2), and X 1 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)
  • R 43 in the above general formula (B1-3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n—.
  • a propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
  • X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
  • n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
  • description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to, and the contents thereof are described in this application. Incorporated in the description.
  • the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably a compound represented by the following general formula (OS-1).
  • R 101 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group.
  • R102 represents an alkyl group or an aryl group.
  • X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups.
  • R 121 ⁇ R 124 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amido group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R 121 to R 124 may be bonded to each other to form a ring.
  • R 121 to R 124 are preferably a hydrogen atom, a halogen atom and an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the aforementioned functional groups may further have a substituent.
  • the compound represented by the general formula (OS-1) is, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is incorporated herein by reference.
  • the compound represented by the general formula (OS-1) that can be suitably used in the present invention include compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b-34), but the present invention is not limited thereto.
  • the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is represented by the following general formula (OS-3), the following general formula (OS-4) or the following general formula (OS- The oxime sulfonate compound represented by 5) is preferred.
  • R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group
  • R 23 , R 26 and R 29 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom
  • R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group.
  • X 1 to X 3 each independently represents an oxygen atom or a sulfur atom
  • n 1 to n 3 each independently represents 1 or 2
  • m 1 to m 3 each independently represents an integer of 0 to 6 Represents.
  • the compound containing an oxime sulfonate structure represented by the above general formula (B1-1) is, for example, a compound represented by the general formula (OS-6) described in paragraph 0117 of JP2012-163937A. Particularly preferred is a compound represented by any of (OS-11), the contents of which are incorporated herein. Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. The contents of which are incorporated herein by reference.
  • oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. The contents of which are incorporated herein by reference. The present invention is not limited to these.
  • the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-4).
  • General formula (B1-4) (In the general formula (B1-4), R 1 represents an alkyl group or an aryl group, R 2 represents an alkyl group, an aryl group, or a heteroaryl group. R 3 to R 6 each represents a hydrogen atom. Represents an alkyl group, an aryl group, or a halogen atom, provided that R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form an alicyclic ring or aromatic ring. , -O- or S-).
  • R 1 represents an alkyl group or an aryl group.
  • the alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
  • the alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable. When the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
  • alkyl group examples include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
  • the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms.
  • Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
  • the alkyl group and aryl group represented by R 1 may have a substituent.
  • substituents examples include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.
  • R 1 is preferably an alkyl group from the viewpoint of transparency, and R 1 has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity.
  • An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. .
  • an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.
  • R 2 represents an alkyl group, an aryl group, or a heteroaryl group.
  • the alkyl group represented by R 2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
  • As the aryl group an aryl group having 6 to 10 carbon atoms is preferable.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
  • Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
  • the alkyl group, aryl group, and heteroaryl group represented by R 2 may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R ⁇ 1 > may have.
  • R 2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group.
  • As the substituent for the phenyl group a methyl group is preferred.
  • R 3 to R 6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom).
  • the alkyl group represented by R 3 to R 6 has the same meaning as the alkyl group represented by R 2 , and the preferred range is also the same.
  • the aryl group represented by R 3 to R 6 has the same meaning as the aryl group represented by R 1 , and the preferred range is also the same.
  • R 3 to R 6 , R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form a ring, and the ring may form an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
  • R 3 to R 6 are a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6
  • a benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are combined to form a benzene ring Is more preferable.
  • Preferred embodiments of R 3 to R 6 are as follows. (Aspect 1) At least two are hydrogen atoms.
  • Ts represents a tosyl group (p-toluenesulfonyl group)
  • Me represents a methyl group
  • Bu represents an n-butyl group
  • Ph represents a phenyl group.
  • each R 7 independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
  • N represents an integer from 0 to 4.
  • X represents an integer from 1 to 20
  • Y represents an integer from 0 to 20
  • Z represents an integer from 0 to 20
  • W represents an integer from 0 to 5.
  • imide sulfonate compound examples include compounds described in paragraph 0084 of JP2012-155115A, the contents of which are incorporated herein.
  • the imidosulfonate compound is also preferably a compound having the following structure.
  • each R independently represents a hydrogen atom and an organic group composed of a carbon atom and / or an oxygen atom. Two or more Rs may be bonded to each other to form a ring. The total number of carbon atoms and oxygen atoms in each R is preferably 16 or less. Examples of such imide sulfonate compounds include the following compounds.
  • the addition amount of the photoacid generator is preferably 0.1 to 10% by mass relative to the total solid content in the photosensitive resin composition of the present invention. More preferably, the content is 5 to 10% by mass.
  • Two or more photoacid generators can be used in combination. When using together 2 or more types of photo-acid generators, it is preferable that the total amount is the said numerical range.
  • the photosensitive resin composition of the present invention contains a solvent.
  • the photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent.
  • a solvent used for the preparation of the composition of the present invention a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
  • known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monomethyl ether.
  • Propylene glycol monoalkyl ethers such as acetate, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers such as diethylene glycol ethyl methyl ether, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, Dipropylene glycol dialkyl ethers, dipropylene glycol monoal Ether acetates, esters, ketones, amides, lactones and the like.
  • the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and paragraph numbers 0167 to 0168 of JP2012-194290A. And the contents thereof are incorporated herein by reference.
  • the solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.
  • the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
  • Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
  • Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
  • the content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass and more preferably 60 to 90 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition. preferable.
  • a sensitizer, a crosslinking agent, an alkoxysilane compound, a basic compound, a surfactant, and an antioxidant can be preferably added to the photosensitive resin composition of the present invention as necessary.
  • the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor.
  • Known additives such as can be added.
  • compounds described in paragraph numbers 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.
  • the photosensitive resin composition of the present invention preferably contains a sensitizer in combination with a photoacid generator in order to promote its decomposition.
  • the sensitizer absorbs actinic rays or radiation and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur.
  • a photo-acid generator raise
  • Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
  • Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene
  • xanthenes Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone
  • cyanines eg, thiacarbocyanine, oxacarbocyanine
  • merocyanines For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, to
  • polynuclear aromatics polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
  • polynuclear aromatics anthracene derivatives are most preferred.
  • the addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 100% by mass with respect to the total solid content in the photosensitive resin composition of the present invention, preferably 0.1 to 50%. More preferably, it is more preferably 0.5 to 20% by mass. Two or more sensitizers can be used in combination.
  • the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
  • the crosslinking agent is not limited as long as a crosslinking reaction is caused by heat. However, in the present invention, the crosslinking agent does not include the case where it is a polymer, that is, the case where it is one of the polymer components (A).
  • a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. can be added.
  • the addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50% by mass with respect to the total solid content in the photosensitive resin composition of the present invention, preferably 0.1 to It is more preferably 30% by mass, and further preferably 0.5 to 20% by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained.
  • a plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.
  • JER152, JER157S70, JER157S65, JER806, JER828, JER1007 are commercially available products described in paragraph No. 0189 of JP2011-221494, etc.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.
  • the compound having two or more oxetanyl groups in the molecule Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
  • alkoxymethyl group-containing crosslinking agents described in paragraph numbers 0107 to 0108 of JP2012-8223A, and compounds having at least one ethylenically unsaturated double bond are also preferable. These contents can be used and are incorporated herein.
  • alkoxymethyl group-containing crosslinking agent alkoxymethylated glycoluril is preferable.
  • a blocked isocyanate compound can also be preferably employed as a crosslinking agent.
  • the blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
  • the blocked isocyanate group in this invention is a group which can produce
  • the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
  • the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
  • the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic.
  • Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3
  • tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
  • the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
  • the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to.
  • a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
  • Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
  • Examples of the lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
  • Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
  • Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
  • Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
  • Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
  • Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
  • Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
  • the blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available.
  • Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL
  • the photosensitive resin composition of the present invention may contain an alkoxysilane compound.
  • an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do.
  • the alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum.
  • the compound improves the adhesion between the insulating film and the insulating film.
  • silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropyl dialkoxysilane, and ⁇ -methacryloxy.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
  • R 1 is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group
  • R 2 is an alkyl group having 1 to 3 carbon atoms or a phenyl group
  • n is an integer of 1 to 3 It is. Specific examples thereof include the following compounds.
  • Ph is a phenyl group.
  • the alkoxysilane compound in the photosensitive resin composition of this invention is not specifically limited to these, A well-known thing can be used.
  • the content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30% by mass, and preferably 0.5 to 20% by mass with respect to the total solid content in the photosensitive resin composition of the present invention. Is more preferable.
  • the photosensitive resin composition of the present invention may contain a basic compound.
  • the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include the compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
  • aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
  • examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, diazabicyclononene, nicotine, nicotinic acid, nicotinamide, quinoline, 8- Oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [ 4.3.0]- And 5-nonene and
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
  • the basic compounds that can be used in the present invention may be used singly or in combination of two or more.
  • the content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3% by mass with respect to the total solid content in the photosensitive resin composition of the present invention, preferably 0.005 to More preferably, it is 1 mass%.
  • the photosensitive resin composition of the present invention may contain a surfactant.
  • a surfactant any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants.
  • KP-341, X-22-822 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow No. 99C manufactured by Kyoeisha Chemical Co., Ltd.
  • F Top manufactured by Mitsubishi Materials Kasei Co., Ltd.
  • MegaFac manufactured by DIC Corporation
  • Florard Novec FC-4430 manufactured by Sumitomo 3M Co., Ltd.
  • Surflon S-242 Manufactured by AGC Seimi Chemical Co., Ltd.
  • PolyFoxPF-6320 manufactured by OMNOVA
  • SH-8400 Toray Dow Corning Silicone
  • footgent FTX-218G manufactured by Neos
  • a and B represented by the following general formula (I-1-1) as a surfactant and tetrahydrofuran (THF) as a solvent.
  • a copolymer having a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferred example.
  • R 401 and R 403 each independently represent a hydrogen atom or a methyl group
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 404 represents hydrogen.
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is 10 mass% to 80 mass%.
  • the following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.
  • L is preferably a branched alkylene group represented by the following general formula (I-1-2).
  • R 405 in formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • These surfactants can be used individually by 1 type or in mixture of 2 or more types.
  • the addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10% by mass or less, and preferably 0.001 to 10% by mass with respect to the total solid content in the photosensitive resin composition of the present invention. More preferably, the content is 0.01 to 3% by mass.
  • the photosensitive resin composition of the present invention may contain an antioxidant.
  • an antioxidant a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
  • antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives.
  • phenolic antioxidants hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur oxidations are particularly preferred from the viewpoint of coloring of the cured film and reduction of the film thickness.
  • Inhibitors are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types. Specific examples include the compounds described in JP-A-2005-29515, paragraphs 0026 to 0031, the contents of which are incorporated herein.
  • Preferred commercial products include ADK STAB AO-60, ADK STAB AO-20, ADK STAB AO-80, ADK STAB LA-52, ADK STAB LA-81, ADK STAB AO-412S, ADK STAB PEP-36, IRGANOX 1035, IRGANOX 1098, and Tinuvin 144. Can be mentioned.
  • the content of the antioxidant is preferably 0.1 to 10% by mass, and more preferably 0.2 to 5% by mass, based on the total solid content in the photosensitive resin composition of the present invention. It is particularly preferably 0.5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
  • an acid proliferating agent can be used for the purpose of improving sensitivity.
  • the acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
  • Specific examples of such an acid proliferating agent include acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.
  • the photosensitive resin composition of the present invention can contain a development accelerator.
  • a development accelerator those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
  • a development accelerator may be used individually by 1 type, and can also use 2 or more types together.
  • the addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition, from the viewpoint of sensitivity and residual film ratio. 1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
  • thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1 can be used. Is incorporated herein by reference.
  • a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio.
  • the composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 ⁇ m.
  • the method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
  • substrate (2) A step of removing the solvent from the applied photosensitive resin composition; (3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays; (4) A step of developing the exposed photosensitive resin composition with an aqueous developer; (5) A post-baking step of thermosetting the developed photosensitive resin composition.
  • Each step will be described below in order.
  • the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
  • substrate cleaning such as alkali cleaning or plasma cleaning
  • the method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
  • the substrate include inorganic substrates, resins, and resin composite materials.
  • the inorganic substrate examples include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
  • the resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide
  • the coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used.
  • the wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 ⁇ m. Further, before applying the composition used in the present invention to the substrate, it is possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
  • the solvent removal step (2) the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.
  • the heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.
  • the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern.
  • the photoacid generator is decomposed to generate an acid.
  • the acid-decomposable group contained in the coating film component is decomposed to generate an acid group such as a carboxyl group or a phenolic hydroxyl group.
  • a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, and i-line (365 nm), h-line (405 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used.
  • irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • the exposure amount is preferably 1 to 500 mJ / cm 2 .
  • PEB Post Exposure Bake
  • PEB can promote the generation of an acid group such as a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group.
  • the temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C.
  • the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate an acid group such as a carboxyl group or a phenolic hydroxyl group, it is not necessarily PEB. It is not indispensable that a positive image can be formed by development.
  • a copolymer having a free carboxyl group or an acid group such as a phenolic hydroxyl group is developed using an alkaline developer.
  • a positive image is formed by removing an exposed area containing a resin composition having an acid group such as a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
  • the developer used in the development step preferably contains a basic compound.
  • Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline hydroxide, and other ammonium hydroxides; sodium silicate, metasilicic acid An aqueous solution such as sodium can be used.
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide
  • alkali metal carbonates such as sodium carbonate and potassium carbonate
  • alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates
  • tetramethylammonium hydroxide tetraethylam
  • An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
  • a 0.4 to 2.5% by mass aqueous solution of tetramethylammonium hydroxide can be mentioned.
  • the pH of the developer is preferably 10.0 to 14.0.
  • the development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
  • a rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like.
  • a known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
  • the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and then crosslinked with a crosslinkable group, a crosslinking agent or the like.
  • a cured film can be formed.
  • This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed.
  • post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process).
  • middle baking it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes.
  • middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking.
  • These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
  • the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film.
  • the preferred exposure amount in the case of including a post-exposure step preferably 100 ⁇ 3,000mJ / cm 2, particularly preferably 100 ⁇ 500mJ / cm 2.
  • the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
  • dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
  • the cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention.
  • the cured film of the present invention can be suitably used as an interlayer insulating film.
  • the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
  • the photosensitive resin composition of the present invention an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for liquid crystal display devices and organic EL display devices.
  • the liquid crystal display device of the present invention comprises the cured film of the present invention.
  • the liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures.
  • An apparatus can be mentioned.
  • specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • the liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. Compensated Bend) method and the like.
  • the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device.
  • the organic insulating film (115) of JP-A-2005-284291 It can be used as an organic insulating film (212).
  • FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10.
  • the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
  • the elements of the TFT 16 corresponding to are arranged.
  • Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
  • an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
  • the light source of the backlight is not particularly limited, and a known light source can be used.
  • a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
  • the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type.
  • the organic EL display device of the present invention comprises the cured film of the present invention.
  • the organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
  • specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • FIG. 1 is a conceptual diagram of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • a bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3.
  • the wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
  • the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
  • a bottom emission type organic EL element is formed on the planarizing film 4. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • the first electrode 5 corresponds to the anode of the organic EL element.
  • An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do. Further, although not shown in FIG.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate.
  • An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it.
  • An EL display device is obtained.
  • the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-mentioned applications, and can be used for various applications.
  • a protective film for the color filter in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
  • a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part.
  • MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
  • the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010-
  • a chemical film (12), a pixel isolation insulating film (14), and the like can also be used to form a chemical film (12), a pixel isolation insulating film (14), and the like.
  • spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.
  • MATHF 2-tetrahydrofuranyl methacrylate (synthetic product)
  • MAEVE 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MATHP Tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • OXE-30 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry) (thermal crosslinking start temperature 151 ° C.)
  • GMA Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) (thermal crosslinking start temperature: 115 ° C.)
  • NBMA n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
  • MAA Methacrylic acid
  • the oily product was distilled under reduced pressure to obtain 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily product having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg (yield: 80%). ).
  • MATHF tetrahydro-2H-furan-2-yl methacrylate
  • the obtained organic layer was washed with saturated brine (50 mL), dried over magnesium sulfate, concentrated under reduced pressure to remove volatile components, and a yellow oil was obtained.
  • Solution B and Solution C were measured by reversed-phase HPLC (* 2), and obtained from the following formula based on the peak area (integrated value) of each monomer obtained by normalization from the peak area (integrated value) of anisole. The obtained value was defined as the hydrolysis rate (%) of each monomer.
  • the structural unit derived from AICA, MAAN, and ⁇ BLMA is a structural unit having a group that generates a carboxyl group by (a4) alkaline hydrolysis.
  • the structural unit derived from PMMA does not satisfy the hydrolyzable condition, it has a lactone ring as a partial structure, but is not a structural unit corresponding to (a4).
  • PGMEA 40 g was placed in a three-necked flask and heated to 75 ° C. in a nitrogen atmosphere.
  • MATH in an amount of 30 mol% in all monomer components
  • GMA in an amount of 12 mol% in all monomer components
  • AICA in an amount of 1.2 mol% in all monomer components
  • MAA in an amount of 10 mol% in all monomer components
  • MMA in an amount of 36.8 mol% in all monomer components
  • St an amount of 10 mol% in all monomer components
  • the total mass of the body was 50 g), and a solution in which V-65 (amount corresponding to 4 mol% with respect to the total of all monomer components) was dissolved in PGMEA (10 g) at room temperature was added dropwise over 2 hours.
  • B-1 Structure shown below (Synthesis example will be described later)
  • B-2 Structure shown below (synthesis example will be described later)
  • B-3 Structure shown below (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)
  • B-4 PAG-103 (trade name, structure shown below, manufactured by BASF)
  • B-5 GSID-26-1, triarylsulfonium salt (manufactured by BASF)
  • B-6 The following compound B-7: Structure shown below (synthesized according to the method described in paragraph No. 0128 of WO2011 / 087011)
  • the obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the mixture was warmed to room temperature and stirred. The reaction was continued for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain the compound of B-1 (the above structure) (2.3 g).
  • Crude B-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-9A.
  • Mix B-2A (1.7 g) and p-xylene (6 mL) add 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and heat at 140 ° C. with stirring for 2 hours. did.
  • water and ethyl acetate were added to the reaction mixture and the phases were separated.
  • MEDG diethylene glycol ethyl methyl ether
  • Hisolv EDM manufactured by Toho Chemical Industry Co., Ltd.
  • PGMEA propylene glycol monomethyl ether acetate
  • H-1 Diazabicyclononene (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • H-2 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • H-3 Compound having the following structure
  • G-1 ⁇ -glycidoxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.)
  • G-2 Bis (triethoxysilylpropyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • G-3 Decyltrimethoxysilane (KBM-3103, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • W-1 Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC) Since W-1 is a polymer, it is treated as one of the polymer components (A) when calculating the content of each component in the present invention.
  • F-1 JER828 (manufactured by Mitsubishi Chemical Holdings Corporation)
  • F-2 JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation)
  • F-3 JER157S65 (Mitsubishi Chemical Holdings Co., Ltd.)
  • F-4 Celoxide 2021P (manufactured by Daicel Corporation)
  • F-5 Duranate 17B-60P (Asahi Kasei Chemicals Corporation)
  • F-6 Denacol EX-321L (manufactured by Nagase ChemteX Corporation)
  • F-7 Takenate B-870N (Mitsui Chemicals, Inc.)
  • J-1 ADK STAB AO-60 (manufactured by ADEKA Corporation)
  • J-2 Irganox 1098 (BASF)
  • J-3 Irganox 1035 (manufactured by BASF)
  • K-1 Joncryl 67 (manufactured by BASF)
  • K-2 ARUFON UC-3910 (manufactured by Toa Gosei Co., Ltd.)
  • ⁇ Adjustment of photosensitive resin composition In each example and each comparative example, polymer components, photoacid generators, sensitizers, crosslinking agents, alkoxysilane compounds, basic compounds, surfactants, and others so that the solid content ratios shown in the following table are obtained. Were dissolved and mixed in PGMEA so that the solid content concentration was 25% by mass and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 ⁇ m to obtain a photosensitive resin composition.
  • an alkaline developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) was used at 23 ° C., 60 ° C. After developing for 2 seconds, it was rinsed with ultrapure water for 1 minute. The obtained board
  • substrate was observed with the optical microscope, and the dimension of the pattern of 10 micrometers line / 10micrometer space was observed. Next, the same operation and observation were performed except that the same operation as described above was performed with a development time of 180 seconds.
  • A, B, and C are practically no problem levels.
  • F The dimensional variation is 1.5 ⁇ m or more.
  • Each photosensitive resin composition was spin-coated on a bare wafer substrate (N-type low resistance) (manufactured by SUMCO), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness was 3.0 ⁇ m.
  • a photosensitive resin composition layer was formed. Subsequently, exposure was performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and the substrate was heated in an oven at 230 ° C./30 minutes.
  • the column of parts by mass in the total solid content of the polymer (A) is a mass part when the total solid content is 100 parts by mass.
  • the composition of the present invention contains (a2) a crosslinkable group and (a4) a group that generates carboxylic acid by alkali hydrolysis in a specific ratio in the (A) polymer component.
  • a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 200 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film. As a pretreatment for improving the wettability between the substrate of paragraph No. 0058 and the interlayer insulating film 17 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the photosensitivity of Example 1 The resin composition was spin-coated and then pre-baked on a hot plate at 90 ° C.
  • HMDS hexamethyldisilazane
  • the obtained photosensitive resin composition layer was subjected to 40 mJ / cm 2 (energy intensity: 20 mW / cm 2 ) through a hole pattern mask of 10 ⁇ m ⁇ using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. , I-line).
  • the exposed photosensitive resin composition layer was subjected to paddle development at 23 ° C./60 seconds with an alkaline developer (0.4% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 20 seconds.
  • the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes.
  • a cured film was obtained.
  • the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking.
  • liquid crystal display device When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 201 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the photosensitive resin composition of Example 1 was applied without the hexamethyldisilazane (HMDS) treatment, which is a pretreatment of the substrate, the resulting cured film was good with no chipping or peeling off of the pattern. It was a state. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate. From the viewpoint of improving productivity, it is also preferable to omit the substrate pretreatment step.
  • HMDS hexamethyldisilazane
  • Example 202 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even if a vacuum drying step (VCD) was introduced after pre-baking, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 200. It is also preferable to introduce a reduced-pressure drying step from the viewpoint of suppressing coating unevenness according to the solid content concentration and the film thickness of the composition.
  • VCD vacuum drying step
  • Example 203 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even if the PEB process was introduced between the development process and the mask exposure, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 200. From the viewpoint of improving dimensional stability, it is also preferable to introduce a PEB process.
  • Example 204 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the alkaline developer is changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 2.38% tetramethylammonium hydroxide aqueous solution, the resulting cured film has good pattern free of chipping and peeling. It was a state. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • Example 205 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the alkali development method was changed from paddle development to shower development, the obtained cured film was in a good state with no pattern chipping or peeling. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • Example 206 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, even when the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution, the resulting cured film was in a good state with no pattern chipping or peeling. It was. Further, the performance as a liquid crystal display device was good as in Example 200. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • Example 207 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, the entire surface exposure step after development and rinsing was omitted, and the cured film was obtained by heating in an oven at 230 ° C. for 30 minutes. The performance of the obtained liquid crystal display device was as good as in Example 200. This seems to be because the composition of the present invention is excellent in chemical resistance. From the viewpoint of improving productivity, it is also preferable to omit the entire exposure process.
  • Example 208> A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, a step of heating on a hot plate at 100 ° C. for 3 minutes was added between the entire surface exposure step and the 230 ° C./30 minute heating step in the oven. The performance of the obtained liquid crystal display device was as good as in Example 200. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.
  • Example 209 A liquid crystal display device similar to that of Example 200 was changed to obtain the same liquid crystal display device. That is, a process of heating on a hot plate at 100 ° C. for 3 minutes was added between the development / rinse process and the entire surface exposure process. The performance of the obtained liquid crystal display device was as good as in Example 200. It is also preferable to add this process from the viewpoint of adjusting the shape of the hole pattern.
  • An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
  • a bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3. .
  • the wiring 2 is used to connect the TFT 1 to the organic EL element formed between the TFTs 1 or in a later process.
  • the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
  • the planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiation with i-line (365 nm) at 45 mJ / cm 2 (energy intensity 20 mW / cm 2 ) using a mercury lamp, development is performed with an alkaline aqueous solution (0.4% TMAH aqueous solution) to form a pattern.
  • the integrated dose was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and a heat treatment was performed at 230 ° C./30 minutes.
  • the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking.
  • the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
  • a bottom emission type organic EL element was formed on the obtained flattening film 4.
  • a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed.
  • pattern processing was performed by wet etching using an ITO etchant.
  • the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials).
  • the first electrode 5 thus obtained corresponds to the anode of the organic EL element.
  • an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed.
  • the photosensitive resin composition of Example 1 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus.
  • a second electrode made of Al was formed on the entire surface above the substrate.
  • substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
  • FIG. 3 is a conceptual diagram of an example of the liquid crystal display device.
  • an array substrate formed up to just before the organic passivation film 109 of the liquid crystal display device described in FIG. 2 of Japanese Patent Application Laid-Open No. 2011-59314 was manufactured.
  • this substrate was exposed to HMDS vapor for 30 seconds, and then the photosensitive resin composition of Example 1 was slit-coated and then pre-baked on a hot plate at 90 ° C.
  • a thick photosensitive resin composition layer was formed.
  • the obtained photosensitive resin composition layer was subjected to 40 mJ / cm 2 (energy intensity: 20 mW / cm) through a 10 ⁇ m diameter hole pattern mask using Canon Inc. MPA 7800CF (high pressure mercury lamp). 2 , i-line) exposure.
  • the exposed resin composition layer was developed with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
  • Example 210 a liquid crystal display device was produced in the same manner as in Example 210 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 19. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 210 a liquid crystal display device was produced in the same manner as in Example 210 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 33. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 210 a liquid crystal display device was produced in the same manner as in Example 210 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 47. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • FIG. 4 is a conceptual diagram of an example of the liquid crystal display device.
  • an array substrate formed until just before the organic insulating film PAS of the liquid crystal display device described in FIG.
  • this substrate was exposed to HMDS vapor for 30 seconds, and then the photosensitive resin composition of Example 1 was slit-coated and then pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent.
  • a thick photosensitive resin composition layer was formed.
  • the obtained photosensitive resin composition layer was subjected to optimum exposure dose mJ / cm 2 (energy intensity: 20 mW / cm 2) through a hole pattern mask having a diameter of 8 ⁇ m using MPA 7800CF manufactured by Canon Inc. , I-line) exposure.
  • the exposed resin composition layer was developed with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
  • the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , measured by i-line), and then the substrate was heated at 230 ° C. in an oven at 30 ° C. An organic passivation film was obtained by heating for a minute. Thereafter, a liquid crystal display device was obtained according to Japanese Patent Application Laid-Open No. 2007-328210. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 215 a liquid crystal display device was produced in the same manner as in Example 214 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 19. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 214 a liquid crystal display device was produced in the same manner as in Example 214 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 33. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 214 a liquid crystal display device was produced in the same manner as in Example 214 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Example 47. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • TFT thin film transistor
  • 2 wiring
  • 3 insulating film
  • 4 flattening film
  • 5 first electrode
  • 6 glass substrate
  • 7 contact hole
  • 8 insulating film
  • 10 liquid crystal display device
  • 12 Backlight unit
  • 15 Glass substrate
  • 16 TFT
  • 17 Cured film
  • 18 Contact hole
  • 19 ITO transparent electrode
  • 20 Liquid crystal
  • 22 Color filter
  • 109 Organic passivation film

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PCT/JP2014/075366 2013-09-25 2014-09-25 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置及び有機ｅｌ表示装置 WO2015046295A1 (ja)

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