WO2014050627A1 - 感光性樹脂組成物、これを用いた硬化膜の製造方法、硬化膜、液晶表示装置および有機ｅｌ表示装置 - Google Patents

感光性樹脂組成物、これを用いた硬化膜の製造方法、硬化膜、液晶表示装置および有機ｅｌ表示装置 Download PDF

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WO2014050627A1
WO2014050627A1 PCT/JP2013/074977 JP2013074977W WO2014050627A1 WO 2014050627 A1 WO2014050627 A1 WO 2014050627A1 JP 2013074977 W JP2013074977 W JP 2013074977W WO 2014050627 A1 WO2014050627 A1 WO 2014050627A1
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group
resin composition
acid
photosensitive resin
compound
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PCT/JP2013/074977
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English (en)
French (fr)
Japanese (ja)
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達也 霜山
政憲 疋田
亮 佐竹
大助 柏木
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富士フイルム株式会社
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Priority to KR1020157006403A priority Critical patent/KR101725810B1/ko
Priority to CN201380049705.6A priority patent/CN104685416B/zh
Priority to JP2014538405A priority patent/JP5933734B2/ja
Publication of WO2014050627A1 publication Critical patent/WO2014050627A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—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
    • 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
    • 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
    • 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
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • G02F1/136227—Through-hole connection of the pixel electrode to the active element through an insulation layer

Definitions

  • the present invention relates to a positive photosensitive resin composition, a method of forming a cured film, a cured film, a liquid crystal display device, and an organic EL display device. More specifically, a positive photosensitive resin composition suitable for forming a planarizing film of an electronic component such as a liquid crystal display, an organic EL display, an integrated circuit element, a solid-state imaging device, a protective film and an interlayer insulating film The present invention relates to a method of forming a cured film using
  • TFTs thin film transistors
  • magnetic head elements magnetic head elements
  • integrated circuit elements solid-state imaging elements
  • solid-state imaging elements etc.
  • interlayer insulation in order to insulate between wirings generally arranged in layers.
  • a membrane is provided.
  • a photosensitive resin composition is widely used because it is preferable that the number of steps for obtaining the required pattern shape be small and the material have sufficient flatness.
  • patent document 1 is mentioned, for example.
  • a variety of chemical solutions are used in the manufacture of electronic components such as display devices, and resistance to these chemical solutions is essential.
  • high panel reliability under high temperature, high humidity, and high pressure conditions is required, and with the recent increase in definition of display devices, the requirement is increasing more and more.
  • an aromatic heterocyclic compound may be added to a photosensitive resin composition used to form an interlayer insulating film in an electronic component as a sensitizer and a photoinitiation aid.
  • these photosensitive resin compositions have low chemical resistance after film curing, and when using these photosensitive resin compositions, panel display unevenness tends to occur in panel reliability tests. It turned out that there is a case.
  • the present invention is intended to solve the above problems, and has high sensitivity, excellent chemical resistance of a cured film, and a photosensitive resin composition in which occurrence of panel display unevenness is suppressed in a panel reliability test. Intended to be provided. Furthermore, it aims at providing the formation method of a cured film using such a photosensitive resin composition, a cured film, an organic electroluminescence display, and a liquid crystal display.
  • the inventor of the present invention has conducted intensive studies and has found that the compound has a predetermined molecular weight, contains at least one nitrogen atom in the aromatic ring, and at least two coordinates in the aromatic ring.
  • the aromatic heterocyclic compound containing an atom it discovered that it was excellent in chemical resistance, maintaining high sensitivity.
  • low molecular weight aromatic heterocyclic compounds move easily to the substrate side, and coordination atoms in the aromatic heterocyclic compounds interact with the underlying substrate, resulting in high temperature, high humidity, It is considered that the degradation products from the photosensitive resin composition generated under high pressure conditions are prevented from entering the underlying substrate, which contributes to the improvement of the panel reliability.
  • the aromatic heterocyclic compound promotes the crosslinking of the cured film, and is considered to contribute to the improvement of the chemical resistance.
  • the means for solving the problems is the means of the following ⁇ 1>, and preferably the means of the following ⁇ 2> to ⁇ 16>.
  • ⁇ 1> A polymer component containing a polymer satisfying at least one of the following (1) and (2), (1) A polymer having a constituent unit having a residue (a1) in which an acid group is protected by an acid-degradable group, and a constituent unit having (a2) a crosslinkable group, (2) (a1) a polymer having a constituent unit having a residue in which an acid group is protected by an acid-degradable group, and (a2) a polymer having a constituent unit having a crosslinkable group, (B) Photo acid generator, (C) aromatic heterocyclic compounds, and (D) solvent, And the (C) aromatic heterocyclic compound has a molecular weight of 1000 or less, contains at least one nitrogen atom in the aromatic ring, and contains at least two coordinating atoms in the aromatic ring.
  • the aromatic heterocyclic compound of (C) is a 5-membered aromatic heterocyclic compound, a 6-membered aromatic heterocyclic compound, a 5-membered aromatic heterocyclic structure and a 6-membered aromatic heterocyclic structure
  • the photosensitive resin composition according to ⁇ 1> which is any one of polycyclic aromatic heterocyclic compounds containing at least one of the following.
  • the photosensitive resin composition as described in ⁇ 1> or ⁇ 2> whose ⁇ 3> above-mentioned coordination atom is either a nitrogen atom, a sulfur atom, and an oxygen atom.
  • the crosslinkable group contained in the structural unit having the (a2) crosslinkable group is an epoxy group, an oxetanyl group, and —NH—CH 2 —O—R (R is hydrogen
  • the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 3> which is at least one selected from an atom or a group represented by an alkyl group having 1 to 20 carbon atoms.
  • ⁇ 8> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the aromatic heterocyclic compound of (C) contains 2 to 3 coordinating atoms in an aromatic ring.
  • ⁇ 12> (1) a coating step of coating the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 11> on a substrate, (2) a solvent removing step of removing the solvent from the applied photosensitive resin composition, (3) an exposure step of exposing the photosensitive resin composition from which the solvent has been removed by actinic light, (4) a development step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) post-baking step of thermally curing the developed photosensitive resin composition, And a method of forming a cured film.
  • the formation method of the cured film as described in ⁇ 12> including the process of carrying out whole surface exposure of the developed photosensitive resin composition after the said image development process and before the said post-baking process.
  • the cured film as described in ⁇ 14> which is a ⁇ 15> interlayer insulation film.
  • the organic electroluminescence display or liquid crystal display device which comprises the cured film as described in ⁇ 16> ⁇ 14> or ⁇ 15>.
  • the photosensitive resin composition which is excellent in chemical resistance, the manufacturing method of a pattern, an organic electroluminescence display, the manufacturing method of a liquid crystal display, and a cured film can be provided, maintaining high sensitivity.
  • FIG. 1 shows a conceptual diagram of an example of a liquid crystal display device.
  • a schematic cross-sectional view of an active matrix substrate in a liquid crystal display device is shown, and it has a cured film 17 which is an interlayer insulating film.
  • the structural conceptual diagram of an example of an organic electroluminescence display is shown.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarization film 4 is provided.
  • alkyl group includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • (meth) acrylic acid means acrylic acid and / or methacrylic acid.
  • the photosensitive resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) comprises (A) a polymer component containing a polymer satisfying at least one of the following (1) and (2): (1) A polymer having a constituent unit having a residue (a1) in which an acid group is protected by an acid-degradable group, and a constituent unit having (a2) a crosslinkable group, (2) (a1) a polymer having a constituent unit having a residue in which an acid group is protected by an acid-degradable group, and (a2) a polymer having a constituent unit having a crosslinkable group, (B) Photo acid generator, (C) aromatic heterocyclic compounds, and (D) solvent, And the (C) aromatic heterocyclic compound has a molecular weight of 1000 or less, contains at least one nitrogen atom in the aromatic ring, and contains at least two coordinating atoms in the aromatic ring. .
  • the photosensitive resin composition of this invention is a chemical amplification positive type photo
  • the composition of the present invention is a polymer having, as a polymer component, a constituent unit having (1) (a1) a group having an acid group protected by an acid-degradable group and a constituent unit having (a2) a crosslinkable group, And (2) (a1) at least one of a polymer having a constituent unit having a group in which an acid group is protected by an acid-degradable group and a polymer having a constituent unit having a crosslinkable group (a2). Furthermore, polymers other than these may be included. Unless otherwise stated, the (A) polymer component (hereinafter referred to as "(A) component”) in the present invention is added to the above (1) and / or (2) and optionally added. And polymers of the formula
  • Component A at least has a constituent unit having a group in which the acid group is protected by an acid-degradable group.
  • component (A) has the structural unit (a1), a photosensitive resin composition with extremely high sensitivity can be obtained.
  • the “group in which the acid group is protected with an acid-degradable group” in the present invention may be any group known as an acid group and an acid-degradable group, and is not particularly limited. As a specific acid group, a carboxyl group and a phenolic hydroxyl group are preferably mentioned.
  • an acetal group such as an ester structure of a group relatively decomposable by acid (for example, an ester structure of a group represented by formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group) Functional groups) and groups which are relatively difficult to be decomposed by acid (for example, tertiary alkyl groups such as tert-butyl ester group, tertiary alkyl carbonate groups such as tert-butyl carbonate group) can be used.
  • an ester structure of a group relatively decomposable by acid for example, an ester structure of a group represented by formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group
  • Functional groups for example, tertiary alkyl groups such as tert-butyl ester group, tertiary alkyl carbonate groups such as
  • the structural unit having a group in which the acid group is protected by an acid degradable group is a structural unit having a protected carboxyl group protected by an acid degradable group, or a protected phenolic compound protected by an acid degradable group It is preferable that it is a structural unit which has a hydroxyl group.
  • the structural unit (a1-1) having a protected carboxyl group protected by an acid degradable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected by an acid degradable group will be sequentially described. Do.
  • the structural unit (a1-1) having a protected carboxyl group protected by an acid degradable group is a protected carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid degradable group described in detail below. It is a structural unit having a group.
  • the structural unit having a carboxyl group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-degradable group is not particularly limited, and known structural units can be used.
  • a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, etc.
  • Examples include structural units (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
  • a constitutional unit derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in a molecule (>> 1-1-1) molecule a constitutional unit derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in a molecule (>> 1-1-1) molecule.
  • the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the above molecule, the following may be used. .
  • unsaturated monocarboxylic acid for example, acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid Leuoxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, etc. may be mentioned.
  • unsaturated dicarboxylic acid maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc. are mentioned, for example.
  • the unsaturated polyvalent carboxylic acid used to obtain the structural unit having a carboxyl group may be the acid anhydride. Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride and the like can be mentioned.
  • the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of polyvalent carboxylic acid, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) and the like.
  • the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of its both terminal dicarboxy polymer, and examples thereof include ⁇ -carboxypolycaprolactone monoacrylate, ⁇ -carboxypolycaprolactone monomethacrylate and the like.
  • unsaturated carboxylic acid acrylic acid 2-carboxyethyl ester, methacrylic acid 2-carboxyethyl ester, monoalkyl ester of maleic acid, monoalkyl ester of fumaric acid, 4-carboxystyrene and the like can also be used.
  • a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule from the viewpoint of developability, acrylic acid, methacrylic acid, 2- (Meth) acryloyloxyethyl-succinic acid, 2- (Meth) acryloyloxyethyl hexahydrophthalic acid, 2- (Meth) acryloyloxyethyl-phthalic acid, or anhydrides of unsaturated polyvalent carboxylic acids It is preferable to use etc., and it is more preferable to use acrylic acid, methacrylic acid and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
  • the structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be constituted singly or in combination of two or more. May be
  • the structural unit (a1-1-2) having both the ethylenically unsaturated group and the structure derived from the acid anhydride is obtained by reacting the acid anhydride with the hydroxyl group present in the structural unit having the ethylenically unsaturated group. It is preferable that it is a unit derived from the obtained monomer.
  • acid anhydrides known ones can be used, and specific examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride and the like.
  • Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride and the like can be mentioned.
  • phthalic anhydride, tetrahydrophthalic anhydride or succinic anhydride is preferable.
  • the reaction rate of the acid anhydride to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.
  • Acid-decomposable group that can be used for the structural unit (a1-1) can be used as the above-mentioned acid-decomposable group which can be used for the structural unit (a1-1) having a protected carboxyl group protected by the above-mentioned acid-degradable group.
  • these acid-decomposable groups it is a protected carboxyl group in which the carboxyl group is protected in the form of acetal. It is preferable from the viewpoint of storage stability of the 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 It has a structure of R 102 (OR 103 ).
  • R 101 and R 102 each represent a hydrogen atom or an alkyl group, except that R 101 and R 102 both represent a hydrogen atom.
  • R 103 represents an alkyl group. And R 101 or R 102 and R 103 may combine to form a cyclic ether).
  • R 101 to R 103 each represent a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic.
  • both of R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
  • R 101 , R 102 and R 103 in the general formula (a1-10) represent an alkyl group
  • the alkyl group may be linear, branched or cyclic.
  • 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.
  • 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 cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group and the like.
  • the alkyl group may have a substituent, and as the substituent, a halogen atom, an aryl group and an alkoxy group can be exemplified.
  • a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when having an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are illustrated, Among these, a fluorine atom or a chlorine atom is preferable.
  • aryl group a C6-C20 aryl group is preferable, More preferably, it is C6-C12,
  • a phenyl group, (alpha)-methylphenyl group, a naphthyl group etc. can specifically be illustrated.
  • the entire alkyl group substituted with an aryl group that is, as an aralkyl group, a benzyl group, an ⁇ -methylbenzyl group, a phenethyl group, a naphthylmethyl group and the like can be exemplified.
  • 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 alkyl group is a cycloalkyl 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 a linear group.
  • it When it is a linear or branched alkyl group, it may have a cycloalkyl group having a carbon number of 3 to 12 as a substituent. These substituents may be further substituted by the above-mentioned substituent.
  • R 101 , R 102 and R 103 in the general formula (a1-10) represent an aryl group
  • the aryl group preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms preferable.
  • the aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms can be preferably exemplified. Examples of the aryl group include phenyl group, tolyl group, cumenyl group, 1-naphthyl group and the like.
  • R 101 , R 102 and R 103 can be bonded to each other to form a ring together with the carbon atom to which they are attached.
  • a ring structure when R 101 and R 102 , R 101 and R 103 or R 102 and R 103 are bonded for example, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, tetrahydrofuranyl group, adamantyl group and tetrahydropyranyl And the like.
  • one of R 101 and R 102 is preferably a hydrogen atom or a methyl group.
  • the radically polymerizable monomer used to form the constituent unit having a protected carboxyl group represented by the above general formula (a1-10) may be a commercially available one, or is synthesized by a known method It is also possible to use one. For example, it can be synthesized by the synthesis method described in paragraph numbers 0037 to 0040 of JP-A-2011-221494.
  • the first preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected by the acid decomposable group is a structural unit represented by the following general formula (A2 ′).
  • R 1 and R 2 each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is an alkyl group or R 1 or R 2 and R 3 may combine to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or 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, phenyl groups are preferred.
  • Each of R 1 and R 2 is 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, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • X represents a single bond or an arylene group, preferably a single bond.
  • the second preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected by the acid-degradable group is a structural unit of the following general formula.
  • 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
  • R 122 to R 128 each represent a hydrogen atom or an alkyl having 1 to 4 carbon atoms Represents a group
  • 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) having a protected phenolic hydroxyl group protected by the acid degradable group is a protected phenolic property in which the structural unit having a phenolic hydroxyl group is protected by an acid degradable group described in detail below. It is a structural unit having a hydroxyl group.
  • ⁇ (a 1-2-1) structural unit having a phenolic hydroxyl group Examples of the structural unit having a phenolic hydroxyl group include a structural unit in a hydroxystyrene-based structural unit and a novolac resin, and among these, a structural unit derived from hydroxystyrene or ⁇ -methylhydroxystyrene is It is preferable from the viewpoint of sensitivity. Further, as a structural unit having a phenolic hydroxyl group, 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 linear or 1 to 5 carbon atoms 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, provided that two or more R 222 exist, these R 222 may be mutually different or the same.
  • R 220 represents a hydrogen atom or a methyl group, preferably a methyl group.
  • R 221 represents a single bond or a divalent linking group. When it is a single bond, the sensitivity can be improved, and the transparency of the cured film can be further improved, which is preferable.
  • 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 And-a butylene group, a pentylene group, an isopentylene group, a neopentylene group, a hexylene group and the like. Among them, R 221 is preferably a single bond, a methylene group or an ethylene group. Moreover, the said bivalent coupling group may have a substituent, and a halogen atom, a hydroxyl group, an alkoxy group etc.
  • 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 ease of production.
  • R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.
  • Specific examples include 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 and the like.
  • a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferable from the viewpoint of easy production.
  • b represents an integer of 0 or 1 to 4.
  • Acid-degradable group that can be used for the structural unit (a1-2) includes a structure having a protected carboxyl group protected by the acid decomposable group A well-known thing can be used similarly to the said acid-degradable group which can be used for a unit (a1-1), It does not specifically limit.
  • the acid-degradable groups it is a structural unit having a protected phenolic hydroxyl group protected with an acetal, the basic physical properties of the photosensitive resin composition, particularly the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, the contact It is preferable from the viewpoint of the formation of holes. Furthermore, among the acid-degradable groups, it is more preferable from the viewpoint of sensitivity that 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 total protected phenolic hydroxyl group is —Ar—O—CR 101 R It has a structure of 102 (OR 103 ).
  • Ar represents an arylene group.
  • acetal protecting group of phenolic hydroxyl group include 1-alkoxyalkyl group, and examples thereof include 1-ethoxyethyl group, 1-methoxyethyl group, 1-n-butoxyethyl group, 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 -Benzyloxyethyl group etc. can be mentioned, and these can be used individually or in combination of 2 or more types.
  • the radically polymerizable monomer used to form the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-degradable group may be a commercially available product, or a known method It is also possible to use one synthesized in For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with a 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 a vinyl ether in the presence of an acid catalyst.
  • ⁇ preferred embodiment of structural unit (a1) When the polymer containing the structural unit (a1) does not substantially contain the structural unit (a2), the structural unit (a1) is 20 to 100 in the polymer containing the structural unit (a1) The mole% is preferred, and 30 to 90 mole% is more preferred. When the polymer containing the structural unit (a1) contains the following structural unit (a2), the single structural unit (a1) contains in the polymer containing the structural unit (a1) and the structural unit (a2) From the viewpoint of sensitivity, 3 to 70 mol% is preferable, and 10 to 60 mol% is more preferable.
  • the above-mentioned acid-degradable group which can be used for the above-mentioned structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of acetal, 20 to 50 mol% is preferable.
  • the structural unit (a1-1) having a protected carboxyl group protected by the acid decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid degradable group. Is fast. Therefore, when it is desired to develop rapidly, the structural unit (a1-1) having a protected carboxyl group protected by an acid-degradable group is preferable. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-degradable group.
  • the structural unit (a1-1) having a protected carboxyl group protected by the acid decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid degradable group. Is fast. Therefore, when it is desired to develop rapidly, the structural unit (a1-1) having a protected carboxyl group protected by an acid-degradable group is preferable. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-degradable group.
  • the component (A) has a structural unit (a2) having a crosslinkable group.
  • the crosslinkable group is not particularly limited as long as it is a group which causes a curing reaction by heat treatment.
  • Preferred embodiments of the constituent unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH 2 —O—R (R is an alkyl group having 1 to 20 carbon atoms), and an ethylenically unsaturated group.
  • the component (A) preferably contains a structural unit containing at least one of an epoxy group and an oxetanyl group. More specifically, the following may be mentioned.
  • the polymer (A) preferably contains a structural unit (structural unit (a2-1)) having an epoxy group and / or an oxetanyl group.
  • the 3-membered cyclic ether group is also referred to as an epoxy group, and the 4-membered cyclic ether group is also referred to as an oxetanyl group.
  • the structural unit (a2-1) having an epoxy group and / or an oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and one or more epoxy groups and one It may have one or more oxetanyl groups, two or more epoxy groups, or 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, It is more preferable to have a total of 1 or 2 of epoxy group and / or oxetanyl group, and it is further preferable to have 1 epoxy group or oxetanyl group.
  • radically polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate , ⁇ -n-Butyl acrylic acid glycidyl, acrylic acid-3, 4- epoxy butyl, methacrylic acid-3, 4- epoxy butyl, acrylic acid-3, 4- epoxycyclohexyl methyl, methacrylic acid-3, 4- epoxy cyclohexyl Methyl, ⁇ -ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, described in paragraph No.
  • radically polymerizable monomer used to form the structural unit (a2-1) having the above epoxy group and / or oxetanyl group include a monomer having a methacrylic acid ester structure, and an acrylic acid ester structure. It is preferable that it is a monomer to contain.
  • glycidyl methacrylate 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetan-3-yl) methyl acrylate, and methacrylic acid 3-ethyloxetan-3-yl) methyl.
  • These constituent units can be used singly or in combination of two or more.
  • R represents a hydrogen atom or a methyl group.
  • a structural unit (a2-2) having an ethylenically unsaturated group may be mentioned as one of the structural units (a2) having a crosslinkable group (hereinafter, also referred to as a “structural unit (a2-2)”).
  • the structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, and has an ethylenically unsaturated group at the terminal and has 3 to 16 carbon atoms.
  • the structural unit having a side chain is more preferable, and the structural unit having a side chain represented by the following general formula (a2-2-1) is more preferable.
  • R 301 represents a divalent linking group having 1 to 13 carbon atoms
  • R 302 represents a hydrogen atom or a methyl group
  • * represents a structural unit having a crosslinkable group ( represents a site linked to the main chain of a2)
  • R 301 is a divalent linking group having a carbon number of 1 to 13, and includes an alkenyl group, a cycloalkenyl group, an arylene group or a group combining them, such as ester bond, ether bond, amide bond, urethane bond and the like It may contain a bond. Further, the divalent linking group may have a substituent such as a hydroxy group or a carboxyl group at any position. Specific examples of R 301 include the following divalent linking groups.
  • aliphatic side chains including the divalent linking group represented by R 301 above are preferable.
  • a constitutional unit having a group represented by (a2-3) —NH—CH 2 —O—R (R is an alkyl group having 1 to 20 carbon atoms) is also preferably a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R is an alkyl group having 1 to 20 carbon atoms).
  • 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 any of linear, branched or cyclic alkyl groups, but is preferably a linear or branched alkyl group.
  • the structural unit (a2) is more preferably a structural unit having a group represented by general formula (a2-30) shown below.
  • General formula (a2-30) (In the general formula (a2-30), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 20 carbon atoms.) R 2 is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be any of linear, branched or cyclic alkyl groups, but is preferably a linear or branched alkyl group.
  • R 2 include methyl, ethyl, n-butyl, i-butyl, cyclohexyl and n-hexyl groups. Among them, i-butyl, n-butyl and methyl are preferable.
  • the structural unit (a2) is 5 to 90 in the polymer containing the structural unit (a2) The mole% is preferred, and 20 to 80 mole% is more preferred.
  • the polymer containing the structural unit (a2) contains the structural unit (a1)
  • the single structural unit (a2) contains in the polymer containing the structural unit (a1) and the structural unit (a2) From the viewpoint of drug resistance, 3 to 70 mol% is preferable, and 10 to 60 mol% is more preferable.
  • the structural unit (a2) is preferably contained in an amount of 3 to 70 mol%, and more preferably 10 to 60 mol%, based on all the structural units of the component (A). preferable.
  • the transparency and chemical resistance of the cured film obtained from the photosensitive resin composition will be good if it is within the above numerical range.
  • the component (A) may have another structural unit (a3) other than these in addition to the above structural units (a1) and / or (a2). These constituent units may be contained in the polymer component (1) and / or (2). In addition to the polymer component (1) or (2), it may have a polymer component having another structural unit (a3) substantially free of (a1) and (a2). .
  • the compounding amount is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less, based on all the polymer components.
  • a monomer used as another structural unit (a3) For example, Styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to.
  • the monomer used as other structural unit (a3) can be used individually or in combination of 2 or more types.
  • First Embodiment The embodiment in which the polymer component (1) further has one or more other structural units (a3).
  • Second Embodiment The polymer having a structural unit having a group in which the (a1) acid group of the polymer component (2) is protected by an acid-degradable group further has one or more other structural units (a3) Aspect.
  • Third Embodiment An embodiment in which the polymer having a structural unit having a crosslinkable group (a2) of the polymer component (2) further has one or more other structural units (a3).
  • an aspect including a structural unit containing at least an acid group as the other structural unit (a3).
  • Sixth Embodiment The form which consists of 2 or more combination of the said 1st-5th embodiment.
  • Seventh Embodiment An embodiment comprising at least the polymer component (2).
  • an aspect including at least the polymer component (2).
  • the structural unit (a3) include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinyl benzoate, and vinyl benzoic acid.
  • styrenes and a group having an alicyclic skeleton are preferable from the viewpoint of electrical characteristics.
  • (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate and the like, and methyl (meth) acrylate is more preferable.
  • 60 mol% or less is preferable, as for the content rate of said structural unit (a3) in the structural unit which comprises a polymer (A), 50 mol% or less is more preferable, and 40 mol% or less is more preferable.
  • the lower limit value may be 0 mol%, but may be, for example, 1 mol% or more, and further 5 mol% or more.
  • the various characteristics of the cured film obtained from the photosensitive resin composition become favorable in it being in the range of said numerical value.
  • the other structural unit (a3) it is preferable to contain an acid group.
  • an acid group By containing an acid group, it becomes easily soluble in an alkaline developer, and the effects of the present invention are more effectively exhibited.
  • the acid group in the present invention means a proton dissociative group having a pKa of less than 7.
  • 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 a structural unit containing such an acid group in the polymer, it tends to be easily soluble in an alkaline developer.
  • those derived from a carboxylic acid group those derived from a sulfonamide group, those derived from a phosphonic acid group, those derived from a sulfonic acid group, those derived from a phenolic hydroxyl group, a sulfone Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
  • the constituent unit containing an acid group used in the present invention is more preferably a constituent unit derived from styrene, a constituent unit derived from a vinyl compound, a constituent unit derived from (meth) acrylic acid and / or an ester thereof .
  • the present invention in particular, it is preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.
  • the structural unit containing an acid group is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, still more preferably 5 to 40 mol%, particularly preferably 5 to 30 mol% of the structural units of all polymer components. And 5 to 20 mol% are particularly preferred.
  • a polymer having another structural unit (a3) may be contained substantially excluding (a1) and (a2), separately from the above polymer component (1) or (2). .
  • a resin having a carboxyl group in a side chain is preferable.
  • a resin having a carboxyl group in a side chain is preferable.
  • acid cellulose derivatives having a carboxyl group polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, and the like, and polymer polymers having a (meth) acryloyl group in a side chain are also preferable.
  • benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, as described in JP-A-7-140654.
  • the known polymer compounds described in JP-A-2003-233179 and JP-A-2009-52020 can be used, and the contents thereof are incorporated in the present specification. These polymers may contain only one type, or two or more types.
  • SMA 1000P As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (manufactured by Sartmar Corporation), ARUFON UC-3000, ARUFON UC-3510, ARUFON Use UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, made by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (made by BASF), etc. You can also.
  • the molecular weight of the polymer (A) is, in terms of polystyrene equivalent weight average molecular weight, preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in it being in the range of said numerical value.
  • the ratio of the number average molecular weight to the weight average molecular weight (degree of dispersion) is preferably 1.0 to 5.0, and more preferably 1.5 to 3.5.
  • the photosensitive resin composition of the present invention preferably contains 50 to 99.9 parts by mass of the component (A), preferably 70 to 98 parts by mass, with respect to 100 parts by mass of the total solid content. More preferable.
  • the photosensitive resin composition of the present invention contains (B) a photoacid generator.
  • a photoacid generator also referred to as "component (B)"
  • a compound which is sensitive to actinic light having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferred. It is not limited by its chemical structure.
  • a photoacid generator which does not directly react to actinic light having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that responds to actinic light having a wavelength of 300 nm or more by using it in combination with a sensitizer.
  • produces the acid of 4 or less pKa is preferable,
  • photoacid generators examples include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators can be used singly or in combination of two or more.
  • Preferred examples of the oxime sulfonate compound ie, a compound having an oxime sulfonate structure, include a compound having an oxime sulfonate structure represented by the following general formula (B1).
  • R 21 represents an alkyl group or an aryl group.
  • the wavy line represents a bond to another group.
  • any group may be substituted, and the alkyl group in R 21 may be linear, branched or cyclic.
  • the permissible substituents are described below.
  • the alkyl group of R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a bridged oil such as a cycloalkyl group (7, 7-dimethyl-2-oxo norbornyl group) It may be substituted with a ring group, preferably a bicycloalkyl group and the like.
  • the aryl group of R 21 is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group.
  • the aryl group of R 21 may be substituted by a lower alkyl group, an alkoxy group or a halogen atom.
  • the above-mentioned compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B2).
  • R 42 represents an alkyl group or an aryl group
  • X represents an alkyl group, an alkoxy group, or a halogen atom
  • m 4 represents an integer of 0 to 3
  • m 4 is 2 or When it is 3, plural X 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. In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is an ortho position, and R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7, 7- Particular preference is given to compounds which are the dimethyl-2-oxonorbornylmethyl group or the p-toluyl group.
  • the compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B3).
  • R 43 has the same meaning as R 42 in the formula (B2), and X 1 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and n4 represents an integer of 0 to 5.
  • R 43 in the above general formula (B3) methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.
  • X 1 an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group is more preferable.
  • n 4 0 to 2 is preferable, and 0 to 1 is particularly preferable.
  • Specific examples of the compound represented by the above general formula (B3) include ⁇ - (methylsulfonyloxyimino) benzyl cyanide, ⁇ - (ethylsulfonyloxyimino) benzyl cyanide, ⁇ - (n-propylsulfonyloxyimino) ) Benzyl cyanide, ⁇ - (n-butylsulfonyloxyimino) benzyl cyanide, ⁇ - (4-toluenesulfonyloxyimino) benzyl cyanide, ⁇ -[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(n-propylsulfonyloxyimino) -4-methoxyphenyl
  • preferable oxime sulfonate compounds include the following compounds (i) to (viii) and the like, and one kind may be used alone, or two or more kinds may be used in combination.
  • Compounds (i) to (viii) can be obtained as commercial products. It can also be used in combination with other types of (B) photoacid generators.
  • the compound containing an oxime sulfonate structure represented by the above general formula (B1) 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.
  • R 102 represents an alkyl group or an aryl group.
  • X 101 is -O -, - S -, - NH -, - NR 105 -, - CH 2 -, - CR 106 H-, or, -CR 105 R 107 - represents, R 105 ⁇ R 107 is an alkyl group Or an aryl group.
  • R 121 to R 124 each independently represent 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 represents an aryl group.
  • R 121 to R 124 may be respectively bonded to each other to form a ring.
  • R 121 to R 124 a hydrogen atom, a halogen atom, and an alkyl group are preferable, and an embodiment in which at least two of R 121 to R 124 bond to each other to form an aryl group is also preferably mentioned.
  • R 121 to R 124 are hydrogen atoms is preferable from the viewpoint of sensitivity.
  • Any of the functional groups described above may further have a substituent.
  • the compound represented by the above general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).
  • R 101 , R 102 and R 121 to R 124 each has the same meaning as in formula (OS-1), and preferred examples are also the same.
  • R 101 in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2)
  • R 101 is a cyano group, a phenyl group or a naphthyl group.
  • the steric structures (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
  • the compound having an oxime sulfonate structure represented by the above general formula (B1) includes the following general formula (OS-3), the following general formula (OS-4) or the following general formula (OS-5) It is preferable that it is an oxime sulfonate compound represented by these.
  • R 22 , R 25 and R 28 each independently represent 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 represent an oxygen atom or a sulfur atom
  • n 1 to n 3 each independently represent 1 or 2
  • m 1 to m 3 each independently represent an integer of 0 to 6 Represents
  • the alkyl group, aryl group or heteroaryl group of R 22 , R 25 and R 28 may have a substituent.
  • the alkyl group for R 22 , R 25 and R 28 is an alkyl group having 1 to 30 carbon atoms in total that may have a substituent. Is preferred.
  • the heteroaryl group for R 1 is preferably a heteroaryl group having 4 to 30 carbon atoms in total that may have a substituent.
  • At least one ring in R 22 , R 25 and R 28 may be a heteroaromatic ring, for example, a heteroaromatic ring and benzene The ring may be fused.
  • R 23, R 26 and R 29 is preferably a hydrogen atom, an alkyl group or an aryl group, and more is a hydrogen atom or an alkyl group preferable.
  • one or two of R 23 , R 26 and R 29 present in the compound at 2 or more are an alkyl group, an aryl group or a halogen atom It is more preferable that one be an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one be an alkyl group and the rest be a hydrogen atom.
  • the alkyl group for R 23 , R 26 and R 29 is preferably an alkyl group having 1 to 12 carbon atoms in total that may have a substituent, and may have 1 to 12 carbon atoms in total optionally having a substituent. More preferably, it is an alkyl group of 6.
  • the aryl group in R 23 , R 26 and R 29 is preferably an aryl group having a total of 6 to 30 carbon atoms which may have a substituent.
  • each of X 1 to X 3 independently represents O or S, and is preferably O.
  • a ring containing X 1 to X 3 as ring members is a 5- or 6-membered ring.
  • n 1 to n 3 each independently represent 1 or 2, and when X 1 to X 3 are O, n 1 to n 3 are each independently Is preferable, and when X 1 to X 3 are S, n 1 to n 3 are preferably each independently 2.
  • 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.
  • R 24 , R 27 and R 30 are preferably each independently an alkyl group or an alkyloxy group.
  • the alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group of R 24 , R 27 and R 30 may have a substituent.
  • the alkyl group for R 24 , R 27 and R 30 is an alkyl group having 1 to 30 carbon atoms in total which may have a substituent. Is preferred.
  • the alkyloxy group in R 24 , R 27 and R 30 is an alkyloxy group having 1 to 30 carbon atoms in total that may have a substituent. Is preferred.
  • m 1 to m 3 each independently represent an integer of 0 to 6, preferably 0 to 2, and 0 or 1. It is more preferable that it be 0, and it is particularly preferable that Moreover, about each substituent of said (OS-3)-(OS-5), substitution of (OS-3)-(OS-5) as described in stage number 0092-0109 of Unexamined-Japanese-Patent No. 2011-221494 is mentioned.
  • the preferred range of groups is likewise preferred.
  • the compound containing an oxime sulfonate structure represented by the above general formula (B1) is particularly preferably an oxime sulfonate compound represented by any of the following general formulas (OS-6) to (OS-11) preferable.
  • R 301 to R 306 represent an alkyl group, an aryl group or a heteroaryl group
  • R 307 represents a hydrogen atom or a bromine atom
  • R 308 to R 310 R 313 , R 316 and R 318 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group
  • R 311 and R 314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group
  • R 312 , R 315 , R 317 and R 319 each independently represent a hydrogen atom or a methyl group.
  • the preferable range in said general formula (OS-6)-(OS-11) is a preferable range of (OS-6)-(OS-11) described in Paragraph No. 0110-0112 of Unexamined-Japanese-Patent No. 2011-221494. Is the same as
  • the oxime sulfonate compound represented by said general formula (OS-3)-said general formula (OS-5) the compound as described in stage number 0114-0120 of Unexamined-Japanese-Patent No. 2011-221494 is mentioned.
  • the present invention is not limited to these.
  • the photoacid generator is based on 100 parts by mass of all resin components (preferably solid content, more preferably total of copolymers) in the photosensitive resin composition. It is preferable to use 0.1 to 10 parts by mass, and it is more preferable to use 0.5 to 10 parts by mass. Two or more types can also be used in combination.
  • the composition of the present invention contains (C) an aromatic heterocyclic compound.
  • the aromatic heterocyclic compound (C) has a molecular weight of 1000 or less, contains at least one nitrogen atom in the aromatic ring, and at least two coordinating atoms in the aromatic ring.
  • chemical resistance can be improved while maintaining the sensitivity.
  • the panel display unevenness of a display apparatus can be improved.
  • the molecular weight of the (C) aromatic heterocyclic compound is 1,000 or less, preferably 750 or less, and more preferably 500 or less. By setting the molecular weight to a low molecular weight, the molecule can easily move to the substrate side.
  • the lower limit value is preferably 1 or more, more preferably 50 or more.
  • the coordinating atom constituting the aromatic heterocyclic ring means an atom having a coordinating ability, and examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and the like, and a nitrogen atom, an oxygen atom, a sulfur atom Atoms are more preferred.
  • the aromatic heterocyclic compound (C) contains at least two coordinating atoms, at least one of which is a nitrogen atom.
  • the number of coordinating atoms is preferably two to three in the aromatic ring of one molecule of (C) aromatic heterocyclic compound.
  • the coordinating atoms at least one is preferably a nitrogen atom and at least two are preferably nitrogen atoms.
  • a hydrogen atom may be bonded to a coordinating atom.
  • the (C) aromatic heterocyclic compound preferably does not contain a basic group, and more preferably does not contain an amino group.
  • the aromatic heterocyclic compound (C) may have a substituent T on the aromatic ring.
  • T for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, an acetyl group, a cyano group, a halogen atom (Fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. These substituents may further have a substituent.
  • the (C) aromatic heterocyclic compound used in the present invention is preferably a compound which is unsubstituted or substituted by a methyl group.
  • an amino group is not contained as a substituent of an aromatic ring from a viewpoint of suppressing the fall of sensitivity.
  • the aromatic heterocyclic compound is not particularly limited as long as it is an aromatic ring, but a 5-membered aromatic heterocyclic compound, a 5-membered aromatic heterocyclic compound, a 5-membered aromatic heterocyclic structure and a 6-membered Polycyclic aromatic heterocyclic compounds containing at least one of the ring aromatic heterocyclic structures are preferred.
  • a polycyclic aromatic heterocyclic compound is a compound in which two or more independent aromatic rings are bonded to each other by a connector (for example, bipyridine etc.), or one or more aromatic rings and one or more aromatic rings Refers to a compound (eg, phenanthroline etc.) in which an aliphatic ring and / or an aromatic ring is fused.
  • any other ring may be used.
  • the other ring is preferably selected from benzene ring, 5-membered aromatic heterocycle and 6-membered aromatic heterocycle, and is selected from benzene ring and 6-membered aromatic heterocycle Is more preferable.
  • the number of rings forming the polycyclic aromatic heterocyclic compound is preferably two or three in one molecule, and more preferably two.
  • an imidazole compound, a pyrazole compound, an oxazole compound, an isoxazole compound, a thiazole compound, an isothiazole compound, a triazole compound, an oxadiazole compound, a thiadiazole compound , Etc. are preferred.
  • imidazole compound imidazole, 1-methylimidazole, 1-ethylimidazole, 1-n-propylimidazole, 1-isopropylimidazole, 1-butylimidazole, 1-decyl-2-methylimidazole, 1,2-dimethylimidazole , 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 1- (heptafluorobutyryl) imidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-benzylimidazole Preferred are 4-methyl-2-phenylimidazole, 1-acetylimidazole, 1-imidazole acetic acid, 4-imidazole carboxylic acid, 4,5-imidazole dicarboxylic acid and the like.
  • pyrazole As a pyrazole type-compound, pyrazole, 1-methylpyrazole, 3-methylpyrazole, 4-methylpyrazole, 1-ethylpyrazole, 3-ethylpyrazole, 4-ethylpyrazole, 4-ethylpyrazole, 1-phenylpyrazole, 3-phenylpyrazole, 4- Phenylpyrazole, 3,5-diisopropylpyrazole, 3- (trifluoromethyl) pyrazole, 4-bromopyrazole, 4-chloropyrazole, 3,5-dimethylpyrazole, 1,3,5-trimethylpyrazole, 3,5-dimethylpyrazole -1-phenylpyrazole, 3- (4-tolyl) pyrazole, 3- (4-methoxyphenyl) pyrazole, 3- (4-bromophenyl) pyrazole, 3-methyl-1-phenylpyrazole, 4-bromo-3- Methyl pyrazole, 3- (4-bromophen
  • oxazole compounds include oxazole, 2,4-dimethyloxazole, 4-phenyloxazole, 5-phenyloxazole, 2,4-diphenyloxazole, 2,5-diphenyloxazole, 2,4,5-trimethyloxazole, and 5-hydroxyoxazole.
  • [3- (Trifluoromethyl) phenyl] oxazole, 2-methyl-4,5-diphenyloxazole, 5-ethoxy-4-methyloxazole, 4-oxazolecarboxylic acid, ethyl 4-oxazolecarboxylate and the like are preferable.
  • isoxazole compounds include isoxazole, 5-methylisoxazole, 3,5-dimethylisoxazole, 4-bromo-3.5-dimethylisoxazole, 3-chloromethyl-5-methylisoxazole, 4- ( Chloromethyl) -3,5-dimethylisoxazole, 4-iodo-3,5-dimethylisoxazole, 3-hydroxy-5-methylisoxazole, 5-methyl-3-isoxazole carboxylic acid, 5-methylisoxazole- 4 Carboxylic acid etc. is preferred.
  • thiazole As a thiazole compound, thiazole, 2-methylthiazole, 2-ethylthiazole, 2-n-propylthiazole, 2-isopropylthiazole, 2-n-butylthiazole, 2-isobutylthiazole, 2-phenylthiazole, 4-methyl Thiazole, 5-methylthiazole, 2,4-dimethylthiazole, 4,5-dimethylthiazole, 2-ethyl-4-methylthiazole, 2-ethyl-4,5-dimethylthiazole, 2-isopropyl-4-methylthiazole, 2-isobutyl-4-methylthiazole, 4-methyl-2-phenylthiazole, 4-methyl-5-vinylthiazole, 2-isobutyl-4,5-dimethylthiazole, 2-methyl-4,5-diphenylthiazole, 2 , 4,5-trimethylthiazole, 2- ( -Tolyl) benzothiazole, 2- (trimethylsilyl) thiazo
  • the isothiazole compound is preferably isothiazole.
  • the triazole compounds 1,2,3-triazole, 1,2,4-triazole, 3-methyl-1H-1,2,4-triazole and the like are preferable.
  • thiadiazole compounds include 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, 1,2,5-thiadiazole, 2,5-dimethyl-1,3,4- Thiadiazole, 4-phenyl-1,2,3-thiadiazole, 4,5-diphenyl-1,2,3-thiadiazole, 3-bromo-5-chloro-1,2,4-thiadiazole, 2-bromo-5- Phenyl-1,3,4-thiadiazole, 2-chloromethyl-5-cyclopropyl-1,3,4-thiadiazole, 3,4-dichloro-1,2,5-thiadiazole, 3,5-dichloro-1, Preferred is 2,4-thiadiazole or the like.
  • a 6-membered ring aromatic heterocyclic compound As a 6-membered ring aromatic heterocyclic compound, a pyrimidine type compound, a pyridazine type compound, a pyrazine type compound, a triazine type compound etc. are preferable.
  • Pyrimidine compounds include pyrimidine, 2-chloropyrimidine, 2-bromopyrimidine, 5-bromopyrimidine, 5-bromo-2-chloropyrimidine, 2-chloro-4-methyl pyrimidine, 2-chloro-5-ethyl pyrimidine, 5-bromo-2,4-dichloropyrimidine, 5-bromo-4,6-dichloropyrimidine, 2-chloro-5-n-decyl pyrimidine, 2-chloro-4,6-dimethyl pyrimidine, 4-chloro-2, 4-chloro-2, 6-dimethylpyrimidine, pyrimidine-5-carboxylic acid, 5-bromo-2-hydroxypyrimidine, 5-bromo-2-methoxypyrimidine, 4,6-dihydroxypyrimidine, 4,6-dimethoxypyrimidine, 4-hydroxypyrimidine, 2 , 4, 5- trihydroxy pyrimidine and the like are preferable.
  • pyridazine compounds include 3-methylpyridazine, 4-methylpyridazine, 3,6-dichloropyridazine, 3,6-dichloro-4-methylpyridazine, 3,4,6-trichloropyridazine, pyridazine-4-carboxylic acid, Pyridazine-4,5-dicarboxylic acid, 3,6-dihydroxy-4-methylpyridazine, 3-methoxypyridazine and the like are preferable.
  • pyrazine compounds pyrazine, 2-methylpyrazine, 2-ethylpyrazine, 2-n-propylpyrazine, 2-isopropylpyrazine, 2-isobutylpyrazine, 2-tert-butylpyrazine, 2-vinylpyrazine, 2-chloro Pyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3-diethylpyrazine, 2,3-diphenylpyrazine, 2-methyl-3-n-propylpyrazine, 2- Ethyl-3-methylpyrazine, 2-isobutyl-3-methylpyrazine, 5-isobutyl-2,3-dimethylpyrazine, 2,3-diethyl-5-methylpyrazine, 3,5-dimethyl-2-ethylpyrazine, 2 , 3,5-trimethylpyrazine, 2,3,5,
  • the triazine compounds include 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine, 2,4, 6-triphenyl-1,3,5-triazine, 2,4,6-tris (trifluoromethyl) -1,3,5-triazine etc., 2,4-dimethoxy-1,3,5-triazine is preferred .
  • polycyclic aromatic heterocyclic compounds examples include benzoimidazole compounds, benzopyrazole compounds, benzoxazole compounds, benzoisoxazole compounds, benzothiazole compounds, benzotriazole compounds, benzooxadiazole compounds and benzothiadiazoles.
  • Preferred are a compound of the formula, a quinazoline compound, a phthalazine compound, a phenanthroline compound and a bipyridine compound.
  • benzimidazole compounds include benzoimidazole, 4-methylbenzimidazole, 5-methylbenzimidazole, 6-methylbenzimidazole, 7-methylbenzimidazole, 4-ethylbenzimidazole, 5-ethylbenzimidazole, 6 -Ethyl benzimidazole, 7-ethyl benzimidazole, 4-n-propyl benzimidazole, 5-n-propyl benzimidazole, 6-n-propyl benzimidazole, 7-n-propyl benzimidazole, 4-isopropyl benzimidazole, 5 -Isopropylbenzimidazole, 6-isopropylbenzimidazole, 7-isopropylbenzimidazole, 1-butylbenzimidazole, 2-acetylbenzimidazole, 2-chloro Nzimidazole, 2- (chloromethyl) benzimidazole, 2,5-
  • benzopyrazole compound 1,2-benzopyrazole, 3-chloro-1H-benzopyrazole and the like are preferable.
  • benzoxazole compounds include benzoxazole, 2-methylbenzoxazole, 5-methylbenzoxazole, 2,6-dichlorobenzoxazole, 2,5-dimethylbenzoxazole, and 5-fluoro-2-methylbenzoxazole. 2,2,5,6-trimethylbenzoxazole, 2-chlorobenzoxazole, 2-methyl-5-phenylbenzoxazole, 2- (2-hydroxyphenyl) benzoxazole and the like are preferable.
  • benzoisoxazole compounds 1,2-benzoisoxazole, 1,2-benzoisoxazole-3-acetic acid and the like are preferable.
  • benzothiazole compound examples include benzothiazole, 2-methylbenzothiazole, 2-ethylbenzothiazole, 2-n-propylbenzothiazole, 2-isopropylbenzothiazole, 2-n-butylbenzothiazole, 2-phenyl Benzothiazole, 2,5-dimethylbenzothiazole, 2,6-dimethylbenzothiazole, 2,5,6-trimethylbenzothiazole, 2-chlorobenzothiazole, 2-chloro-5-chloromethylthiazole, 6-bromo-2 -Chlorobenzothiazole, 5-bromo-2-methylbenzothiazole, 2,6-dichlorobenzothiazole, 2-fluorobenzothiazole, 5-chloro-2-methylbenzothiazole, 5-fluoro-2-methylbenzothiazole, 2 -(4-bromo Eniru) benzothiazole, 2-acetyl-benzothiazole, 2-hydroxy-(2-
  • benzoxadiazole compounds include 2,1,3-benzoxadiazole, 4-fluoro-2,1,3-benzoxadiazole, 4-chloro-2,1,3-benzoxadiazole, etc. preferable.
  • benzothiadiazole compounds include 2,1,3-benzothiadiazole, 4,7-dibromo-2,1,3-benzothiadiazole, 5,6-dibromo-2,1,3-benzothiadiazole, 2,1,3 -Benzothiadiazole-5-carboxylic acid, 2-mercaptobenzothiazole, 6-amino-2-mercaptobenzothiazole and the like are preferable.
  • Preferred quinazoline compounds are quinazoline, 4-chloroquinazoline, 2,4-dichloroquinazoline, 4-hydroxyquinazoline, 5-fluoro-4-hydroxyquinazoline and the like.
  • phthalazine-based compounds phthalazine, 6-methyl phthalazine, 1-chlorophthalazine, 1,4-dichloro phthalazine and the like are preferable.
  • 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2-chloro-1,10-phenanthroline, 5-chloro-1,10-phenanthroline, 3,8-dimethyl-1, 10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 2,9-dibutyl-1,10-phenanthroline, 4,7-diphenyl-1,10- Phenanthroline, 4,7-dichloro-1,10-phenanthroline, 3-bromo-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 4,7-dihydroxy-1,10 -Phenanthroline, 1,10-phenanthroline-2,9-dicarboxylic acid, etc. are preferred There.
  • bipyridine compounds include 2,2'-bipyridine, 2,4'-bipyridine, 4,4'-bipyridine, 5-phenyl-2,2'-bipyridine, 5-phenyl-2,3'-bipyridine, -Phenyl-2,4'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 6,6'-dimethyl-2,2'- Bipyridine, 4,4'-dinonyl-2,2'-bipyridine, 4,4'-dibromo-2,2'-bipyridine, 6,6'-dibromo-2,2'-bipyridine, 4,4'-bis (Chloromethyl) -2,2'-bipyridine, 5,5'-dichloro-2,2'-bipyridine, 5-bromo-2,2'-bipyridine, 5-bromo-2,3'-bipyridine, 5- Brom
  • oxazole 2,4,5-trimethyloxazole, isoxazole, 5-methylisoxazole, thiazole, 5-methylthiazole, isothiazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,5-oxadiazole, 1,2.
  • the addition amount of the aromatic heterocyclic compound in the photosensitive resin composition of the present invention is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition.
  • the content is more preferably 01 to 8 parts by mass, and still more preferably 0.01 to 5 parts by mass.
  • the photosensitive resin composition of the present invention contains (D) 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 the (D) solvent.
  • solvent (D) used for the photosensitive resin composition of the present invention known solvents can be used, and ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Monoalkyl ether acetates, esters, ketones, amides, lactones and the like can be exemplified.
  • benzyl ethyl ether dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal according to need.
  • Solvents such as benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate can also be added. These solvents can be used singly or in combination of two or more.
  • the solvents that can be used in the present invention are preferably used singly or in combination of two, more preferably used in combination of two, and propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates More preferably, a combination of diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates is used.
  • Component D is preferably a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., a solvent having a boiling point of 160 ° C. or more, or a mixture thereof.
  • solvents having a boiling point of 130 ° C. or more and less than 160 ° C. 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.).
  • the content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, and 60 to 90 parts by mass with respect to 100 parts by mass of all resin components in the photosensitive resin composition. It is further preferred that
  • the photosensitive resin composition of the present invention in addition to the above components, (E) alkoxysilane compound, (F) crosslinking agent, (G) sensitizer, (H) basic compound, (E) I) Surfactant, (J) Antioxidant, can be preferably added. Furthermore, the photosensitive resin composition of the present invention includes an acid multiplying 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. And the like can be added.
  • the photosensitive resin composition of the present invention is characterized by containing (E) an alkoxysilane compound (also referred to as “component (E)”).
  • component (E) an alkoxysilane compound
  • adhesion between a film formed by the photosensitive resin composition of the present invention and a substrate can be improved, or the properties of a film formed by the photosensitive resin composition of the present invention can be adjusted.
  • an alkoxysilane compound a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable.
  • the carbon number of the alkoxy group which the alkoxysilane compound has is preferably 1 to 5.
  • the (E) alkoxysilane compound which can be used for the photosensitive resin composition of the present invention is an inorganic substance as a base material, for example, silicon compounds such as silicon, silicon oxide, silicon nitride, gold, copper, molybdenum, titanium, aluminum
  • the compound is preferably a compound that improves the adhesion between the metal and the insulating film.
  • known silane coupling agents are also effective.
  • silane coupling agent for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrialkoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, ⁇ -methacryloxy Propyltrialkoxysilane, ⁇ -methacryloxypropylalkyldialkoxysilane, ⁇ -chloropropyltrialkoxysilane, ⁇ -mercaptopropyltrialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. More preferable. These can be used singly or in combination of two or more.
  • Ph is a phenyl group.
  • the (E) alkoxysilane compound in the photosensitive resin composition of the present invention known compounds can be used without particular limitation thereto.
  • the content of the (E) alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition. 20 parts by mass is more preferable.
  • the photosensitive resin composition of this invention contains a crosslinking agent as needed.
  • the crosslinking agent is not particularly limited as long as the crosslinking reaction occurs by heat.
  • Excluding component A For example, compounds having two or more epoxy groups or oxetanyl groups in the molecule described below, alkoxymethyl group-containing crosslinking agents, compounds having at least one ethylenically unsaturated double bond, blocked isocyanate compounds, etc. It 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 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. More preferably, it is part by mass and more preferably 0.5 to 20 parts by mass. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained.
  • a plurality of crosslinking agents can be used in combination, in which case all the crosslinking agents are added to calculate the content.
  • Compound having two or more epoxy groups or oxetanyl groups in the molecule Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, aliphatic epoxy resin and the like. Can.
  • JP-A-2011-221494 commercially available products described in paragraph No. 0189 of JP-A-2011-221494, such as JER 157 S70, JER 157 S 65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), etc. may be mentioned.
  • ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, made by ADEKA Co., Ltd.), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX- 832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX- 14L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203,
  • bisphenol A epoxy resin bisphenol F epoxy resin, phenol novolac epoxy resin, aliphatic epoxy, and aliphatic epoxy resin are more preferable, and bisphenol A epoxy resin is particularly preferable.
  • aron oxetane OXT-121, OXT-221, OX-SQ, PNOX all manufactured by Toagosei Co., Ltd.
  • the compound containing an oxetanyl group is preferably used alone or in combination with a compound containing an epoxy group.
  • alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP-A-2012-8223, and compounds having at least one ethylenically unsaturated double bond are also preferably used. The contents of which are incorporated herein.
  • alkoxymethyl group-containing crosslinking agent alkoxymethylated glycoluril is preferable.
  • a blocked isocyanate compound can also be preferably employed as the crosslinking agent.
  • the blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but from the viewpoint of curability, a compound having two or more blocked isocyanate groups in one molecule is preferable.
  • the block isocyanate group in this invention is group which can produce
  • 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 one having two isocyanate groups in one molecule, and it may be aliphatic, alicyclic or aromatic.
  • the polyisocyanate may be, 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 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3
  • TKI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • a biuret type, an isocyanurate type, an adduct type, a bifunctional prepolymer type etc. can be mentioned.
  • the blocking agent forming 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, imide compounds and the like be able to.
  • blocking agents selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds and pyrazole compounds are particularly preferable.
  • Examples of the oxime compounds include oximes and ketoximes, and specific examples thereof include acetoxy, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
  • Examples of the lactam compound include ⁇ -caprolactam, ⁇ -butyrolactam and the like.
  • Examples of the phenol compound include phenol, naphthol, cresol, xylenol, halogen-substituted phenol and the like.
  • Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, alkyl lactate and the like.
  • Examples of the amine compound include primary amines and secondary amines. Any of aromatic amines, aliphatic amines and alicyclic amines may be used, and aniline, diphenylamine, ethyleneimine, polyethyleneimine and the like can be exemplified.
  • 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, methyl pyrazole, dimethyl pyrazole and the like.
  • Examples of the mercaptan compound include alkyl mercaptan and aryl mercaptan.
  • Blocked isocyanate compounds that can be used for the photosensitive resin composition of the present invention are commercially available products, for example, Coronate AP table M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all, above) Nippon Polyurethane Industry Co., Ltd., Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all 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 (or more) , Asahi Kasei Chemicals Co., Ltd., Death Module B 1100, BL1265 MPA / X, BL35
  • the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote the decomposition thereof in combination with the photoacid generator (B).
  • the sensitizer absorbs actinic rays or radiation to be in an electronically excited state.
  • the sensitizer in the electronically excited state comes into contact with the photoacid generator to produce actions such as electron transfer, energy transfer and heat generation.
  • the photoacid generator chemically changes and decomposes to generate an acid.
  • preferable sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength range of 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 eg, For example, merocyanine, carbomerocyanine
  • rhodacyanines oxonols
  • thiazines eg, thionine,
  • polynuclear aromatics polynuclear aromatics, acridones, styryls, base styryls and coumarins are preferable, and polynuclear aromatics are more preferable.
  • Anthracene derivatives are most preferable among polynuclear aromatics.
  • the addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by mass, and 10 to 500 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition. Is more preferably 50 to 200 parts by mass. Two or more types can also be used in combination.
  • the photosensitive resin composition of the present invention may contain (H) a basic compound.
  • a basic compound any compound selected from those used in chemically amplified resists can be used.
  • aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids and the like can be mentioned. Specific examples thereof include the compounds described in paragraph Nos. 0204 to 0207 of JP-A-2011-221494, the contents of which are incorporated in the present specification.
  • thioureas such as N-cyclohexyl-N '-[2- (4-morpholinyl) ethyl] thiourea may be used.
  • the basic compounds that can be used in the present invention may be used alone or in combination of two or more.
  • the content of the (H) other basic compound in the photosensitive resin composition of the present invention is, when it contains another basic compound, 0.1 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition.
  • the amount is preferably 001 to 3 parts by mass, and more preferably 0.005 to 1 parts by mass.
  • the photosensitive resin composition of the present invention may contain (I) a surfactant.
  • a surfactant any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. .
  • KP made by Shin-Etsu Chemical Co., Ltd.
  • Polyflow made by Kyoeisha Chemical Co., Ltd.
  • F-top made by JEMCO
  • Megafac made by DIC
  • Florard Florard
  • Sitomo 3M Florard
  • Manufactured by Asahi Kasei Corp. Asahi Guard
  • Surfron manufactured by Asahi Glass Co., Ltd.
  • PolyFox manufactured by OMNOVA
  • SH-8400 Toray Dow Corning Silicone
  • Copolymers having a 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 represent a hydrogen atom or a methyl group
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 404 represents a hydrogen atom or carbon atoms
  • L represents an alkyl group having 1 to 4 carbon atoms
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q each represent a polymerization percentage
  • p represents a numerical value of 10% to 80% by mass
  • Q represents a numerical value of 20% by mass to 90% by mass
  • r represents an integer of 1 to 18 and s represents an integer of 1 to 10).
  • the above L is preferably a branched alkylene group represented by the following general formula (I-2).
  • R 405 in the general formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the surface to be coated, carbon
  • the alkyl group of several 2 or 3 is more preferable.
  • the weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.
  • the addition amount of (I) surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, relative to 100 parts by mass of the total solid content in the photosensitive resin composition, and 0.001 The amount is more preferably 10 parts by mass, further preferably 0.01 to 3 parts 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, it is possible to prevent coloring of the cured film, or to reduce a decrease in film thickness due to decomposition, and also have an advantage of being excellent in heat-resistant transparency. Examples of such an antioxidant include phosphorus-based antioxidants, amides, hydrazides, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, saccharides, Nitrate, sulfite, thiosulfate, hydroxylamine derivative and the like can be mentioned.
  • phenol-based antioxidants amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring of the cured film and reduction in film thickness. These may be used singly or in combination of two or more.
  • Adekastab AO-15 Adekastab AO-18, Adekastab AO-20, Adekastab AO-23, Adekastab AO-30, Adekastab AO-37, Adekastab AO-40, Adekastab AO -50, Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab AO-412S, Adekastab AO-503, Adekastab A-611, Adekastab A-612, Adekastab A -613, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab PEP-36, Adekastab PEP-36Z, Adekastab HP-1 , Adeka stub 2112, Adeka stub 260, Adeka s
  • the content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, relative to the total solid content of the photosensitive resin composition. Particularly preferred is 5 to 4% by mass. By setting this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation also becomes good.
  • additives other than antioxidants various ultraviolet light absorbers described in “New development of polymer additives (Nihon Kogyo Shimbun Co., Ltd.)”, metal deactivators, etc. You may add to a resin composition.
  • the photosensitive resin composition of this invention can use an acid multiplication agent for the purpose of a sensitivity improvement.
  • the acid multiplying agent which can be used in the present invention is a compound which can further generate an acid by an acid catalyzed reaction to increase the acid concentration in the reaction system, and is a compound which is stably present in the absence of the acid. is there. Such a compound is generated here because one or more acids increase in one reaction, so the reaction proceeds at an accelerated pace as the reaction proceeds, but the generated acid itself induces self-decomposition.
  • the acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less. As specific examples of the acid multiplying agent, paragraph Nos.
  • the acid proliferating agent which can be used in the present invention is decomposed by the acid generated from the acid generator, and pKa of dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, phenylphosphonic acid, etc. Mention may be made of compounds which generate an acid of 3 or less. In particular Etc.
  • the content of the acid multiplying agent in the photosensitive composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator from the viewpoint of the dissolution contrast between the exposed area and the unexposed area. Preferably, it is more preferably 20 to 500 parts by mass.
  • the photosensitive resin composition of the present invention can contain a development accelerator.
  • a development accelerator the description in paragraph Nos. 0171 to 0172 of JP-A-2012-042837 can be referred to, and such contents are incorporated in the present specification.
  • the development accelerator may be used alone or in combination of two or more.
  • 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 rate.
  • the amount is more preferably 1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass.
  • a thermal radical generator described in paragraphs 0120 to 0121 of JP 2012-8223 A, a nitrogen-containing compound described in WO 2011/136074 A1 and a thermal acid generator can also be used, and these may be used. The contents of are incorporated herein by reference.
  • the components are mixed in a predetermined ratio and in an arbitrary method, and dissolved by stirring to prepare a photosensitive resin composition.
  • the components may be respectively dissolved in advance in a solvent, and then these may be mixed at a predetermined ratio to prepare a resin composition.
  • the composition solution prepared as described above can also be used after being filtered using a filter with a pore size of 0.2 ⁇ m or the like.
  • the method for producing a cured film of the present invention preferably includes the following steps (1) to (5). (1) a step of applying the photosensitive resin composition of the present invention on a substrate; (2) removing the solvent from the applied photosensitive resin composition; (3) exposing the photosensitive resin composition from which the solvent has been removed to actinic radiation; (4) developing the exposed photosensitive resin composition with an aqueous developer; (5) A post-baking step of heat curing the developed photosensitive resin composition. Each step will be described in order below.
  • the photosensitive resin composition of the present invention it is preferable to apply the photosensitive resin composition of the present invention on a substrate to form a wet film containing a solvent. It is preferable to wash the substrate such as alkali washing and plasma washing before applying the photosensitive resin composition to the substrate, and it is more preferable to treat the surface of the substrate with hexamethyldisilazane after washing the substrate. By performing this treatment, the adhesion of the photosensitive resin composition to the substrate tends to be improved.
  • the method for treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
  • Examples of the above-mentioned substrate include inorganic substrates, resins, resin composite materials and the like.
  • the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper or the like is vapor-deposited on a substrate such as them.
  • polystyrene polycarbonate, polysulfone, polyether sulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamide imide, polyether imide, poly Benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, fluorocarbon resin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aroma Made of synthetic resin such as aliphatic ether, maleimido olefin, cellulose and episulfide compound
  • substrates which may be mentioned are less if used while the above embodiment, normally, depending on the form of the final product, for example, multi-
  • the method of coating on a substrate is not particularly limited, and for example, methods such as slit coating, spraying, roll coating, spin coating, cast coating, slit and spin may be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
  • the wet film thickness when applied is not particularly limited, and the film thickness can be applied according to the application, but it is usually used in the range of 0.5 to 10 ⁇ m.
  • the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating on the substrate.
  • the heating conditions for the solvent removal step are preferably about 70 to 130 ° C. for about 30 to 300 seconds. When the temperature and time are in the above range, the adhesion of the pattern tends to be better and the residue can be further reduced.
  • the substrate provided with the coating film is irradiated with an actinic ray through a mask having a predetermined pattern.
  • the photoacid generator is decomposed to generate an acid.
  • the acid-degradable group contained in the coating film component is hydrolyzed to form a carboxyl group or a phenolic hydroxyl group.
  • Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, LED light sources, excimer laser generators and the like can be used as exposure light sources for actinic light, and g-line (436 nm), i-line (365 nm), h-line An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as 405 nm) can be preferably used.
  • a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed.
  • PEB Post Exposure Bake
  • the temperature for PEB is preferably 30 ° C. or more and 130 ° C. or less, more preferably 40 ° C. or more and 110 ° C.
  • the acid-degradable group in the present invention has a low activation energy for acid decomposition, and is easily decomposed by an acid generator-derived acid upon exposure to form a carboxyl group or a phenolic hydroxyl group, so PEB is not necessarily performed. Positive images can also be formed by development.
  • the polymer having free carboxyl group or phenolic hydroxyl group is developed using an alkaline developer.
  • a positive image is formed by removing an exposed area including a resin composition having a carboxyl group or a phenolic hydroxyl group which is easily dissolved in an alkaline developer.
  • the developing solution used in the developing step preferably contains a basic compound.
  • Examples of basic compounds 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; ammonium hydroxides such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of the above-mentioned alkalis can also be used as a developer.
  • 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
  • a 0.4% aqueous solution of tetraethylammonium hydroxide, a 0.5% aqueous solution, a 0.7% aqueous solution, and a 2.38% aqueous solution 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 method of development may be any of a liquid deposition method, a dip method and the like. After development, running water washing can be carried out usually for 30 to 300 seconds to form a desired pattern.
  • a rinse process can also be performed after image development. In the rinse step, the substrate after development is washed with pure water or the like to remove the attached developer and to remove the development residue.
  • the rinse method can use a well-known method. For example, shower rinse and dip rinse can be mentioned.
  • the obtained positive image is heated to thermally decompose the acid-degradable group to form a carboxyl group or a phenolic hydroxyl group, and crosslink it with a crosslinkable group, a crosslinking agent, etc. And a cured film can be formed.
  • This heating is performed by heating at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on a hot plate, or 30 to 120 minutes in an oven, using a heating device such as a hot plate or an oven.
  • a protective film or an interlayer insulating film can be formed which is more excellent in heat resistance, hardness, and the like.
  • the transparency can be further improved.
  • post-baking can also be performed after baking at a relatively low temperature (addition of a middle-baking step).
  • middle baking it is preferable to perform post baking 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 divided into three or more stages and heated. The taper angle of the pattern can be adjusted by means of such middle baking and post baking.
  • the heating may be performed using a known heating method such as a hot plate, an oven, or an infrared heater.
  • a known heating method such as a hot plate, an oven, or an infrared heater.
  • the substrate on which a pattern has been formed is re-exposed (post-exposed) over the entire surface with actinic light and then post-baked to generate an acid from the photoacid generator present in the unexposed area. It can function as a promoting catalyst 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 such as ashing, plasma etching, or ozone etching can be performed as the etching treatment.
  • the cured film of the present invention is a cured film obtained by curing the 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.
  • an interlayer insulating film having excellent insulation and high transparency even when baked at high temperature can be obtained.
  • the interlayer insulating film formed using the photosensitive resin composition of the present invention has high transparency and is excellent in cured film physical properties, and thus is useful for applications of organic EL display devices and liquid crystal display devices.
  • the liquid crystal display device of the present invention is characterized by comprising 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 by 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 the 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 cured film of the present invention can also be used in a liquid crystal display device of a COA (Color Filter on Allay) system, and, for example, the organic insulating film (115) of JP-A 2005-284291 or It can be used as the organic insulating film (212) described in JP-A-346054.
  • COA Color Filter on Allay
  • the rubbing orientation method, the optical orientation method, etc. are mentioned.
  • the polymer orientation may be supported by the PSA (Polymer Sustained Alignment) technology described in JP-A-2003-149647 and JP-A-2011-257734.
  • the photosensitive resin composition of this invention and the cured film of this invention can be used for various uses, without being limited to the said use.
  • FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix 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 is all pixels disposed between two glass substrates 14 and 15 to which a polarizing film is attached.
  • an ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17.
  • an RGB color filter 22 in which a layer of liquid crystal 20 and a black matrix are arranged is provided.
  • the light source for the backlight is not particularly limited, and any known light source can be used. For example, white LEDs, multicolor LEDs such as blue, red and green, fluorescent lamps (cold cathode tubes), organic EL and the like can be mentioned.
  • the liquid crystal display device may be a 3D (stereoscopic) type or a touch panel type.
  • the organic EL display device of the present invention is characterized by comprising 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 planarizing film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures are used.
  • An organic EL display device and a liquid crystal display device can be mentioned.
  • specific examples of TFTs (Thin-Film Transistors) included in the organic EL display device of the present invention include amorphous silicon-TFTs, low temperature polysilicon-TFTs, oxide semiconductor TFTs, and the like.
  • FIG. 2 is a structural conceptual view of an example of the 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 planarization 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 in a state of covering the TFT 1.
  • a contact hole not shown
  • a wire 2 (height 1.0 ⁇ m) connected to the TFT 1 via the contact hole is formed on the insulating film 3.
  • the wiring 2 is for connecting the TFT 1 to an organic EL element formed between the TFTs 1 or in a later step. Furthermore, in order to planarize the unevenness due to the formation of the wiring 2, the planarization layer 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is embedded. A bottom emission type organic EL element is formed on the planarization film 4. That is, the first electrode 5 made of ITO is formed on the planarization 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, and the provision of the insulating film 8 prevents a short circuit between the first electrode 5 and a second electrode to be formed in a later step. can do. Furthermore, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then the entire surface of the substrate is made of Al. An active matrix type organic is formed by forming two electrodes and bonding them together by using a sealing glass plate and an ultraviolet curable epoxy resin and connecting each organic EL element to the TFT 1 for driving the same. An EL display device is obtained.
  • a resist pattern formed using the photosensitive resin composition of the present invention is used as a partition, or mechanically driven as a structural member of a MEMS device. Used incorporated as part of parts.
  • a MEMS device include parts such as a SAW filter, a BAW filter, a gyro sensor, a micro shutter for display, an image sensor, an electronic paper, an inkjet head, a biochip, a sealant, and the like. More specific examples are illustrated in JP-A-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 flattening film (57) described in FIG. 2 of JP-A-2011-107476, JP-A 2010-
  • MATHF tetrahydrofuran-2-yl methacrylate (synthetic product)
  • MAEVE 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MACHOE 1- (Cyclohexyloxy) ethyl methacrylate (synthetic)
  • MATHP tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • GMA glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • OXE-30 Methacrylic acid (3-ethyloxetan-3-yl) methyl (Osaka Organic Chemical Industry Co., Ltd.
  • NBMA n-butoxymethyl acrylamide (manufactured by Mitsubishi Rayon Co., Ltd.)
  • MAA methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
  • HEMA 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MMA methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • St Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)
  • DCPM dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
  • V-601 Dimethyl-2,2'-azobis (2-methyl propionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
  • V-65 2,2'-azobis (2,4-dimethyl valeronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MEDG Diethylene glycol
  • MACHOE was synthesized in the same manner as the aforementioned MATHF except that 2-dihydrofuran was changed to the corresponding compound.
  • oxime compound (2.4 g) After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
  • the obtained oxime compound (1.8 g) is dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) are added under ice-cooling, and the temperature is raised to room temperature. It was made to react for time. 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 B1 (2.3 g).
  • the reaction solution was poured into 1N aqueous HCl solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid, and 30 g of polyphosphoric acid was added and reacted at 170 ° C. for 30 minutes.
  • the reaction solution was poured into water (300 mL), ethyl acetate (300 mL) was added to separate it, and the organic layer was concentrated and then purified by silica gel column chromatography to obtain a ketone compound (10 g).
  • Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g) and magnesium sulfate (4.5 g) were added to a suspension of the obtained ketone compound (10.0 g) and methanol (100 mL) for 24 hours. Heated to reflux. After allowing to cool, water (150 mL) and ethyl acetate (150 mL) are added and separated, and the organic layer is separated four times with 80 mL of water, concentrated and then purified by silica gel column chromatography to obtain an oxime compound (5.8 g) I got The obtained oxime (3.1 g) was sulfonated in the same manner as B1 to obtain B2 (3.2 g).
  • B3 was synthesized in the same manner as B1, except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in B1.
  • H1 1,5-Diazabicyclo [4,3,0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • H2 compound of the following structure
  • F1 JER 157 S 65 (Mitsubishi Chemical Corporation)
  • F2 Duranate 17B-60P (manufactured by Asahi Kasei Chemicals Corporation)
  • F3 Death Module BL4265SN (manufactured by Sumika Bayer Urethane Co., Ltd.)
  • J1 Irganox 1035FF (antioxidant, manufactured by BASF)
  • J2 Irganox 1098 (antioxidant, manufactured by BASF)
  • J3 Adekastab AO-60 (antioxidant, manufactured by ADEKA Co., Ltd.)
  • the photosensitive resin composition layer after exposure was developed with an alkaline developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
  • the optimum i-line exposure (Eopt) when resolving a 5 ⁇ m hole by these operations was taken as the sensitivity.
  • a liquid crystal display device using a thin film transistor (TFT) was manufactured by the following method (see FIG. 2).
  • a cured film 17 was formed as an interlayer insulating film as follows to obtain a liquid crystal display device. That is, the bottom gate type TFT 1 was formed on the glass substrate 6, and the insulating film 3 made of Si 3 N 4 was formed in a state of covering the TFT 1. Next, after forming a contact hole in the insulating film 3, a wire 2 (height 1.0 ⁇ m) connected to the TFT 1 via the contact hole was formed on the insulating film 3.
  • the planarizing film 4 was formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is embedded.
  • the formation of the planarizing film 4 on the insulating film 3 is carried out by spin-coating the photosensitive resin compositions of Examples and Comparative Examples on the substrate and prebaking (90.degree. C..times.2 minutes) on a hot plate, followed by a mask.
  • i-line (365 nm) is irradiated with 25 mJ / cm 2 (energy intensity 20 mW / cm 2 ) using a high pressure mercury lamp, then developed with an alkaline aqueous solution to form a pattern, and heat treatment at 230 ° C for 60 minutes went.
  • the coatability at the time of applying the photosensitive resin composition was good, and no wrinkles or cracks were found in the cured film obtained after exposure, development and baking.
  • the average step difference of the wiring 2 was 500 nm, and the film thickness of the manufactured planarization film 4 was 2,000 nm.
  • a driving voltage is applied to the obtained liquid crystal display device, a gray test signal is input, the panel is continuously lit in an environment of 60 ° C., 90%, and the gray display after lighting for 1000 hours is visually observed.
  • the occurrence of display unevenness was evaluated according to the following evaluation criteria.
  • C There is slight unevenness in the display, but it is at a practical level (normal)
  • D There is unevenness in the display (somewhat bad)
  • E Strong unevenness in display (very bad)
  • the photosensitive resin composition of the present invention has high sensitivity, is excellent in chemical resistance of a cured film, and suppresses the occurrence of panel display unevenness in a panel reliability test.
  • the photosensitive resin composition of the comparative example did not satisfy all the items of sensitivity, chemical resistance and panel display unevenness.
  • Example 74 was carried out in the same manner as Example 1 except that the exposure apparatus was changed from Canon Inc. MPA 5500 CF to Nikon Inc. FX-803M (gh-line stepper). Evaluations of sensitivity, chemical resistance and panel display unevenness were at the same level as in Example 1.
  • Example 75 was carried out in the same manner as in Example 1 except that the exposure device was changed from MPA 5500CF manufactured by Canon Inc. to a 355 nm laser exposure device and the 355 nm laser exposure was performed.
  • the 355 nm laser exposure apparatus “AEGIS” manufactured by Vu-Technologies Corporation was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR. Evaluations of sensitivity, chemical resistance and panel display unevenness were at the same level as in Example 1.
  • Example 76 was carried out in the same manner as in Example 1 except that the exposure device was changed from MPA 5500CF manufactured by Canon Inc. to a UV-LED light source exposure device. Evaluations of sensitivity, chemical resistance and panel display unevenness were at the same level as in Example 1.
  • Example 77 A liquid crystal display similar to that of Example 1 was obtained by changing only the coating process described below. That is, after the photosensitive resin composition of Example 1 was applied by a slit coating method, the solvent was removed by heating on a hot plate at 90 ° C. for 120 seconds, and a photosensitive resin composition layer having a film thickness of 3.0 ⁇ m was obtained. It formed. The obtained coating film was flat and had a good surface condition without unevenness. Further, the performance as a liquid crystal display was also good as in Example 1.
  • the photosensitive resin composition of an Example is excellent in a sensitivity and chemical resistance irrespective of an exposure machine or a coating method, and can obtain a liquid crystal display with high panel reliability.
  • Example 78 An organic EL display device using thin film transistors (TFTs) was manufactured 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 in a state of covering the TFT 1.
  • a wire 2 (height 1.0 ⁇ m) connected to the TFT 1 via the contact hole was formed on the insulating film 3.
  • the wiring 2 is for connecting the TFT 1 to an organic EL element formed between the TFTs 1 or in a later step.
  • the planarizing film 4 was formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is embedded.
  • the planarizing film 4 was formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 16 on a substrate and prebaking (90 ° C./120 seconds) on a hot plate, high pressure is applied from above the mask After i-line (365 nm) was irradiated at 45 mJ / cm 2 (energy intensity: 20 mW / cm 2 ) using a mercury lamp, development was performed with an alkaline aqueous solution to form a pattern, and heat treatment was performed at 230 ° C./30 minutes.
  • the coatability at the time of applying the photosensitive resin composition was good, and no wrinkles or cracks were found in the cured film obtained after exposure, development and baking. Furthermore, the average step difference of the wiring 2 was 500 nm, and the film thickness of the manufactured planarization film 4 was 2,000 nm.
  • a bottom emission type organic EL element was formed on the obtained planarization film 4.
  • the first electrode 5 made of ITO was formed on the planarization film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • the resist was applied, prebaked, exposed through a mask of a desired pattern, and developed. Pattern processing was performed by wet etching using an ITO etchant using this resist pattern as a mask. Thereafter, the resist pattern was peeled at 50 ° C. using a resist peeling solution (remover 100, manufactured by AZ Electronic Materials).
  • the first electrode 5 thus obtained corresponds to the anode of the organic EL element.
  • the insulating film 8 having a shape covering the periphery of the first electrode 5 was formed.
  • the insulating film 8 was formed on the insulating film 8 using the photosensitive resin composition of Example 1 by the same method as described above. By providing this insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent steps can be prevented.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited and provided in a vacuum deposition apparatus via a desired pattern mask. Then, a second electrode made of Al was formed on the entire surface of the substrate. The obtained substrate was taken out of the vapor deposition machine, and sealed by using a sealing glass plate and an ultraviolet curable epoxy resin to bond them.
  • an active matrix organic EL display device was obtained in which each organic EL element was connected with a TFT 1 for driving the organic EL element.
  • a voltage was applied through the drive circuit, it was found that the organic EL display device exhibited excellent display characteristics and was highly reliable.

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015087759A (ja) * 2013-09-24 2015-05-07 住友化学株式会社 レジスト組成物及びレジストパターンの製造方法
JP2015176124A (ja) * 2014-03-18 2015-10-05 Jsr株式会社 ポジ型感光性樹脂組成物
JP2015191216A (ja) * 2014-03-28 2015-11-02 Jsr株式会社 感放射線性樹脂組成物及びレジストパターン形成方法
CN106047371A (zh) * 2015-04-09 2016-10-26 Jsr株式会社 液晶取向剂、液晶取向膜以及液晶元件
KR20170016791A (ko) * 2015-08-04 2017-02-14 신에쓰 가가꾸 고교 가부시끼가이샤 화학 증폭 포지티브형 레지스트 조성물 및 패턴 형성 방법
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012029758A1 (ja) * 2010-08-30 2012-03-08 富士フイルム株式会社 感光性樹脂組成物、オキシムスルホネート化合物、硬化膜の形成方法、硬化膜、有機ｅｌ表示装置、及び、液晶表示装置
JP2012098557A (ja) * 2010-11-02 2012-05-24 Fujifilm Corp Ｍｅｍｓ構造部材用感光性樹脂組成物、パターン作製方法、並びに、ｍｅｍｓ構造体及びその作製方法
CN102540726A (zh) * 2010-12-13 2012-07-04 富士胶片株式会社 正型感光性树脂组成物、硬化膜及其形成方法、层间绝缘膜以及显示装置
JP2012128198A (ja) * 2010-12-15 2012-07-05 Fujifilm Corp 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機ｅｌ表示装置、及び、液晶表示装置
JP2012155115A (ja) * 2011-01-26 2012-08-16 Jsr Corp ポジ型感放射線性組成物、層間絶縁膜及びその形成方法
JP2012173438A (ja) * 2011-02-18 2012-09-10 Fujifilm Corp パターン形成方法、感活性光線性又は感放射線性樹脂組成物、及びレジスト膜
JP2012181488A (ja) * 2010-11-02 2012-09-20 Fujifilm Corp エッチングレジスト用感光性樹脂組成物、パターン作製方法、ｍｅｍｓ構造体及びその作製方法、ドライエッチング方法、ウェットエッチング方法、ｍｅｍｓシャッターデバイス、並びに、画像表示装置
JP2012226181A (ja) * 2011-04-20 2012-11-15 Jsr Corp 感放射線性樹脂組成物、表示素子用層間絶縁膜及びその形成方法
JP2012234148A (ja) * 2011-04-20 2012-11-29 Jsr Corp ポジ型感光性樹脂組成物、表示素子用層間絶縁膜及びその形成方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08240908A (ja) * 1994-12-29 1996-09-17 Tokyo Ohka Kogyo Co Ltd 感光性樹脂組成物、それを用いた感光性平版印刷版、および平版印刷用版材の製造方法
JP2004272182A (ja) * 2002-04-24 2004-09-30 Mitsubishi Chemicals Corp 画像形成方法
JP4683182B2 (ja) * 2004-09-28 2011-05-11 山栄化学株式会社 感光性熱硬化性樹脂組成物、並びにレジスト被覆プリント配線板及びその製造法
WO2006099380A2 (en) * 2005-03-11 2006-09-21 E.I. Dupont De Nemours And Company Photoimageable, thermosettable fluorinated resists
JP2009288343A (ja) * 2008-05-27 2009-12-10 Fujifilm Corp ポジ型レジスト組成物、及び該組成物を用いたパターン形成方法
JP5451570B2 (ja) 2009-10-16 2014-03-26 富士フイルム株式会社 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機ｅｌ表示装置、及び、液晶表示装置
JP5524037B2 (ja) * 2010-01-19 2014-06-18 富士フイルム株式会社 感光性樹脂組成物、硬化膜、硬化膜の形成方法、有機ｅｌ表示装置、及び、液晶表示装置
EP2447773B1 (en) * 2010-11-02 2013-07-10 Fujifilm Corporation Method for producing a pattern, method for producing a MEMS structure, use of a cured film of a photosensitive composition as a sacrificial layer or as a component of a MEMS structure
JP5417422B2 (ja) * 2010-12-13 2014-02-12 富士フイルム株式会社 ポジ型感光性樹脂組成物
JP5642578B2 (ja) * 2011-01-28 2014-12-17 富士フイルム株式会社 感光性樹脂組成物、硬化膜の製造方法、硬化膜、有機ｅｌ表示装置および液晶表示装置

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012029758A1 (ja) * 2010-08-30 2012-03-08 富士フイルム株式会社 感光性樹脂組成物、オキシムスルホネート化合物、硬化膜の形成方法、硬化膜、有機ｅｌ表示装置、及び、液晶表示装置
JP2012098557A (ja) * 2010-11-02 2012-05-24 Fujifilm Corp Ｍｅｍｓ構造部材用感光性樹脂組成物、パターン作製方法、並びに、ｍｅｍｓ構造体及びその作製方法
JP2012181488A (ja) * 2010-11-02 2012-09-20 Fujifilm Corp エッチングレジスト用感光性樹脂組成物、パターン作製方法、ｍｅｍｓ構造体及びその作製方法、ドライエッチング方法、ウェットエッチング方法、ｍｅｍｓシャッターデバイス、並びに、画像表示装置
CN102540726A (zh) * 2010-12-13 2012-07-04 富士胶片株式会社 正型感光性树脂组成物、硬化膜及其形成方法、层间绝缘膜以及显示装置
JP2012128198A (ja) * 2010-12-15 2012-07-05 Fujifilm Corp 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機ｅｌ表示装置、及び、液晶表示装置
JP2012155115A (ja) * 2011-01-26 2012-08-16 Jsr Corp ポジ型感放射線性組成物、層間絶縁膜及びその形成方法
JP2012173438A (ja) * 2011-02-18 2012-09-10 Fujifilm Corp パターン形成方法、感活性光線性又は感放射線性樹脂組成物、及びレジスト膜
JP2012226181A (ja) * 2011-04-20 2012-11-15 Jsr Corp 感放射線性樹脂組成物、表示素子用層間絶縁膜及びその形成方法
JP2012234148A (ja) * 2011-04-20 2012-11-29 Jsr Corp ポジ型感光性樹脂組成物、表示素子用層間絶縁膜及びその形成方法

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WO2019064961A1 (ja) * 2017-09-29 2019-04-04 富士フイルム株式会社 感光性樹脂組成物、レジスト膜、パターン形成方法及び電子デバイスの製造方法
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