WO2014050627A1 - Photosensitive resin composition, method for forming cured film using same, cured film, liquid crystal display device, and organic el display device - Google Patents

Photosensitive resin composition, method for forming cured film using same, cured film, liquid crystal display device, and organic el display device Download PDF

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Publication number
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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French (fr)
Japanese (ja)
Inventor
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 JP2014538405A priority Critical patent/JP5933734B2/en
Priority to KR1020157006403A priority patent/KR101725810B1/en
Priority to CN201380049705.6A priority patent/CN104685416B/en
Publication of WO2014050627A1 publication Critical patent/WO2014050627A1/en

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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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Abstract

Provided is a photosensitive resin composition having superior chemical resistance while maintaining high sensitivity. The photosensitive resin composition contains: a polymer having (a1) a constituent unit having a group such that an acid group is protected by an acid-labile group and (a2) a constituent unit having a cross-linkable group, or (2) (a1) a polymer having a constituent unit having a group such that an acid group is protected by an acid-labile group and (a2) a polymer having a constituent unit having a cross-linkable group; (B) a photoacid generator; (C) an aromatic heterocyclic compound having a molecular weight of no greater than 1000, containing at least one nitrogen atom in the aromatic ring, and containing at least two coordinating atoms in the aromatic ring; and (D) a solvent.

Description

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PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR PRODUCING CURED FILM USING SAME, CURED FILM, LIQUID CRYSTAL DISPLAY DEVICE, AND ORGANIC EL DISPLAY DEVICE
　本発明は、ポジ型感光性樹脂組成物、硬化膜の形成方法、硬化膜、液晶表示装置、および、有機ＥＬ表示装置に関する。さらに詳しくは、液晶表示装置、有機ＥＬ表示装置、集積回路素子、固体撮像素子などの電子部品の平坦化膜、保護膜や層間絶縁膜の形成に好適な、ポジ型感光性樹脂組成物およびそれを用いた硬化膜の形成方法に関する。 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
　薄膜トランジスタ（以下、「ＴＦＴ」と記す。）型液晶表示素子や磁気ヘッド素子、集積回路素子、固体撮像素子などの電子部品には、一般に層状に配置される配線の間を絶縁するために層間絶縁膜が設けられている。層間絶縁膜を形成する材料としては、必要とするパターン形状を得るための工程数が少なくしかも十分な平坦性を有するものが好ましいことから、感光性樹脂組成物が幅広く使用されている。このような感光性樹脂組成物としては、例えば、特許文献１が挙げられる。 In electronic components such as thin film transistors (hereinafter referred to as "TFTs") type liquid crystal display elements, magnetic head elements, integrated circuit elements, solid-state imaging elements, etc., interlayer insulation in order to insulate between wirings generally arranged in layers. A membrane is provided. As a material for forming the interlayer insulating film, 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. As such a photosensitive resin composition, patent document 1 is mentioned, for example.
特開２０１１－２０９６８１号公報JP, 2011-209681, A
　かかる表示装置などの電子部品の製造には、多様な薬液が使用され、これらの薬液に対する耐性が必須となる。また、高温度、高湿度、高圧力条件下での高いパネル信頼性が要求され、近年の表示装置の高精細化に伴い、その要求は益々高まってきている。 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. In addition, 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.
　また、電子部品における層間絶縁膜を形成するために使用される感光性樹脂組成物には、増感剤や光開始助剤として芳香族複素環化合物が添加されることがある。しかし、本願発明者が検討したところ、これらの感光性樹脂組成物は膜硬化後の耐薬品性が低く、これら感光性樹脂組成物を用いると、パネル信頼性試験においてパネル表示ムラが生じやすくなる場合があることが分かった。 In addition, 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. However, when examined by the inventors of the present invention, 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.
　本発明は上記課題を解決することを目的としたものであって、感度が高く、硬化膜の耐薬品性が優れ、パネル信頼性試験においてパネル表示ムラの発生を抑制した感光性樹脂組成物を提供することを目的とする。さらに、このような感光性樹脂組成物を用いた硬化膜の形成方法、硬化膜、有機ＥＬ表示装置、および、液晶表示装置を提供することを目的とする。 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.
　かかる状況のもと、本願発明者が鋭意検討を行い、検討を行った結果、所定の分子量を有し、芳香環中に少なくとも１つの窒素原子を含み、且つ芳香環中に少なくとも２つの配位原子を含む芳香族複素環化合物を用いることによって、高い感度を維持しつつ、耐薬品性に優れることを見出した。このメカニズムは定かではないが、低分子量の芳香族複素環化合物は、基板側に容易に移動し、芳香族複素環化合物中の配位原子が下地基板と相互作用し、高温度、高湿度、高圧力条件下で発生する感光性樹脂組成物からの分解物が下地基板に侵入することを抑制し、パネル信頼性の向上に寄与していると考えられる。また、芳香族複素環化合物が硬化膜の架橋を促進していると推定され、耐薬品性の向上に寄与しているものと考えられる。 Under such circumstances, 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. By using the aromatic heterocyclic compound containing an atom, it discovered that it was excellent in chemical resistance, maintaining high sensitivity. Although the mechanism is not clear, 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. Moreover, it is presumed that the aromatic heterocyclic compound promotes the crosslinking of the cured film, and is considered to contribute to the improvement of the chemical resistance.
　前記課題を解決するための手段は、下記＜１＞の手段であり、好ましくは、下記＜２＞～＜１６＞の手段である。
＜１＞（Ａ）下記（１）および（２）の少なくとも一方を満たす重合体を含む重合体成分、
（１）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位、および（ａ２）架橋性基を有する構成単位、を有する重合体、
（２）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位を有する重合体、および（ａ２）架橋性基を有する構成単位を有する重合体、
（Ｂ）光酸発生剤、
（Ｃ）芳香族複素環化合物、および、
（Ｄ）溶剤、
を含み、前記（Ｃ）芳香族複素環化合物が、分子量１０００以下であり、芳香環中に少なくとも１つの窒素原子を含み、且つ芳香環中に少なくとも２つの配位原子を含むことを特徴とする感光性樹脂組成物。
＜２＞前記（Ｃ）の芳香族複素環化合物が、５員環芳香族複素環化合物、６員環芳香族複素環化合物、５員環芳香族複素環構造および６員環芳香族複素環構造の少なくとも一方を含む多環式芳香族複素環化合物のいずれかであることを特徴とする、＜１＞に記載の感光性樹脂組成物。
＜３＞前記配位原子が窒素原子、硫黄原子、酸素原子のいずれかである、＜１＞または＜２＞に記載の感光性樹脂組成物。
＜４＞前記（Ａ）の重合体において、（ａ２）架橋性基を有する構成単位に含まれる架橋性基が、エポキシ基、オキセタニル基、および－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは水素原子または炭素数１～２０のアルキル基）で表される基から選ばれる少なくとも１種である、＜１＞～＜３＞のいずれかに記載の感光性樹脂組成物。
＜５＞前記酸分解性基がアセタールの形で保護された構造を有する基である、＜１＞～＜４＞のいずれかに記載の感光性樹脂組成物。
＜６＞前記（Ａ）の重合体成分のいずれかが、さらに、酸基を含有する重合体である、＜１＞～＜５＞のいずれかに記載の感光性樹脂組成物。
＜７＞前記（Ｂ）の光酸発生剤が、オキシムスルホネート化合物である、＜１＞～＜６＞のいずれかに記載の感光性樹脂組成物。
＜８＞前記（Ｃ）の芳香族複素環化合物が、芳香環中に２～３つの配位原子を含む、＜１＞～＜７＞のいずれかに記載の感光性樹脂組成物。
＜９＞前記（Ｃ）の芳香族複素環化合物が、芳香環中に少なくとも２つの窒素原子を含む、＜１＞～＜８＞のいずれかに記載の感光性樹脂組成物。
＜１０＞前記（Ｃ）芳香族複素環化合物が有する環が、単環、ならびに／または、２つもしくは３つの環の縮合環である、＜１＞～＜９＞のいずれかに記載の感光性樹脂組成物。
＜１１＞前記（Ｃ）芳香族複素環化合物における芳香環が有する置換基としてアミノ基を含まないことを特徴とする、＜１＞～＜１０＞のいずれかに記載の感光性樹脂組成物。
＜１２＞（１）＜１＞～＜１１＞のいずれかに記載の感光性樹脂組成物を基板上に塗布する塗布工程、
　（２）塗布された感光性樹脂組成物から溶剤を除去する溶剤除去工程、
　（３）溶剤が除去された感光性樹脂組成物を活性光線により露光する露光工程、
　（４）露光された感光性樹脂組成物を水性現像液により現像する現像工程、および、
　（５）現像された感光性樹脂組成物を熱硬化するポストベーク工程、
を含む硬化膜の形成方法。
＜１３＞前記現像工程後、前記ポストベーク工程前に、現像された感光性樹脂組成物を全面露光する工程を含む、＜１２＞に記載の硬化膜の形成方法。
＜１４＞＜１２＞または＜１３＞に記載の方法により形成された硬化膜。
＜１５＞層間絶縁膜である、＜１４＞に記載の硬化膜。
＜１６＞＜１４＞または＜１５＞に記載の硬化膜を具備する有機ＥＬ表示装置または液晶表示装置。 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) 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. Photosensitive resin composition.
<2> 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.
<4> In the polymer of (A), 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.
<5> The photosensitive resin composition according to any one of <1> to <4>, which is a group having a structure in which the acid decomposable group is protected in the form of acetal.
The photosensitive resin composition according to any one of <1> to <5>, wherein any one of the polymer components of <6> the above (A) is a polymer further containing an acid group.
The photosensitive resin composition as described in any one of <1>-<6> whose photo-acid generator of <7> said (B) is an oxime sulfonate compound.
<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.
<9> The aromatic heterocyclic compound of component (C), comprising at least two nitrogen atoms in the aromatic ring, <1> to the photosensitive resin composition according to any one of <8>.
<10> The photosensitive group according to any one of <1> to <9>, wherein the ring of the (C) aromatic heterocyclic compound is a single ring and / or a fused ring of two or three rings. Resin composition.
<11> The photosensitive resin composition according to any one of <1> to <10>, which does not contain an amino group as a substituent which the aromatic ring in the (C) aromatic heterocyclic compound has.
<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 formed by the method as described in <14><12> or <13>.
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>.
　本発明によれば、高い感度を維持しつつ、耐薬品性に優れる感光性樹脂組成物、パターンの製造方法、有機ＥＬ表示装置、液晶表示装置の製造方法および硬化膜を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, 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.
液晶表示装置の一例の構成概念図を示す。液晶表示装置におけるアクティブマトリックス基板の模式的断面図を示し、層間絶縁膜である硬化膜１７を有している。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. 有機ＥＬ表示装置の一例の構成概念図を示す。ボトムエミッション型の有機ＥＬ表示装置における基板の模式的断面図を示し、平坦化膜４を有している。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.
　以下において、本発明の内容について詳細に説明する。以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。尚、本願明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。 Hereinafter, the contents of the present invention will be described in detail. Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments. In the present specification, “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.
　なお、本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　さらに、（メタ）アクリル酸とは、アクリル酸および／またはメタクリル酸を意味する。 In the description of groups (atomic groups) in the present specification, the notations not describing substitution and non-substitution include those having no substituent and those having a substituent. For example, the "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).
Furthermore, (meth) acrylic acid means acrylic acid and / or methacrylic acid.
　本発明の感光性樹脂組成物（以下、「本発明の組成物」ということがある。）は、（Ａ）下記（１）および（２）の少なくとも一方を満たす重合体を含む重合体成分、
（１）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位、および（ａ２）架橋性基を有する構成単位、を有する重合体、
（２）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位を有する重合体、および（ａ２）架橋性基を有する構成単位を有する重合体、
（Ｂ）光酸発生剤、
（Ｃ）芳香族複素環化合物、および、
（Ｄ）溶剤、
を含み、前記（Ｃ）芳香族複素環化合物が、分子量１０００以下であり、芳香環中に少なくとも１つの窒素原子を含み、且つ芳香環中に少なくとも２つの配位原子を含むことを特徴とする。また、本発明の感光性樹脂組成物は、化学増幅ポジ型感光性樹脂組成物であることが好ましい。
　以下、本発明の組成物について詳細に説明する。 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. . Moreover, it is preferable that the photosensitive resin composition of this invention is a chemical amplification positive type photosensitive resin composition.
Hereinafter, the composition of the present invention will be described in detail.
＜（Ａ）重合体成分＞
　本発明の組成物は、重合体成分として、（１）（ａ１）酸基が酸分解性基で保護された基を有する構成単位および（ａ２）架橋性基を有する構成単位を有する重合体、ならびに（２）（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体および（ａ２）架橋性基を有する構成単位を有する重合体、の少なくとも一方を含む。さらに、これら以外の重合体を含んでいてもよい。本発明における（Ａ）重合体成分（以下、「（Ａ）成分」というがある）は、特に述べない限り、上記（１）および／または（２）に加え、必要に応じて添加される他の重合体を含めたものを意味する。 <(A) Polymer component>
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
＜＜構成単位（ａ１）＞＞
　成分Ａは、（ａ１）酸基が酸分解性基で保護された基を有する構成単位を少なくとも有する。（Ａ）成分が構成単位（ａ１）を有することにより、極めて高感度な感光性樹脂組成物とすることができる。
　本発明における「酸基が酸分解性基で保護された基」は、酸基および酸分解性基として公知のものを使用でき、特に限定されない。具体的な酸基としては、カルボキシル基、および、フェノール性水酸基が好ましく挙げられる。また、酸分解性基としては、酸により比較的分解し易い基（例えば、後述する式（Ａ１）で表される基のエステル構造、テトラヒドロピラニルエステル基、または、テトラヒドロフラニルエステル基等のアセタール系官能基）や酸により比較的分解し難い基（例えば、ｔｅｒｔ－ブチルエステル基等の第三級アルキル基、ｔｅｒｔ－ブチルカーボネート基等の第三級アルキルカーボネート基）を用いることができる。 << Constituent Unit (a1) >>
Component A at least has a constituent unit having a group in which the acid group is protected by an acid-degradable group. When the 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. Moreover, as an acid decomposable group, 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.
　（ａ１）酸基が酸分解性基で保護された基を有する構成単位は、酸分解性基で保護された保護カルボキシル基を有する構成単位、または、酸分解性基で保護された保護フェノール性水酸基を有する構成単位であることが好ましい。
　以下、酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）と、酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）について、順にそれぞれ説明する。 (A1) 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.
Hereinafter, 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.
＜＜＜（ａ１－１）酸分解性基で保護された保護カルボキシル基を有する構成単位＞＞＞
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）は、カルボキシル基を有する構成単位のカルボキシル基が、以下で詳細に説明する酸分解性基によって保護された保護カルボキシル基を有する構成単位である。
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）に用いることができる上記カルボキシル基を有する構成単位としては、特に制限はなく公知の構成単位を用いることができる。例えば、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和トリカルボン酸などの、分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）や、エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位（ａ１－１－２）が挙げられる。
　以下、上記カルボキシル基を有する構成単位として用いられる（ａ１－１－１）分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位と、（ａ１－１－２）エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位について、それぞれ順に説明する。 <<< (Structural unit having a protected carboxyl group protected by (a1-1) acid decomposable group >>>
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. For example, 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.
Hereinafter, a structural unit derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in a molecule (a1-1-1) used as a structural unit having a carboxyl group, and (a1-1-2) ethylene Constituent units having both an unsaturated unsaturated group and a structure derived from an acid anhydride will be described in order.
＜＜＜＜（ａ１－１－１）分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位＞＞＞＞
　上記分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）として本発明で用いられる不飽和カルボン酸としては以下に挙げるようなものが用いられる。すなわち、不飽和モノカルボン酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸、α－クロロアクリル酸、けい皮酸、2－（メタ）アクリロイロキシエチル－コハク酸、2－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、2－（メタ）アクリロイロキシエチル－フタル酸、などが挙げられる。また、不飽和ジカルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸などが挙げられる。また、カルボキシル基を有する構成単位を得るために用いられる不飽和多価カルボン酸は、その酸無水物であってもよい。具体的には、無水マレイン酸、無水イタコン酸、無水シトラコン酸などが挙げられる。また、不飽和多価カルボン酸は、多価カルボン酸のモノ（２－メタクリロイロキシアルキル）エステルであってもよく、例えば、コハク酸モノ（２－アクリロイロキシエチル）、コハク酸モノ（２－メタクリロイロキシエチル）、フタル酸モノ（２－アクリロイロキシエチル）、フタル酸モノ（２－メタクリロイロキシエチル）などが挙げられる。さらに、不飽和多価カルボン酸は、その両末端ジカルボキシポリマーのモノ（メタ）アクリレートであってもよく、例えば、ω－カルボキシポリカプロラクトンモノアクリレート、ω－カルボキシポリカプロラクトンモノメタクリレートなどが挙げられる。また、不飽和カルボン酸としては、アクリル酸－２－カルボキシエチルエステル、メタクリル酸－２－カルボキシエチルエステル、マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、４－カルボキシスチレン等も用いることができる。
　中でも、現像性の観点から、上記分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）を形成するためには、アクリル酸、メタクリル酸、2－（メタ）アクリロイロキシエチル－コハク酸、2－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、2－（メタ）アクリロイロキシエチル－フタル酸、または不飽和多価カルボン酸の無水物等を用いることが好ましく、アクリル酸、メタクリル酸、2－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、を用いることがより好ましい。
　上記分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）は、１種単独で構成されていてもよいし、２種以上で構成されていてもよい。 <<<< 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 >>
As 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. . That is, as unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid, α-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. Moreover, as unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc. are mentioned, for example. Moreover, 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. Furthermore, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of its both terminal dicarboxy polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate and the like. Further, as the 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.
Above all, in order to form 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
　＜＜＜＜（ａ１－１－２）エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位＞＞＞＞
　エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位（ａ１－１－２）は、エチレン性不飽和基を有する構成単位中に存在する水酸基と酸無水物とを反応させて得られたモノマーに由来する単位であることが好ましい。
　上記酸無水物としては、公知のものが使用でき、具体的には、無水マレイン酸、無水コハク酸、無水イタコン酸、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水クロレンド酸等の二塩基酸無水物；無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物、ビフェニルテトラカルボン酸無水物などの酸無水物が挙げられる。これらの中では、現像性の観点から、無水フタル酸、テトラヒドロ無水フタル酸、または無水コハク酸、が好ましい。
　上記酸無水物の水酸基に対する反応率は、現像性の観点から、好ましくは１０～１００モル％、より好ましくは３０～１００モル％である。 <<<< (a1-1-2) structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>
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.
As the above 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. Among these, from the viewpoint of developability, 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.
　＜＜＜＜構成単位（ａ１－１）に用いることができる酸分解性基＞＞＞＞
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）に用いることができる上記酸分解性基としては上述の酸分解性基を用いることができる。
　これらの酸分解性基の中でもカルボキシル基がアセタールの形で保護された保護カルボキシル基であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、コンタクトホールの形成性、感光性樹脂組成物の保存安定性の観点から好ましい。さらに酸分解性基の中でもカルボキシル基が下記一般式（ａ１－１０）で表されるアセタールの形で保護された保護カルボキシル基であることが、感度の観点からより好ましい。なお、カルボキシル基が下記一般式（ａ１－１０）で表されるアセタールの形で保護された保護カルボキシル基である場合、保護カルボキシル基の全体としては、－（Ｃ＝Ｏ）－Ｏ－ＣＲ101Ｒ102（ＯＲ103）の構造となっている。 <<<< Acid-decomposable group that can be used for the structural unit (a1-1) >>
The above-mentioned acid-decomposable group 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.
Among 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. Further, among the acid-degradable groups, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10). When 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 ).
一般式（ａ１－１０）
Figure JPOXMLDOC01-appb-C000001
 　（式（ａ１－１０）中、Ｒ101およびＲ102は、それぞれ水素原子またはアルキル基を表し、但し、Ｒ101とＲ102とが共に水素原子の場合を除く。Ｒ103は、アルキル基を表す。Ｒ101またはＲ102と、Ｒ103とが連結して環状エーテルを形成してもよい。） General formula (a1-10)
Figure JPOXMLDOC01-appb-C000001
 (In formula (a1-10), 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).
　上記一般式（ａ１－１０）中、Ｒ101～Ｒ103は、それぞれ水素原子またはアルキル基を表し、上記アルキル基は直鎖状、分岐鎖状、環状のいずれでもよい。ここで、Ｒ101およびＲ102の双方が水素原子を表すことはなく、Ｒ101およびＲ102の少なくとも一方はアルキル基を表す。 In the above general formula (a1-10), R 101 to R 103 each represent a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic. Here, 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.
　上記一般式（ａ１－１０）において、Ｒ101、Ｒ102およびＲ103がアルキル基を表す場合、上記アルキル基は直鎖状、分岐鎖状または環状のいずれであってもよい。
　上記直鎖状または分岐鎖状のアルキル基としては、炭素数１～１２であることが好ましく、炭素数１～６であることがより好ましく、炭素数１～４であることがさらに好ましい。具体的には、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｎ－ヘキシル基、テキシル基（２，３－ジメチル－２－ブチル基）、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基、ｎ－ノニル基、ｎ－デシル基等を挙げることができる。 When 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. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n And -hexyl, texyl (2,3-dimethyl-2-butyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl and the like.
　上記環状アルキル基としては、炭素数３～１２であることが好ましく、炭素数４～８であることがより好ましく、炭素数４～６であることがさらに好ましい。上記環状アルキル基としては、例えばシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルニル基、イソボルニル基等を挙げることができる。 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.
　上記アルキル基は、置換基を有していてもよく、置換基としては、ハロゲン原子、アリール基、アルコキシ基が例示できる。置換基としてハロゲン原子を有する場合、Ｒ101、Ｒ102、Ｒ103はハロアルキル基となり、置換基としてアリール基を有する場合、Ｒ101、Ｒ102、Ｒ103はアラルキル基となる。
　上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が例示され、これらの中でもフッ素原子または塩素原子が好ましい。
　また、上記アリール基としては、炭素数６～２０のアリール基が好ましく、より好ましくは炭素数６～１２であり、具体的には、フェニル基、α－メチルフェニル基、ナフチル基等が例示でき、アリール基で置換されたアルキル基全体、すなわち、アラルキル基としては、ベンジル基、α－メチルベンジル基、フェネチル基、ナフチルメチル基等が例示できる。
　上記アルコキシ基としては、炭素数１～６のアルコキシ基が好ましく、より好ましくは炭素数１～４であり、メトキシ基またはエトキシ基がより好ましい。
　また、上記アルキル基がシクロアルキル基である場合、上記シクロアルキル基は置換基として炭素数１～１０の直鎖状または分岐鎖状のアルキル基を有していてもよく、アルキル基が直鎖状または分岐鎖状のアルキル基である場合には、置換基として炭素数３～１２のシクロアルキル基を有していてもよい。
　これらの置換基は、上記置換基でさらに置換されていてもよい。 The alkyl group may have a substituent, and as the substituent, a halogen atom, an aryl group and an alkoxy group can be exemplified. When having 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.
As said 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.
Moreover, as said 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. And the entire alkyl group substituted with an aryl group, that is, as an aralkyl group, a benzyl group, an α-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.
When 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. 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.
　上記一般式（ａ１－１０）において、Ｒ101、Ｒ102およびＲ103がアリール基を表す場合、上記アリール基は炭素数６～１２であることが好ましく、炭素数６～１０であることがより好ましい。上記アリール基は置換基を有していてもよく、上記置換基としては炭素数１～６のアルキル基が好ましく例示できる。アリール基としては、例えば、フェニル基、トリル基、クメニル基、１－ナフチル基等が例示できる。 When 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.
　また、Ｒ101、Ｒ102およびＲ103は互いに結合して、それらが結合している炭素原子と一緒になって環を形成することができる。Ｒ101とＲ102、Ｒ101とＲ103またはＲ102とＲ103が結合した場合の環構造としては、例えばシクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、テトラヒドロフラニル基、アダマンチル基およびテトラヒドロピラニル基等を挙げることができる。 Also, 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. As 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.
　なお、上記一般式（ａ１－１０）において、Ｒ101およびＲ102のいずれか一方が、水素原子またはメチル基であることが好ましい。 In the general formula (a1-10), one of R 101 and R 102 is preferably a hydrogen atom or a methyl group.
　上記一般式（ａ１－１０）で表される保護カルボキシル基を有する構成単位を形成するために用いられるラジカル重合性単量体は、市販のものを用いてもよいし、公知の方法で合成したものを用いることもできる。例えば、特開２０１１－２２１４９４号公報の段落番号００３７～００４０に記載の合成方法などで合成することができる。 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.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）の第一の好ましい態様は、下記一般式（Ａ２’）で表される構成単位である。
Figure JPOXMLDOC01-appb-C000002
 　（式中、Ｒ1およびＲ2は、それぞれ、水素原子、アルキル基またはアリール基を表し、少なくともＲ1およびＲ2のいずれか一方がアルキル基またはアリール基であり、Ｒ3は、アルキル基またはアリール基を表し、Ｒ1またはＲ2と、Ｒ3とが連結して環状エーテルを形成してもよく、Ｒ4は、水素原子またはメチル基を表し、Ｘは単結合またはアリーレン基を表す。）
　Ｒ1およびＲ2がアルキル基の場合、炭素数は１～１０のアルキル基が好ましい。Ｒ1およびＲ2がアリール基の場合、フェニル基が好ましい。Ｒ1およびＲ2は、それぞれ、水素原子または炭素数１～４のアルキル基が好ましい。
　Ｒ3は、アルキル基またはアリール基を表し、炭素数１～１０のアルキル基が好ましく、１～６のアルキル基がより好ましい。
　Ｘは単結合またはアリーレン基を表し、単結合が好ましい。 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 ′).
Figure JPOXMLDOC01-appb-C000002
 (Wherein, 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. )
When R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When 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.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）の第二の好ましい態様は、下記一般式の構造単位である。
Figure JPOXMLDOC01-appb-C000003
 　（式中、Ｒ121は水素原子または炭素数１～４のアルキル基を表し、Ｌ1はカルボニル基またはフェニレン基を表し、Ｒ122～Ｒ128はそれぞれ、水素原子または炭素数１～４のアルキル基を表す。）
　Ｒ121は水素原子またはメチル基が好ましい。
　Ｌ1はカルボニル基が好ましい。
　Ｒ122～Ｒ128は、水素原子が好ましい。 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.
Figure JPOXMLDOC01-appb-C000003
 (Wherein, R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenylene group, and R 122 to R 128 each 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.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）の好ましい具体例としては、下記の構成単位が例示できる。なお、Ｒは水素原子またはメチル基を表す。 As preferable specific examples of the structural unit (a1-1) having a protected carboxyl group protected by the acid-degradable group, the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
＜＜＜（ａ１－２）酸分解性基で保護された保護フェノール性水酸基を有する構成単位＞＞＞
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）は、フェノール性水酸基を有する構成単位が、以下で詳細に説明する酸分解性基によって保護された保護フェノール性水酸基を有する構成単位である。 <<< (a1-2) structural unit having a protected phenolic hydroxyl group protected by an acid degradable 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.
＜＜＜＜（ａ１－２－１）フェノール性水酸基を有する構成単位＞＞＞＞
　上記フェノール性水酸基を有する構成単位としては、ヒドロキシスチレン系構成単位やノボラック系の樹脂における構成単位が挙げられるが、これらの中では、ヒドロキシスチレン、またはα－メチルヒドロキシスチレンに由来する構成単位が、感度の観点から好ましい。またフェノール性水酸基を有する構成単位として、下記一般式（ａ１－２０）で表される構成単位も、感度の観点から好ましい。 <<<< (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 α-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.
一般式（ａ１－２０）
Figure JPOXMLDOC01-appb-C000005
 　（一般式（ａ１－２０）中、Ｒ220は水素原子またはメチル基を表し、Ｒ221は単結合または二価の連結基を表し、Ｒ222はハロゲン原子または炭素数１～５の直鎖または分岐鎖状のアルキル基を表し、ａは１～５の整数を表し、ｂは０～４の整数を表し、ａ＋ｂは５以下である。なお、Ｒ222が２以上存在する場合、これらのＲ222は相互に異なっていてもよいし同じでもよい。） General formula (a1-20)
Figure JPOXMLDOC01-appb-C000005
 (In the general formula (a1-20), 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, and a + b is 5 or less, provided that two or more R 222 exist, these R 222 may be mutually different or the same.)
　上記一般式（ａ１－２０）中、Ｒ220は水素原子またはメチル基を表し、メチル基であることが好ましい。
　また、Ｒ221は単結合または二価の連結基を示す。単結合である場合には、感度を向上させることができ、さらに硬化膜の透明性を向上させることができるので好ましい。Ｒ221の二価の連結基としてはアルキレン基が例示でき、Ｒ221がアルキレン基である具体例としては、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ｎ－ブチレン基、イソブチレン基、ｔｅｒｔ－ブチレン基、ペンチレン基、イソペンチレン基、ネオペンチレン基、ヘキシレン基等が挙げられる。中でも、Ｒ221が単結合、メチレン基、エチレン基であることが好ましい。また、上記二価の連結基は、置換基を有していてもよく、置換基としては、ハロゲン原子、水酸基、アルコキシ基等が挙げられる。また、ａは１～５の整数を表すが、本発明の効果の観点や、製造が容易であるという点から、ａは１または２であることが好ましく、ａが１であることがより好ましい。
　また、ベンゼン環における水酸基の結合位置は、Ｒ221と結合している炭素原子を基準（１位）としたとき、４位に結合していることが好ましい。
　Ｒ222はハロゲン原子または炭素数１～５の直鎖または分岐鎖状のアルキル基である。具体的には、フッ素原子、塩素原子、臭素原子、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。中でも製造が容易であるという点から、塩素原子、臭素原子、メチル基またはエチル基であることが好ましい。
　また、ｂは０または１～４の整数を表す。 In the above general formula (a1-20), R 220 represents a hydrogen atom or a methyl group, preferably a methyl group.
Further, 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. are mentioned as a substituent. Furthermore, 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. .
In addition, it is preferable that the bonding position of the hydroxyl group in the benzene ring be bonded to the 4-position, with the carbon atom bonded to R 221 as a reference (1-position).
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. Be Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferable from the viewpoint of easy production.
And b represents an integer of 0 or 1 to 4.
＜＜＜＜構成単位（ａ１－２）に用いることができる酸分解性基＞＞＞＞
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）に用いることができる上記酸分解性基としては、上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）に用いることができる上記酸分解性基と同様に、公知のものを使用でき、特に限定されない。酸分解性基の中でもアセタールで保護された保護フェノール性水酸基を有する構成単位であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、感光性樹脂組成物の保存安定性、コンタクトホールの形成性の観点から好ましい。さらに、酸分解性基の中でもフェノール性水酸基が上記一般式（ａ１－１０）で表されるアセタールの形で保護された保護フェノール性水酸基であることが、感度の観点からより好ましい。なお、フェノール性水酸基が上記一般式（ａ１－１０）で表されるアセタールの形で保護された保護フェノール性水酸基である場合、保護フェノール性水酸基の全体としては、－Ａｒ－Ｏ－ＣＲ101Ｒ102（ＯＲ103）の構造となっている。なお、Ａｒはアリーレン基を表す。 <<<< Acid-degradable group that can be used for the structural unit (a1-2) >>
The acid decomposable group that can be used for the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid decomposable group 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. Among 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). When 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.
　フェノール性水酸基のアセタールエステル構造の好ましい例は、Ｒ101＝Ｒ102＝Ｒ103＝メチル基やＲ101＝Ｒ102＝メチル基でＲ103＝ベンジル基の組み合わせが例示できる。 Preferred examples of acetal ester structure of the phenolic hydroxyl group, a combination of R 103 = benzyl group in R 101 = R 102 = R 103 = methyl and R 101 = R 102 = methyl group can be exemplified.
　また、フェノール性水酸基がアセタールの形で保護された保護フェノール性水酸基を有する構成単位を形成するために用いられるラジカル重合性単量体としては、例えば、特開２０１１－２１５５９０号公報の段落番号００４２に記載のものなどが挙げられる。
　これらの中で、４－ヒドロキシフェニルメタクリレートの１－アルコキシアルキル保護体、４－ヒドロキシフェニルメタクリレートのテトラヒドロピラニル保護体、が透明性の観点から好ましい。 Moreover, as a radically polymerizable monomer used in order to form the structural unit which has a protected phenolic hydroxyl group by which the phenolic hydroxyl group was protected in the form of an acetal, Paragraph No. 0042 of Unexamined-Japanese-Patent No. 2011-215590, for example. And the like.
Among these, a 1-alkoxyalkyl protected form of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protected form of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
　フェノール性水酸基のアセタール保護基の具体例としては、１－アルコキシアルキル基が挙げられ、例えば、１－エトキシエチル基、１－メトキシエチル基、１－ｎ－ブトキシエチル基、１－イソブトキシエチル基、１－（２－クロロエトキシ）エチル基、１－（２－エチルヘキシルオキシ）エチル基、１－ｎ－プロポキシエチル基、１－シクロヘキシルオキシエチル基、１－（２－シクロヘキシルエトキシ）エチル基、１－ベンジルオキシエチル基などを挙げることができ、これらは単独または２種類以上を組み合わせて使用することができる。 Specific examples of the 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.
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）を形成するために用いられるラジカル重合性単量体は、市販のものを用いてもよいし、公知の方法で合成したものを用いることもできる。例えば、フェノール性水酸基を有する化合物を酸触媒の存在下でビニルエーテルと反応させることにより合成することができる。上記の合成はフェノール性水酸基を有するモノマーをその他のモノマーと予め共重合させておき、その後に酸触媒の存在下でビニルエーテルと反応させてもよい。 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.
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）の好ましい具体例としては、下記の構成単位が例示できるが、本発明はこれらに限定されるものではない。 Although the following structural units can be illustrated as a preferable specific example of a structural unit (a1-2) which has the protected phenolic hydroxyl group protected by the said acid-degradable group, This invention is not limited to these.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
＜＜＜構成単位（ａ１）の好ましい態様＞＞＞
　上記構成単位（ａ１）を含有する重合体が、実質的に、構成単位（ａ２）を含まない場合、構成単位（ａ１）は、該構成単位（ａ１）を含有する重合体中、２０～１００モル％が好ましく、３０～９０モル％がより好ましい。
　上記構成単位（ａ１）を含有する重合体が、下記構成単位（ａ２）を含有する場合、単構成単位（ａ１）は、該構成単位（ａ１）と構成単位（ａ２）を含有する重合体中、感度の観点から３～７０モル％が好ましく、１０～６０モル％がより好ましい。また、特に上記構成単位（ａ１）に用いることができる上記酸分解性基がカルボキシル基がアセタールの形で保護された保護カルボキシル基を有する構成単位である場合、２０～５０モル％が好ましい。 <<< 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. In particular, when 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.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）は、上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）に比べると、現像が速いという特徴がある。よって、速く現像したい場合には酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）が好ましい。逆に現像を遅くしたい場合には酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）を用いることが好ましい。
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）は、上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）に比べると、現像が速いという特徴がある。よって、速く現像したい場合には酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）が好ましい。逆に現像を遅くしたい場合には酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）を用いることが好ましい。 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.
＜＜（ａ２）架橋性基を有する構成単位＞＞
　（Ａ）成分は、架橋性基を有する構成単位（ａ２）を有する。上記架橋性基は、加熱処理で硬化反応を起こす基であれば特に限定はされない。好ましい架橋性基を有する構成単位の態様としては、エポキシ基、オキセタニル基、－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは炭素数１～２０のアルキル基）で表される基およびエチレン性不飽和基よりなる群から選ばれた少なくとも１つを含む構成単位が挙げられ、エポキシ基、オキセタニル基、および、－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは炭素数１～２０のアルキル基）で表される基から選ばれる少なくとも１種であることが好ましい。その中でも、本発明の感光性樹脂組成物は、上記（Ａ）成分が、エポキシ基およびオキセタニル基のうち少なくとも１つを含む構成単位を含むことが好ましい。より詳細には、以下のものが挙げられる。 << (a2) Structural Unit Having Crosslinkable 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. Structural unit containing at least one selected from the group consisting of groups, epoxy group, oxetanyl group, and -NH-CH 2 -O-R (R is an alkyl group having 1 to 20 carbon atoms). It is preferable that it is at least one selected from the group Among them, in the photosensitive resin composition of the present invention, 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.
＜＜＜（ａ２－１）エポキシ基および／またはオキセタニル基を有する構成単位＞＞＞
　上記（Ａ）重合体は、エポキシ基および／またはオキセタニル基を有する構成単位（構成単位（ａ２－１））を含有することが好ましい。上記３員環の環状エーテル基はエポキシ基とも呼ばれ、４員環の環状エーテル基はオキセタニル基とも呼ばれる。
　上記エポキシ基および／またはオキセタニル基を有する構成単位（ａ２－１）は、１つの構成単位中にエポキシ基またはオキセタニル基を少なくとも１つ有していればよく、１つ以上のエポキシ基および１つ以上オキセタニル基、２つ以上のエポキシ基、または、２つ以上のオキセタニル基を有していてもよく、特に限定されないが、エポキシ基および／またはオキセタニル基を合計１～３つ有することが好ましく、エポキシ基および／またはオキセタニル基を合計１または２つ有することがより好ましく、エポキシ基またはオキセタニル基を１つ有することがさらに好ましい。 <<< (a2-1) structural unit having an epoxy group and / or an oxetanyl group >>>
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.
　エポキシ基を有する構成単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、アクリル酸グリシジル、メタクリル酸グリシジル、α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、アクリル酸－３，４－エポキシブチル、メタクリル酸－３，４－エポキシブチル、アクリル酸－３，４－エポキシシクロヘキシルメチル、メタクリル酸－３，４－エポキシシクロヘキシルメチル、α－エチルアクリル酸－３，４－エポキシシクロヘキシルメチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、特許第４１６８４４３号公報の段落番号００３１～００３５に記載の脂環式エポキシ骨格を含有する化合物などが挙げられ、これらの内容は本願明細書に組み込まれる。
　オキセタニル基を有する構成単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、特開２００１－３３０９５３号公報の段落番号００１１～００１６に記載のオキセタニル基を有する（メタ）アクリル酸エステルなどが挙げられ、これらの内容は本願明細書に組み込まれる。
　上記エポキシ基および／またはオキセタニル基を有する構成単位（ａ２－１）を形成するために用いられるラジカル重合性単量体の具体例としては、メタクリル酸エステル構造を含有するモノマー、アクリル酸エステル構造を含有するモノマーであることが好ましい。 Specific examples of the radically polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate , Α-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, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, described in paragraph No. 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic And compounds containing epoxy backbone can be cited, the contents of which are incorporated herein.
As a specific example of the radically polymerizable monomer used in order to form the structural unit which has an oxetanyl group, it has an oxetanyl group as described in stage number 0011 of the Unexamined-Japanese-Patent No. 2001-330953 (meth), for example Acrylates and the like are included, the contents of which are incorporated herein.
Specific examples of the 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.
　これらの中でも好ましいものは、メタクリル酸グリシジル、アクリル酸３，４－エポキシシクロヘキシルメチル、メタクリル酸３，４－エポキシシクロヘキシルメチル、アクリル酸（３－エチルオキセタン－３－イル）メチル、および、メタクリル酸（３－エチルオキセタン－３－イル）メチルである。これらの構成単位は、１種単独または２種類以上を組み合わせて使用することができる。 Among them, preferred are 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.
　上記エポキシ基および／またはオキセタニル基を有する構成単位（ａ２－１）の好ましい具体例としては、下記の構成単位が例示できる。なお、Ｒは、水素原子またはメチル基を表す。 As preferable specific examples of the structural unit (a2-1) having the epoxy group and / or the oxetanyl group, the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
＜＜＜（ａ２－２）エチレン性不飽和基を有する構成単位＞＞＞
　上記架橋性基を有する構成単位（ａ２）の１つとして、エチレン性不飽和基を有する構成単位（ａ２－２）が挙げられる（以下、「構成単位（ａ２－２）」ともいう。）。上記エチレン性不飽和基を有する構成単位（ａ２－２）としては、側鎖にエチレン性不飽和基を有する構成単位が好ましく、末端にエチレン性不飽和基を有し、炭素数３～１６の側鎖を有する構成単位がより好ましく、下記一般式（ａ２－２－１）で表される側鎖を有する構成単位がさらに好ましい。 <<< (a2-2) structural unit having an ethylenically unsaturated 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.
一般式（ａ２－２－１）
Figure JPOXMLDOC01-appb-C000010
  　（一般式（ａ２－２－１）中、Ｒ301は炭素数１～１３の二価の連結基を表し、Ｒ302は水素原子またはメチル基を表し、＊は架橋性基を有する構成単位（ａ２）の主鎖に連結する部位を表す。） General formula (a2-2-1)
Figure JPOXMLDOC01-appb-C000010
 (In general formula (a2-2-1), R 301 represents a divalent linking group having 1 to 13 carbon atoms, R 302 represents a hydrogen atom or a methyl group, and * represents a structural unit having a crosslinkable group ( represents a site linked to the main chain of a2))
　Ｒ301は、炭素数１～１３の二価の連結基であって、アルケニル基、シクロアルケニル基、アリーレン基またはこれらを組み合せた基を含み、エステル結合、エーテル結合、アミド結合、ウレタン結合等の結合を含んでいてもよい。また、二価の連結基は、任意の位置にヒドロキシ基、カルボキシル基等の置換基を有していてもよい。Ｒ301の具体例としては、下記の二価の連結基が挙げられる。 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.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記一般式（ａ２－２－１）で表される側鎖の中でも、上記Ｒ301で表される２価の連結基を含めて脂肪族の側鎖が好ましい。 Among the side chains represented by the above general formula (a2-2-1), aliphatic side chains including the divalent linking group represented by R 301 above are preferable.
　その他（ａ２－２）エチレン性不飽和基を有する構成単位については、特開２０１１－２１５５８０号公報の段落番号００７２～００９０の記載を参酌でき、これらの内容は本願明細書に組み込まれる。 Others (a2-2) The structural unit having an ethylenically unsaturated group can be referred to the description of Paragraph Nos. 0072 to 0090 of JP-A-2011-215580, the contents of which are incorporated in the present specification.
＜＜＜（ａ２－３）－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは炭素数１～２０のアルキル基）で表される基を有する構成単位＞＞＞
　本発明で用いる重合体は、－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは炭素数１～２０のアルキル基）で表される基を有する構成単位（ａ２－３）も好ましい。構成単位（ａ２－３）を有することで、緩やかな加熱処理で硬化反応を起こすことができ、諸特性に優れた硬化膜を得ることができる。ここで、Ｒは炭素数１～９のアルキル基が好ましく、炭素数１～４のアルキル基がより好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。構成単位（ａ２）は、より好ましくは、下記一般式（ａ２－３０）で表される基を有する構成単位である。
一般式（ａ２－３０）
Figure JPOXMLDOC01-appb-C000012
 （一般式（ａ２－３０）中、Ｒ1は水素原子またはメチル基を表し、Ｒ2は炭素数１～２０のアルキル基を表す。）
　Ｒ2は、炭素数１～９のアルキル基が好ましく、炭素数１～４のアルキル基がさらに好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。
　Ｒ2の具体例としては、メチル基、エチル基、ｎ－ブチル基、ｉ－ブチル基、シクロヘキシル基、およびｎ－ヘキシル基を挙げることができる。中でもｉ－ブチル基、ｎ－ブチル基、メチル基が好ましい。 <<< 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) >>
The polymer used in the present invention 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). By having the structural unit (a2-3), a curing reaction can be caused by mild heat treatment, and a cured film excellent in various properties can be obtained. Here, 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)
Figure JPOXMLDOC01-appb-C000012
 (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.
Specific examples of R 2 include methyl, ethyl, n-butyl, i-butyl, cyclohexyl and n-hexyl groups. Among them, i-butyl, n-butyl and methyl are preferable.
＜＜＜構成単位（ａ２）の好ましい態様＞＞＞
　上記構成単位（ａ２）を含有する重合体が、実質的に、構成単位（ａ１）を含まない場合、構成単位（ａ２）は、該構成単位（ａ２）を含有する重合体中、５～９０モル％が好ましく、２０～８０モル％がより好ましい。
　上記構成単位（ａ２）を含有する重合体が、上記構成単位（ａ１）を含有する場合、単構成単位（ａ２）は、該構成単位（ａ１）と構成単位（ａ２）を含有する重合体中、薬品耐性の観点から３～７０モル％が好ましく、１０～６０モル％がより好ましい。
　本発明では、さらに、いずれの態様にかかわらず、（Ａ）成分の全構成単位中、構成単位（ａ２）を３～７０モル％含有することが好ましく、１０～６０モル％含有することがより好ましい。 <<< preferred embodiment of structural unit (a2) >>
When the polymer containing the structural unit (a2) does not substantially contain the structural unit (a1), 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.
When 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.
In the present invention, regardless of any embodiment, 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.
　上記の数値の範囲内であると、感光性樹脂組成物から得られる硬化膜の透明性および薬品耐性が良好となる。 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.
＜＜（ａ３）その他の構成単位＞＞
　本発明において、（Ａ）成分は、上記構成単位（ａ１）および／または（ａ２）に加えて、これら以外の他の構成単位（ａ３）を有していてもよい。これらの構成単位は、上記重合体成分（１）および／または（２）が含んでいてもよい。また、上記重合体成分（１）または（２）とは別に、実質的に（ａ１）および（ａ２）を含まずに他の構成単位（ａ３）を有する重合体成分を有していてもよい。上記重合体成分（１）または（２）とは別に、実質的に（ａ１）および（ａ２）を含まずに他の構成単位（ａ３）を有する重合体成分を含む場合、該重合体成分の配合量は、全重合体成分中、６０質量％以下であることが好ましく、４０質量％以下であることがより好ましく、２０質量％以下であることがさらに好ましい。 << (a3) Other constituent units >>
In the present invention, 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). . When a polymer component having another structural unit (a3) substantially free of (a1) and (a2) separately from the above polymer component (1) or (2) is contained in the polymer component, 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.
　その他の構成単位（ａ３）となるモノマーとしては、特に制限はなく、例えば、スチレン類、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸環状アルキルエステル、（メタ）アクリル酸アリールエステル、不飽和ジカルボン酸ジエステル、ビシクロ不飽和化合物類、マレイミド化合物類、不飽和芳香族化合物、共役ジエン系化合物、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和ジカルボン酸無水物、その他の不飽和化合物を挙げることができる。また、後述するとおり、酸基を有する構成単位を有していてもよい。その他の構成単位（ａ３）となるモノマーは、単独または２種類以上を組み合わせて使用することができる。 There is no restriction | limiting in particular as 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. Moreover, you may have a structural unit which has an acidic radical, as mentioned later. The monomer used as other structural unit (a3) can be used individually or in combination of 2 or more types.
　以下に、本発明の重合体成分の好ましい実施形態を挙げるが、本発明はこれらに限定されるものではない。 Hereinafter, preferred embodiments of the polymer component of the present invention will be listed, but the present invention is not limited thereto.
（第１の実施形態）
　重合体成分（１）が、さらに、１種または２種以上のその他の構成単位（ａ３）を有する態様。
（第２の実施形態）
　重合体成分（２）の（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体が、さらに、１種または２種以上のその他の構成単位（ａ３）を有する態様。
（第３の実施形態）
　重合体成分（２）の（ａ２）架橋性基を有する構成単位を有する重合体が、さらに、１種または２種以上のその他の構成単位（ａ３）を有する態様。 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).
（第４の実施形態）
　上記第１～第３の実施形態のいずれかにおいて、その他の構成単位（ａ３）として、少なくとも酸基を含む構成単位を含む態様。 Fourth Embodiment
In any one of the first to third embodiments, an aspect including a structural unit containing at least an acid group as the other structural unit (a3).
（第５の実施形態）
　上記重合体成分（１）または（２）とは別に、さらに、実質的に（ａ１）および（ａ２）を含まずに他の構成単位（ａ３）を有する重合体を有する態様。 Fifth Embodiment
The aspect which has a polymer which has another structural unit (a3) without containing (a1) and (a2) substantially separately from the said polymer component (1) or (2).
（第６の実施形態）
　上記第１～第５の実施形態の２以上の組み合わせからなる形態。
（第７の実施形態）
　重合体成分（２）を少なくとも含む態様。特に、上記第１～第６の実施形態において、少なくとも重合体成分（２）を含む態様。 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). In particular, in the first to sixth embodiments, an aspect including at least the polymer component (2).
　構成単位（ａ３）は、具体的には、スチレン、ｔｅｒｔ－ブトキシスチレン、メチルスチレン、ヒドロキシスチレン、α－メチルスチレン、アセトキシスチレン、メトキシスチレン、エトキシスチレン、クロロスチレン、ビニル安息香酸メチル、ビニル安息香酸エチル、４－ヒドロキシ安息香酸（３－メタクリロイルオキシプロピル）エステル、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸イソボルニル、アクリロニトリル、エチレングリコールモノアセトアセテートモノ（メタ）アクリレートなどによる構成単位を挙げることができる。この他、特開２００４－２６４６２３号公報の段落番号００２１～００２４に記載の化合物を挙げることができる。 Specific examples of the structural unit (a3) include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinyl benzoate, and vinyl benzoic acid. Ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylate Isopropyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate Mention may be made of a structural unit due to theft. Other than these, the compounds described in paragraphs [0021] to [0024] of JP-A-2004-264623 can be mentioned.
　また、その他の構成単位（ａ３）としてスチレン類、脂環式骨格を有する基が、電気特性の観点で好ましい。具体的にはスチレン、ｔｅｒｔ－ブトキシスチレン、メチルスチレン、ヒドロキシスチレン、α－メチルスチレン、ジシクロペンタニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート等が挙げられる。 Further, as the other structural unit (a3), styrenes and a group having an alicyclic skeleton are preferable from the viewpoint of electrical characteristics. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate and the like It can be mentioned.
　さらにまた、その他の構成単位（ａ３）として（メタ）アクリル酸アルキルエステルが、密着性の観点で好ましい。具体的には（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ－ブチル等が挙げられ、（メタ）アクリル酸メチルがより好ましい。重合体（Ａ）を構成する構成単位中、上記の構成単位（ａ３）の含有率は、６０モル％以下が好ましく、５０モル％以下がより好ましく、４０モル％以下がさらに好ましい。下限値としては、０モル％でもよいが、例えば、１モル％以上とすることができ、さらには、５モル％以上とすることができる。上記の数値の範囲内であると、感光性樹脂組成物から得られる硬化膜の諸特性が良好となる。 Furthermore, as the other structural unit (a3), (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.
　その他の構成単位（ａ３）として、酸基を含むことが好ましい。酸基を含むことにより、アルカリ性の現像液に溶けやすくなり、本発明の効果がより効果的に発揮される。本発明における酸基とは、ｐＫａが７より小さいプロトン解離性基を意味する。酸基は、通常、酸基を形成しうるモノマーを用いて、酸基を含む構成単位として、重合体に組み込まれる。このような酸基を含む構成単位を重合体中に含めることにより、アルカリ性の現像液に対して溶けやすくなる傾向にある。
　本発明で用いられる酸基としては、カルボン酸基由来のもの、スルホンアミド基に由来のもの、ホスホン酸基に由来のもの、スルホン酸基に由来のもの、フェノール性水酸基に由来するもの、スルホンアミド基、スルホニルイミド基等が例示され、カルボン酸基由来のものおよび／またはフェノール性水酸基に由来のものが好ましい。
　本発明で用いられる酸基を含む構成単位は、スチレンに由来する構成単位や、ビニル化合物に由来する構成単位、（メタ）アクリル酸および／またはそのエステルに由来する構成単位であることがより好ましい。 As the other structural unit (a3), it is preferable to contain 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.
As the acid group used in the present invention, 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 .
　本発明では、特に、カルボキシル基を有する構成単位、または、フェノール性水酸基を有する構成単位を含有することが、感度の観点で好ましい。 In 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.
　酸基を含む構成単位は、全重合体成分の構成単位の１～８０モル％が好ましく、１～５０モル％がより好ましく、５～４０モル％がさらに好ましく、５～３０モル％が特に好ましく、５～２０モル％が特に好ましい。 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.
　本発明では、上記重合体成分（１）または（２）とは別に、実質的に（ａ１）および（ａ２）を含まずに他の構成単位（ａ３）を有する重合体を含んでいても良い。 In the present invention, a polymer having another structural unit (a3) may be contained substantially excluding (a1) and (a2), separately from the above polymer component (1) or (2). .
　このような重合体としては、側鎖にカルボキシル基を有する樹脂が好ましい。例えば、特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５９－５３８３６号、特開昭５９－７１０４８号の各公報に記載されているような、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体等、並びに側鎖にカルボキシル基を有する酸性セルロース誘導体、水酸基を有するポリマーに酸無水物を付加させたもの等が挙げられ、さらに側鎖に（メタ）アクリロイル基を有する高分子重合体も好ましいものとして挙げられる。 As such a polymer, a resin having a carboxyl group in a side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836 and JP-A-59-71048. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. and side chains as described And 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.
　例えば、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、２－ヒドロキシエチル（メタ）アクリレート／ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、特開平７－１４０６５４号公報に記載の、２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体などが挙げられる。
　その他にも、特開平７－２０７２１１号公報、特開平８－２５９８７６号公報、特開平１０－３００９２２号公報、特開平１１－１４０１４４号公報、特開平１１－１７４２２４号公報、特開２０００－５６１１８号公報、特開２００３－２３３１７９号公報、特開２００９－５２０２０号公報等に記載の公知の高分子化合物を使用することができ、これらの内容は本願明細書に組み込まれる。
　これらの重合体は、１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。 For example, 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. 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Copolymer and the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118. 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.
　これらの重合体として、市販されている、ＳＭＡ　１０００Ｐ、ＳＭＡ　２０００Ｐ、ＳＭＡ　３０００Ｐ、ＳＭＡ　１４４０Ｆ、ＳＭＡ　１７３５２Ｐ、ＳＭＡ　２６２５Ｐ、ＳＭＡ　３８４０Ｆ（以上、サートマー社製）、ＡＲＵＦＯＮ　ＵＣ－３０００、ＡＲＵＦＯＮ　ＵＣ－３５１０、ＡＲＵＦＯＮ　ＵＣ－３９００、ＡＲＵＦＯＮ　ＵＣ－３９１０、ＡＲＵＦＯＮ　ＵＣ－３９２０、ＡＲＵＦＯＮ　ＵＣ－３０８０（以上、東亞合成（株）製）、Ｊｏｎｃｒｙｌ　６９０、Ｊｏｎｃｒｙｌ　６７８、Ｊｏｎｃｒｙｌ　６７、Ｊｏｎｃｒｙｌ　５８６（以上、ＢＡＳＦ製）等を用いることもできる。 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.
＜＜（Ａ）重合体の分子量＞＞
　（Ａ）重合体の分子量は、ポリスチレン換算重量平均分子量で、好ましくは１，０００～２００，０００、より好ましくは２，０００～５０，０００の範囲である。上記の数値の範囲内であると、諸特性が良好である。数平均分子量と重量平均分子量の比（分散度）は１．０～５．０が好ましく１．５～３．５がより好ましい。 << Molecular weight of (A) polymer >>
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.
＜＜（Ａ）重合体の製造方法＞＞
　また、（Ａ）成分の合成法についても、様々な方法が知られているが、一例を挙げると、少なくとも上記（ａ１）および上記（ａ３）で表される構成単位を形成するために用いられるラジカル重合性単量体を含むラジカル重合性単量体混合物を有機溶剤中、ラジカル重合開始剤を用いて重合することにより合成することができる。また、いわゆる高分子反応で合成することもできる。 << (A) Method for producing polymer >>
Moreover, although various methods are known also about the synthesis | combining method of (A) component, if an example is given, it will be used in order to form the structural unit represented by at least said (a1) and said (a3), It can synthesize | combine by polymerizing the radically polymerizable monomer mixture containing a radically polymerizable monomer in the organic solvent using a radical polymerization initiator. Moreover, it can also be synthesized by so-called polymer reaction.
　本発明の感光性樹脂組成物は、全固形分１００質量部に対し、（Ａ）成分を５０～９９．９質量部の割合で含むことが好ましく、７０～９８質量部の割合で含むことがより好ましい。 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.
＜（Ｂ）光酸発生剤＞
　本発明の感光性樹脂組成物は、（Ｂ）光酸発生剤を含有する。本発明で使用される光酸発生剤（「（Ｂ）成分」ともいう。）としては、波長３００ｎｍ以上、好ましくは波長３００～４５０ｎｍの活性光線に感応し、酸を発生する化合物が好ましいが、その化学構造に制限されるものではない。また、波長３００ｎｍ以上の活性光線に直接感応しない光酸発生剤についても、増感剤と併用することによって波長３００ｎｍ以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく用いることができる。本発明で使用される光酸発生剤としては、ｐＫａが４以下の酸を発生する光酸発生剤が好ましく、ｐＫａが３以下の酸を発生する光酸発生剤がより好ましく、２以下の酸を発生する光酸発生剤が最も好ましい。 <(B) Photoacid Generator>
The photosensitive resin composition of the present invention contains (B) a photoacid generator. As the photo-acid generator (also referred to as "component (B)") used in the present invention, 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. In addition, 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. It can be preferably used in combination. As a photo-acid generator used by this invention, the photo-acid generator which generate | occur | produces the acid of 4 or less pKa is preferable, The photo-acid generator which generate the acid of 3 or less pKa is more preferable, The acid of 2 or less is more preferable Most preferred are photoacid generators that generate.
　光酸発生剤の例として、トリクロロメチル－ｓ－トリアジン類、スルホニウム塩やヨードニウム塩、第四級アンモニウム塩類、ジアゾメタン化合物、イミドスルホネート化合物、および、オキシムスルホネート化合物などを挙げることができる。これらの中でも、絶縁性の観点から、オキシムスルホネート化合物を用いることが好ましい。これら光酸発生剤は、１種単独または２種類以上を組み合わせて使用することができる。トリクロロメチル－ｓ－トリアジン類、ジアリールヨードニウム塩類、トリアリールスルホニウム塩類、第四級アンモニウム塩類、およびジアゾメタン誘導体の具体例としては、特開２０１１－２２１４９４号公報の段落番号００８３～００８８に記載の化合物が例示できる。 Examples of photoacid generators 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. As specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives, compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be used. It can be illustrated.
　オキシムスルホネート化合物、すなわち、オキシムスルホネート構造を有する化合物としては、下記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する化合物が好ましく例示できる。 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).
一般式（Ｂ１）
Figure JPOXMLDOC01-appb-C000013
 （一般式（Ｂ１）中、Ｒ21は、アルキル基またはアリール基を表す。波線は他の基との結合を表す。） General formula (B1)
Figure JPOXMLDOC01-appb-C000013
 (In the general formula (B1), R 21 represents an alkyl group or an aryl group. The wavy line represents a bond to another group.)
　いずれの基も置換されてもよく、Ｒ21におけるアルキル基は直鎖状でも分岐状でも環状でもよい。許容される置換基は以下に説明する。
　Ｒ21のアルキル基としては、炭素数１～１０の、直鎖状または分岐状アルキル基が好ましい。Ｒ21のアルキル基は、炭素数６～１１のアリール基、炭素数１～１０のアルコキシ基、または、シクロアルキル基（７，７－ジメチル－２－オキソノルボルニル基などの有橋式脂環基を含む、好ましくはビシクロアルキル基等）で置換されてもよい。
　Ｒ21のアリール基としては、炭素数６～１１のアリール基が好ましく、フェニル基またはナフチル基がより好ましい。Ｒ21のアリール基は、低級アルキル基、アルコキシ基あるいはハロゲン原子で置換されてもよい。 Any group may be substituted, and the alkyl group in R 21 may be linear, branched or cyclic. The permissible substituents are described below.
As the alkyl group for R 21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. 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.
　上記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する上記化合物は、下記一般式（Ｂ２）で表されるオキシムスルホネート化合物であることも好ましい。 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).
Figure JPOXMLDOC01-appb-C000014
 （式（Ｂ２）中、Ｒ42は、アルキル基またはアリール基を表し、Ｘは、アルキル基、アルコキシ基、または、ハロゲン原子を表し、ｍ４は、０～３の整数を表し、ｍ４が２または３であるとき、複数のＸは同一でも異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000014
 (In 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.)
　Ｘとしてのアルキル基は、炭素数１～４の直鎖状または分岐状アルキル基が好ましい。
Ｘとしてのアルコキシ基は、炭素数１～４の直鎖状または分岐状アルコキシ基が好ましい。
　Ｘとしてのハロゲン原子は、塩素原子またはフッ素原子が好ましい。　ｍ４は、０または１が好ましい。上記一般式（Ｂ２）中、ｍ４が１であり、Ｘがメチル基であり、Ｘの置換位置がオルト位であり、Ｒ42が炭素数１～１０の直鎖状アルキル基、７，７－ジメチル－２－オキソノルボルニルメチル基、またはｐ－トルイル基である化合物が特に好ましい。 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.
　上記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する化合物は、下記一般式（Ｂ３）で表されるオキシムスルホネート化合物であることも好ましい。 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).
Figure JPOXMLDOC01-appb-C000015
 （式（Ｂ３）中、Ｒ43は式（Ｂ２）におけるＲ42と同義であり、Ｘ1は、ハロゲン原子、水酸基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、シアノ基またはニトロ基を表し、ｎ４は０～５の整数を表す。）
Figure JPOXMLDOC01-appb-C000015
 (In the 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.)
　上記一般式（Ｂ３）におけるＲ43としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－オクチル基、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロ－ｎ－プロピル基、パーフルオロ－ｎ－ブチル基、ｐ－トリル基、４－クロロフェニル基またはペンタフルオロフェニル基が好ましく、ｎ－オクチル基が特に好ましい。
　Ｘ1としては、炭素数１～５のアルコキシ基が好ましく、メトキシ基がより好ましい。
　ｎ４としては、０～２が好ましく、０～１が特に好ましい。 As 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.
As X 1 , an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group is more preferable.
As n 4, 0 to 2 is preferable, and 0 to 1 is particularly preferable.
　上記一般式（Ｂ３）で表される化合物の具体例としては、α－（メチルスルホニルオキシイミノ）ベンジルシアニド、α－（エチルスルホニルオキシイミノ）ベンジルシアニド、α－（ｎ－プロピルスルホニルオキシイミノ）ベンジルシアニド、α－（ｎ－ブチルスルホニルオキシイミノ）ベンジルシアニド、α－（４－トルエンスルホニルオキシイミノ）ベンジルシアニド、α－〔（メチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（エチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（ｎ－プロピルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（ｎ－ブチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（４－トルエンスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリルを挙げることができる。 Specific examples of the compound represented by the above general formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) ) Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4- 4 Methoxyphenyl] acetonitrile, α-[(4 It can be given toluenesulfonyl) -4-methoxyphenyl] acetonitrile.
　好ましいオキシムスルホネート化合物の具体例としては、下記化合物（ｉ）～（ｖｉｉｉ）等が挙げられ、１種単独で使用、または、２種類以上を併用することができる。化合物（ｉ）～（ｖｉｉｉ）は、市販品として、入手することができる。また、他の種類の（Ｂ）光酸発生剤と組み合わせて使用することもできる。 Specific examples of 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.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する化合物としては、下記一般式（ＯＳ－１）で表される化合物であることも好ましい。 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).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記一般式（ＯＳ－１）中、Ｒ101は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基、または、ヘテロアリール基を表す。Ｒ102は、アルキル基、または、アリール基を表す。
　Ｘ101は－Ｏ－、－Ｓ－、－ＮＨ－、－ＮＲ105－、－ＣＨ2－、－ＣＲ106Ｈ－、または、－ＣＲ105Ｒ107－を表し、Ｒ105～Ｒ107はアルキル基、または、アリール基を表す。
　Ｒ121～Ｒ124は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基、または、アリール基を表す。Ｒ121～Ｒ124のうち２つは、それぞれ互いに結合して環を形成してもよい。
　Ｒ121～Ｒ124としては、水素原子、ハロゲン原子、および、アルキル基が好ましく、また、Ｒ121～Ｒ124のうち少なくとも２つが互いに結合してアリール基を形成する態様もまた、好ましく挙げられる。中でも、Ｒ121～Ｒ124がいずれも水素原子である態様が感度の観点から好ましい。
　既述の官能基は、いずれも、さらに置換基を有していてもよい。 In the above 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. Two of R 121 to R 124 may be respectively bonded to each other to form a ring.
As 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. Among them, an embodiment in which all of 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.
　上記一般式（ＯＳ－１）で表される化合物は、下記一般式（ＯＳ－２）で表される化合物であることがより好ましい。 The compound represented by the above general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記一般式（ＯＳ－２）中、Ｒ101、Ｒ102、Ｒ121～Ｒ124は、それぞれ式（ＯＳ－１）におけるのと同義であり、好ましい例もまた同様である。
　これらの中でも、上記一般式（ＯＳ－１）および上記一般式（ＯＳ－２）におけるＲ101がシアノ基、または、アリール基である態様がより好ましく、上記一般式（ＯＳ－２）で表され、Ｒ101がシアノ基、フェニル基またはナフチル基である態様が最も好ましい。 In the above 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.
Among these, an embodiment in which 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) Most preferred is an embodiment in which R 101 is a cyano group, a phenyl group or a naphthyl group.
　また、上記オキシムスルホネート化合物においてオキシムやベンゾチアゾール環の立体構造（Ｅ，Ｚ等）のついてはそれぞれ、どちらか一方であっても、混合物であってもよい。 In the oxime sulfonate compound, the steric structures (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
　本発明に好適に用いうる上記一般式（ＯＳ－１）で表される化合物の具体例としては、特開２０１１－２２１４９４号公報の段落番号０１２８～０１３２に記載の化合物（例示化合物ｂ－１～ｂ－３４）が挙げられるが、本発明はこれに限定されない。 Specific examples of the compound represented by the above general formula (OS-1) which can be suitably used in the present invention include the compounds described in paragraph Nos. 0128 to 0132 of JP-A-2011-221494 (exemplified compounds b-1 to b-34), but the present invention is not limited thereto.
　本発明では、上記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する化合物としては、下記一般式（ＯＳ－３）、下記一般式（ＯＳ－４）または下記一般式（ＯＳ－５）で表されるオキシムスルホネート化合物であることが好ましい。 In the present invention, 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.
Figure JPOXMLDOC01-appb-C000019
 　（一般式（ＯＳ－３）～一般式（ＯＳ－５）中、Ｒ22、Ｒ25およびＲ28はそれぞれ独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ23、Ｒ26およびＲ29はそれぞれ独立に水素原子、アルキル基、アリール基またはハロゲン原子を表し、Ｒ24、Ｒ27およびＲ30はそれぞれ独立にハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基またはアルコキシスルホニル基を表し、Ｘ1～Ｘ3はそれぞれ独立に酸素原子または硫黄原子を表し、ｎ1～ｎ3はそれぞれ独立に１または２を表し、ｍ1～ｍ3はそれぞれ独立に０～６の整数を表す。）
Figure JPOXMLDOC01-appb-C000019
 (In the general formula (OS-3) to the general formula (OS-5), 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 And 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, and m 1 to m 3 each independently represent an integer of 0 to 6 Represents
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25およびＲ28におけるアルキル基、アリール基またはヘテロアリール基は、置換基を有していてもよい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25およびＲ28におけるアルキル基としては、置換基を有していてもよい総炭素数１～３０のアルキル基であることが好ましい。 In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group of R 22 , R 25 and R 28 may have a substituent.
In the above formulas (OS-3) to (OS-5), 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.
　また、上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25およびＲ28におけるアリール基としては、置換基を有してもよい総炭素数６～３０のアリール基が好ましい。 In the general formulas (OS-3) to (OS-5), as the aryl group for R 22 , R 25 and R 28, an aryl group having a total of 6 to 30 carbon atoms which may have a substituent is preferred. preferable.
　また、上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ1におけるヘテロアリール基としては、置換基を有してもよい総炭素数４～３０のヘテロアリール基が好ましい。 In the general formulas (OS-3) to (OS-5), the heteroaryl group for R 1 is preferably a heteroaryl group having 4 to 30 carbon atoms in total that may have a substituent.
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25およびＲ28におけるヘテロアリール基は、少なくとも１つの環が複素芳香環であればよく、例えば、複素芳香環とベンゼン環とが縮環していてもよい。 In the above general formulas (OS-3) to (OS-5), 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.
上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ23、Ｒ26およびＲ29は、水素原子、アルキル基またはアリール基であることが好ましく、水素原子またはアルキル基であることがより好ましい。
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、化合物中に２以上存在するＲ23、Ｒ26およびＲ29のうち、１つまたは２つがアルキル基、アリール基またはハロゲン原子であることが好ましく、１つがアルキル基、アリール基またはハロゲン原子であることがより好ましく、１つがアルキル基であり、かつ残りが水素原子であることが特に好ましい。 In the general formula (OS-3) ~ (OS -5), 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.
In the above general formulas (OS-3) to (OS-5), 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.
　Ｒ23、Ｒ26およびＲ29におけるアルキル基としては、置換基を有してもよい総炭素数１～１２のアルキル基であることが好ましく、置換基を有してもよい総炭素数１～６のアルキル基であることがより好ましい。 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.
　Ｒ23、Ｒ26およびＲ29におけるアリール基としては、置換基を有してもよい総炭素数６～３０のアリール基であることが好ましい。 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.
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｘ1～Ｘ3はそれぞれ独立にＯまたはＳを表し、Ｏであることが好ましい。
上記一般式（ＯＳ－３）～（ＯＳ－５）において、Ｘ1～Ｘ3を環員として含む環は、５員環または６員環である。
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、ｎ1～ｎ3はそれぞれ独立に１または２を表し、Ｘ1～Ｘ3がＯである場合、ｎ1～ｎ3はそれぞれ独立に１であることが好ましく、また、Ｘ1～Ｘ3がＳである場合、ｎ1～ｎ3はそれぞれ独立に２であることが好ましい。 In the general formulas (OS-3) to (OS-5), each of X 1 to X 3 independently represents O or S, and is preferably O.
In the above general formulas (OS-3) to (OS-5), a ring containing X 1 to X 3 as ring members is a 5- or 6-membered ring.
In the above general formulas (OS-3) to (OS-5), 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.
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27およびＲ30はそれぞれ独立にハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基またはアルコキシスルホニル基を表す。その中でも、Ｒ24、Ｒ27およびＲ30はそれぞれ独立にアルキル基またはアルキルオキシ基であることが好ましい。
　Ｒ24、Ｒ27およびＲ30におけるアルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基およびアルコキシスルホニル基は、置換基を有していてもよい。
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27およびＲ30におけるアルキル基としては、置換基を有していてもよい総炭素数１～３０のアルキル基であることが好ましい。 In the above general formulas (OS-3) to (OS-5), 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. Represent. Among them, 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.
In the above general formulas (OS-3) to (OS-5), 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.
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27およびＲ30におけるアルキルオキシ基としては、置換基を有してもよい総炭素数１～３０のアルキルオキシ基であることが好ましい。 In the above general formulas (OS-3) to (OS-5), 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.
　また、上記一般式（ＯＳ－３）～（ＯＳ－５）中、ｍ1～ｍ3はそれぞれ独立に０～６の整数を表し、０～２の整数であることが好ましく、０または１であることがより好ましく、０であることが特に好ましい。
　また、上記（ＯＳ－３）～（ＯＳ－５）のそれぞれの置換基について、特開２０１１－２２１４９４号公報の段落番号００９２～０１０９に記載の（ＯＳ－３）～（ＯＳ－５）の置換基の好ましい範囲も同様に好ましい。 In the general formulas (OS-3) to (OS-5), 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.
　また、上記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する化合物は、下記一般式（ＯＳ－６）～（ＯＳ－１１）のいずれかで表されるオキシムスルホネート化合物であることが特に好ましい。 Further, 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.
Figure JPOXMLDOC01-appb-C000020
 （式（ＯＳ－６）～（ＯＳ－１１）中、Ｒ301～Ｒ306はアルキル基、アリール基またはヘテロアリール基を表し、Ｒ307は、水素原子または臭素原子を表し、Ｒ308～Ｒ310、Ｒ313、Ｒ316およびＲ318はそれぞれ独立に水素原子、炭素数１～８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基またはクロロフェニル基を表し、Ｒ311およびＲ314はそれぞれ独立に水素原子、ハロゲン原子、メチル基またはメトキシ基を表し、Ｒ312、Ｒ315、Ｒ317およびＲ319はそれぞれ独立には水素原子またはメチル基を表す。）
Figure JPOXMLDOC01-appb-C000020
 In formulas (OS-6) to (OS-11), 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, and 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, and R 312 , R 315 , R 317 and R 319 each independently represent a hydrogen atom or a methyl group.)
　上記一般式（ＯＳ－６）～（ＯＳ－１１）における好ましい範囲は、特開２０１１－２２１４９４号公報の段落番号０１１０～０１１２に記載される（ＯＳ－６）～（ＯＳ－１１）の好ましい範囲と同様である。 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
　上記一般式（ＯＳ－３）～上記一般式（ＯＳ－５）で表されるオキシムスルホネート化合物の具体例としては、特開２０１１－２２１４９４号公報の段落番号０１１４～０１２０に記載の化合物が挙げられるが、本発明は、これらに限定されるものではない。 As a specific example of 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. However, the present invention is not limited to these.
　本発明の感光性樹脂組成物において、（Ｂ）光酸発生剤は、感光性樹脂組成物中の全樹脂成分（好ましくは固形分、より好ましくは共重合体の合計）１００質量部に対して、０．１～１０質量部使用することが好ましく、０．５～１０質量部使用することがより好ましい。２種以上を併用することもできる。 In the photosensitive resin composition of the present invention, (B) 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.
＜（Ｃ）芳香族複素環化合物＞
　本発明の組成物は、（Ｃ）芳香族複素環化合物を含有する。（Ｃ）芳香族複素環化合物は、分子量が１０００以下であり、であり、芳香環中に少なくとも１つの窒素原子を含み、且つ芳香環中に少なくとも２つの配位原子を含む。芳香族複素環化合物を含有させることにより、感度を維持しつつ、耐薬品性を向上させることができる。また、本発明の組成物で形成された硬化膜を表示装置に使用すると、表示装置のパネル表示ムラを改善することができる。 <(C) aromatic heterocyclic compound>
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. By containing the aromatic heterocyclic compound, chemical resistance can be improved while maintaining the sensitivity. Moreover, when the cured film formed with the composition of this invention is used for a display apparatus, the panel display unevenness of a display apparatus can be improved.
　（Ｃ）芳香族複素環化合物の分子量は、１０００以下であり、７５０以下が好ましく、５００以下がより好ましい。分子量を低分子とすることにより、基板側へ分子が移動しやすくなる。下限値としては１以上が好ましく、５０以上がより好ましい。 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.
　芳香族複素環を構成する配位原子とは、配位結合能を有する原子のことをいい、例えば、窒素原子、酸素原子、硫黄原子、リン原子などが例示され、窒素原子、酸素原子、硫黄原子がより好ましい。（Ｃ）芳香族複素環化合物は、配位原子を少なくとも２つ含んでおり、そのうち少なくとも１つは窒素原子である。配位原子は、（Ｃ）芳香族複素環化合物１分子の芳香環に２～３つ含むことが好ましい。配位原子のうち、少なくとも１つは窒素原子であり、少なくとも２つが窒素原子であることが好ましい。また、配位原子に水素原子が結合している態様であってもよい。また、（Ｃ）芳香族複素環化合物は、塩基性基を含まないことが好ましく、さらにアミノ基を含まないことが好ましい。 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. Of the coordinating atoms, at least one is preferably a nitrogen atom and at least two are preferably nitrogen atoms. In addition, 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.
　（Ｃ）芳香族複素環化合物は、芳香環に置換基Ｔを有していてもよい。置換基Ｔとしては、例えば、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～１０のチオアルコキシ基、ヒドロキシル基、カルボキシル基、アセチル基、シアノ基、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）などが挙げられる。これら置換基は、さらに置換基を有していてもよい。しかしながら、本発明で用いる（Ｃ）芳香族複素環化合物は、無置換またはメチル基で置換された化合物であることが好ましい。
　なお、感度の低下を抑制する観点から、芳香環の置換基として、アミノ基を含まないことが好ましい。 The aromatic heterocyclic compound (C) may have a substituent T on the aromatic ring. As the substituent 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. However, the (C) aromatic heterocyclic compound used in the present invention is preferably a compound which is unsubstituted or substituted by a methyl group.
In addition, it is preferable that an amino group is not contained as a substituent of an aromatic ring from a viewpoint of suppressing the fall of sensitivity.
　（Ｃ）芳香族複素環化合物は、芳香族環であれば特に限定されないが、５員環芳香族複素環化合物、５員環芳香族複素環化合物、５員環芳香族複素環構造および６員環芳香族複素環構造の少なくとも一方を含む多環式芳香族複素環化合物が好ましい。
　多環式芳香族複素環化合物とは、２つ以上の独立した芳香族環が互いに結合子によって結合している化合物（例えば、ビピリジンなど）、または、１つ以上の芳香環と１つ以上の脂肪族環および／または芳香族環が縮合している化合物（例えば、フェナントロリンなど）をいう。本発明では、多環式芳香族複素環化合物を構成する少なくとも１つの環が５員環芳香族複素環構造または６員環芳香族複素環構造であれば、他の環はどのような環であってもよいが、他の環は、ベンゼン環、５員環芳香族複素環および６員環芳香族複素環から選択されることが好ましく、ベンゼン環および６員環芳香族複素環から選択されることがより好ましい。多環式芳香族複素環化合物を形成する環の数は、１分子中２つまたは３つであることが好ましく、２つがより好ましい。 (C) 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. In the present invention, as long as at least one ring constituting the polycyclic aromatic heterocyclic compound has a five-membered aromatic heterocyclic structure or a six-membered aromatic heterocyclic structure, any other ring may be used. And 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.
　５員環芳香族複素環化合物としては、イミダゾール系化合物、ピラゾール系化合物、オキサゾール系化合物、イソオキサゾール系化合物、チアゾール系化合物、イソチアゾール系化合物、トリアゾール系化合物、オキサジアゾール系化合物、チアジアゾール系化合物、等が好ましい。 As a five-membered ring aromatic heterocyclic compound, 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.
　イミダゾール系化合物としては、イミダゾール、１－メチルイミダゾール、１－エチルイミダゾール、１－ｎ－プロピルイミダゾール、１－イソプロピルイミダゾール、１－ブチルイミダゾール、１－デシル－２－メチルイミダゾール、１，２－ジメチルイミダゾール、２－エチル－４－メチルイミダゾール、２－ヘプタデシルイミダゾール、１－（ヘプタフルオロブチリル）イミダゾール、２－メチルイミダゾール、４－メチルイミダゾール、２－フェニルイミダゾール、４－フェニルイミダゾール、１－ベンジルイミダゾール、４－メチル－２－フェニルイミダゾール、１－アセチルイミダゾール、１－イミダゾール酢酸、４－イミダゾールカルボン酸、４，５－イミダゾールジカルボン酸、等が好ましい。 As an 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.
　ピラゾール系化合物としては、ピラゾール、１－メチルピラゾール、３－メチルピラゾール、４－メチルピラゾール、１－エチルピラゾール、３－エチルピラゾール、４－エチルピラゾール、１－フェニルピラゾール、３－フェニルピラゾール、４－フェニルピラゾール、３，５－ジイソプロピルピラゾール、３－（トリフルオロメチル）ピラゾール、４－ブロモピラゾール、４－クロロピラゾール、３，５－ジメチルピラゾール、１，３，５－トリメチルピラゾール、３，５－ジメチル－１－フェニルピラゾール、３－（４－トリル）ピラゾール、３－（４－メトキシフェニル）ピラゾール、３－（４－ブロモフェニル）ピラゾール、３－メチル－１－フェニルピラゾール、４－ブロモ－３－メチルピラゾール、３－（４－ブロモフェニル）ピラゾール、３－（４－フルオロフェニル）ピラゾール、４－ブロモ－３，５－ジメチルピラゾール、４－ブロモ－１－フェニルピラゾール、３－（４－クロロフェニル）ピラゾール、３，５－ジメチル－１－ヒドロキシメチルピラゾール、ピラゾール－３－カルボン酸、ピラゾール－４－カルボン酸、等が好ましい。 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-bromopheny ) Pyrazole, 3- (4-fluorophenyl) pyrazole, 4-bromo-3,5-dimethylpyrazole, 4-bromo-1-phenylpyrazole, 3- (4-chlorophenyl) pyrazole, 3,5-dimethyl-1-yl Preferred are hydroxymethylpyrazole, pyrazole-3-carboxylic acid, pyrazole-4-carboxylic acid and the like.
　オキサゾール系化合物としては、オキサゾール、２，４－ジメチルオキサゾール、４－フェニルオキサゾール、５－フェニルオキサゾール、２，４－ジフェニルオキサゾール、２，５－ジフェニルオキサゾール、２，４，５－トリメチルオキサゾール、５－［３－（トリフルオロメチル）フェニル］オキサゾール、２－メチル－４，５－ジフェニルオキサゾール、５－エトキシ－４－メチルオキサゾール、４－オキサゾールカルボン酸、４－オキサゾールカルボン酸エチル等が好ましい。 Examples of 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.
　イソオキサゾール系化合物としては、イソオキサゾール、５－メチルイソオキサゾール、３，５－ジメチルイソオキサゾール、４－ブロモ－３．５－ジメチルイソオキサゾール、３－クロロメチル－５－メチルイソオキサゾール、４－（クロロメチル）－３，５－ジメチルイソオキサゾール、４－ヨードー３，５－ジメチルイソオキサゾール、３－ヒドロキシ－５－メチルイソオキサゾール、５－メチル－３－イソオキサゾールカルボン酸、５－メチルイソオキサゾール－４カルボン酸等が好ましい Examples of 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
　チアゾール系化合物としては、チアゾール、２－メチルチアゾール、２－エチルチアゾール、２－ｎ－プロピルチアゾール、２－イソプロピルチアゾール、２－ｎ－ブチルチアゾール、２－イソブチルチアゾール、２－フェニルチアゾール、４－メチルチアゾール、５－メチルチアゾール、２，４－ジメチルチアゾール、４，５－ジメチルチアゾール、２－エチル－４－メチルチアゾール、２－エチル－４，５－ジメチルチアゾール、２－イソプロピル－４－メチルチアゾール、２－イソブチル－４－メチルチアゾール、４－メチル－２－フェニルチアゾール、４－メチル－５－ビニルチアゾール、２－イソブチル－４，５－ジメチルチアゾール、２－メチル－４，５－ジフェニルチアゾール、２，４，５－トリメチルチアゾール、２－（ｏ－トリル）ベンゾチアゾール、２－（トリメチルシリル）チアゾール、２－ブロモチアゾール、４－ブロモチアゾール、５－ブロモチアゾール、２－ブロモ－４－メチルチアゾール、4－ｔｅｒｔ－ブチル－２－メチルチアゾール、２－ｓ－ブチルチアゾール、２，４－ジブロモチアゾール、２，５－ジブロモチアゾール、２，４－ジクロロチアゾール、４，５－ジメチル－２－エチルチアゾール、４，５－ジメチル－２－イソプロピルチアゾール、２－アセチルチアゾール、２－アセチル－４，５－ジメチルチアゾール等、２－エトキシチアゾール、５－ヒドロキシメチルチアゾール、２－ヒドロキシ－４－フェニルチアゾール、２－メトキシチアゾールが好ましい。 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) thiazole, 2-bromothiazole, 4-bromothiazole, 5-bromothiazole, 2-bromo-4-methylthiazole, 4-tert-butyl-2-methylthiazole, 2- s-Butylthiazole, 2,4-dibromothiazole, 2,5-dibromothiazole, 2,4-dichlorothiazole, 4,5-dimethyl-2-ethylthiazole, 4,5-dimethyl-2-isopropylthiazole, 2- Acetylthiazole, 2-acetyl-4,5-dimethylthiazole, etc., 2-ethoxythiazole, 5-hydroxymethylthiazole, 2-hydroxy-4-phenylthiazole, 2-methoxythiazole are preferred.
　イソチアゾール系化合物としては、イソチアゾールが好ましい。
　トリアゾール系化合物としては、１，２，３－トリアゾール、１，２，４－トリアゾール、３－メチル－１Ｈ－１，２，４－トリアゾール等が好ましい。 The isothiazole compound is preferably isothiazole.
As the triazole compounds, 1,2,3-triazole, 1,2,4-triazole, 3-methyl-1H-1,2,4-triazole and the like are preferable.
　オキサジアゾール系化合物としては、１，２，３－オキサジアゾール、１，２，４－オキサジアゾール、１，３，４－オキサジアゾール、１，２，５－オキサジアゾール、２－クロロメチル－５－（４－メチルフェニル）－１，３，４－オキサジアゾール、３－（クロロメチル）－１，２，４－オキサジアゾール、３－（クロロメチル）－５－フェニル－１，２，４－オキサジアゾール、２，５－ジフェニル－１，３，４－オキサジアゾール、５－メチル－３－フェニル－１，２，４－オキサジアゾール、２－（２－メトキシフェニル）－５－フェニル－１，３，４－オキサジアゾール、エチル－１，２，４－オキサジアゾール－３－カルボン酸等が好ましい。 As the oxadiazole compounds, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,5-oxadiazole, 2- Chloromethyl-5- (4-methylphenyl) -1,3,4-oxadiazole, 3- (chloromethyl) -1,2,4-oxadiazole, 3- (chloromethyl) -5-phenyl- 1,2,4-oxadiazole, 2,5-diphenyl-1,3,4-oxadiazole, 5-methyl-3-phenyl-1,2,4-oxadiazole, 2- (2-methoxy Phenyl) -5-phenyl-1,3,4-oxadiazole, ethyl-1,2,4-oxadiazole-3-carboxylic acid and the like are preferable.
　チアジアゾール系化合物としては、１，２，３－チアジアゾール、１，２，４－チアジアゾール、１，３，４－チアジアゾール、１，２，５－チアジアゾール、２，５－ジメチル－１，３，４－チアジアゾール、４－フェニル－１，２，３－チアジアゾール、４，５－ジフェニル－１，２，３－チアジアゾール、３－ブロモ－５－クロロ－１，２，４－チアジアゾール、２－ブロモ－５－フェニル－１，３，４－チアジアゾール、２－クロロメチル－５－シクロプロピル－１，３，４－チアジアゾール、３，４－ジクロロ－１，２，５－チアジアゾール、３，５－ジクロロ－１，２，４－チアジアゾール等が好ましい。 Examples of 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.
　６員環芳香族複素環化合物としては、ピリミジン系化合物、ピリダジン系化合物、ピラジン系化合物、トリアジン系化合物等が好ましい。 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.
　ピリミジン系化合物としては、ピリミジン、２－クロロピリミジン、２－ブロモピリミジン、５－ブロモピリミジン、５－ブロモ－２－クロロピリミジン、２－クロロ－４－メチルピリミジン、２－クロロ－５－エチルピリミジン、５－ブロモ－２，４－ジクロロピリミジン、５－ブロモ－４，６－ジクロロピリミジン、２－クロロ－５－ｎ－デシルピリミジン、２－クロロ－４，６－ジメチルピリミジン、４－クロロ－２，６－ジメチルピリミジン、ピリミジン－５－カルボン酸、５－ブロモ－２－ヒドロキシピリミジン、５－ブロモ－２－メトキシピリミジン、４，６－ジヒドロキシピリミジン、４，６－ジメトキシピリミジン、４－ヒドロキシピリミジン、２，４，５－トリヒドロキシピリミジン等が好ましい。 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.
　ピリダジン系化合物としては、３－メチルピリダジン、４－メチルピリダジン、３，６－ジクロロピリダジン、３，６－ジクロロ－４－メチルピリダジン、３，４，６－トリクロロピリダジン、ピリダジン－４－カルボン酸、ピリダジン－４，５－ジカルボン酸、３，６－ジヒドロキシ－４－メチルピリダジン、３－メトキシピリダジン等が好ましい。 Examples of 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.
　ピラジン系化合物としては、ピラジン、２－メチルピラジン、２－エチルピラジン、２－ｎ－プロピルピラジン、２－イソプロピルピラジン、２－イソブチルピラジン、２－ｔｅｒｔ－ブチルピラジン、２－ビニルピラジン、２－クロロピラジン、２，３－ジメチルピラジン、２，５－ジメチルピラジン、２，６－ジメチルピラジン、２，３－ジエチルピラジン、２，３－ジフェニルピラジン、２－メチル－３－ｎ－プロピルピラジン、２－エチル－３－メチルピラジン、２－イソブチル－３－メチルピラジン、５－イソブチル－２，３－ジメチルピラジン、２，３－ジエチル－５－メチルピラジン、３，５－ジメチル－２－エチルピラジン、２，３，５－トリメチルピラジン、２，３，５，６－テトラメチルピラジン、２，３－ジメチル－５－イソプロピルピラジン、２，３－ジクロロピラジン、２，６－ジクロロピラジン、２－アセチル－３－メチルピラジン、２－メトキシピラジン、２－エトキシピラジン、２－エトキシ－３－メチルピラジン、２－エチル－３－メトキシピラジン、２－イソプロピル－３－メトキシピラジン、２－イソブチル－３－メトキシピラジン、２－アセチルピラジン、２－アセチル－３－エチルピラジン、ピラジンカルボン酸、ピラジン－２－カルボン酸メチル等が好ましい。 As 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, 2,3,5,6-tetramethylpyrazine, 2,3-dimethyl 5-isopropylpyrazine, 2,3-dichloropyrazine, 2,6-dichloropyrazine, 2-acetyl-3-methylpyrazine, 2-methoxypyrazine, 2-ethoxypyrazine, 2-ethoxy-3-methylpyrazine, 2-ethyl -3-methoxypyrazine, 2-isopropyl-3-methoxypyrazine, 2-isobutyl-3-methoxypyrazine, 2-acetylpyrazine, 2-acetyl-3-ethylpyrazine, pyrazinecarboxylic acid, methyl pyrazine-2-carboxylate and the like Is preferred.
　トリアジン系化合物としては、１，２，３－トリアジン、１，２，４－トリアジン、１，３，５－トリアジン、２，４，６－トリクロロ－１，３，５－トリアジン、２，４，６－トリフェニル－１，３，５－トリアジン、２，４，６－トリス（トリフルオロメチル）－１，３，５－トリアジン等、２，４－ジメトキシ－１，３，５－トリアジンが好ましい。 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 .
　多環式芳香族複素環化合物としては、ベンゾイミダゾール系化合物、ベンゾピラゾール系化合物、ベンゾオキサゾール系化合物、ベンゾイソオキサゾール系化合物、ベンゾチアゾール系化合物、ベンゾトリアゾール系化合物、ベンゾオキサジアゾール系、ベンゾチアジアゾール系化合物、キナゾリン系化合物、フタラジン系化合物、フェナントロリン系化合物、ビピリジン系化合物が好ましい。 Examples of polycyclic aromatic heterocyclic compounds 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.
　ベンゾイミダゾール系化合物の具体例としては、ベンゾイミダゾール、４－メチルベンゾイミダゾール、５－メチルベンゾイミダゾール、６－メチルベンゾイミダゾール、７－メチルベンゾイミダゾール、４－エチルベンゾイミダゾール、５－エチルベンゾイミダゾール、６－エチルベンゾイミダゾール、７－エチルベンゾイミダゾール、４－ｎ－プロピルベンゾイミダゾール、５－ｎ－プロピルベンゾイミダゾール、６－ｎ－プロピルベンゾイミダゾール、７－ｎ－プロピルベンゾイミダゾール、４－イソプロピルベンゾイミダゾール、５－イソプロピルベンゾイミダゾール、６－イソプロピルベンゾイミダゾール、７－イソプロピルベンゾイミダゾール、１－ブチルベンゾイミダゾール、２－アセチルベンゾイミダゾール、２－クロロベンゾイミダゾール、２－（クロロメチル）ベンゾイミダゾール、２，５－ジメチルベンゾイミダゾール、５－ベンゾイミダゾールカルボン酸、２－ヒドロキシベンゾイミダゾール、２－（ヒドロキシメチル）ベンゾイミダゾール、２－（３－ヒドロキシプロピル）ベンゾイミダゾール、２－（１－ヒドロキシエチル）ベンゾイミダゾール、５－ベンゾイミダゾールカルボン酸、２－ヒドロキシベンゾイミダゾール等が好ましい。 Specific examples of the 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-dimethylbenzimidazole, 5-benzimidazole carboxylic acid, 2-hydroxybenzimidazole, 2- (hydroxymethyl) benzimidazole, 2- (3-hydroxypropyl) 2.) Benzoimidazole, 2- (1-hydroxyethyl) benzimidazole, 5-benzimidazole carboxylic acid, 2-hydroxybenzimidazole and the like are preferable.
　ベンゾピラゾール系化合物の具体例としては、１，２－ベンゾピラゾール、３－クロロ－１Ｈ－ベンゾピラゾール等が好ましい。 As specific examples of the benzopyrazole compound, 1,2-benzopyrazole, 3-chloro-1H-benzopyrazole and the like are preferable.
　ベンゾオキサゾール系化合物の具体例としては、ベンゾオキサゾール、２－メチルベンゾオキサゾール、５－メチルベンゾオキサゾール、２，６－ジクロロベンゾオキサゾール、２，５－ジメチルベンゾオキサゾール、５－フルオロ－２－メチルベンゾオキサゾール、２，５，６－トリメチルベンゾオキサゾール、２－クロロベンゾオキサゾール、２－メチル－５－フェニルベンゾオキサゾール、２－（２－ヒドロキシフェニル）ベンゾオキサゾール等が好ましい。 Specific examples of the 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.
　ベンゾイソオキサゾール系化合物の具体例としては、１，２－ベンゾイソオキサゾール、１，２－ベンゾイソオキサゾール－３－酢酸等が好ましい。 As specific examples of the benzoisoxazole compounds, 1,2-benzoisoxazole, 1,2-benzoisoxazole-3-acetic acid and the like are preferable.
　ベンゾチアゾール系化合物の具体例としては、ベンゾチアゾール、２－メチルベンゾチアゾール、２－エチルベンゾチアゾール、２－ｎ－プロピルベンゾチアゾール、２－イソプロピルベンゾチアゾール、２－ｎ－ブチルベンゾチアゾール、２－フェニルベンゾチアゾール、２，５－ジメチルベンゾチアゾール、２，６－ジメチルベンゾチアゾール、２，５，６－トリメチルベンゾチアゾール、２－クロロベンゾチアゾール、２－クロロ－５－クロロメチルチアゾール、６－ブロモ－２－クロロベンゾチアゾール、５－ブロモ－２－メチルベンゾチアゾール、２，６－ジクロロベンゾチアゾール、２－フルオロベンゾチアゾール、５－クロロ－２－メチルベンゾチアゾール、５－フルオロ－２－メチルベンゾチアゾール、２－（４－ブロモフェニル）ベンゾチアゾール、２－アセチルベンゾチアゾール、２－ヒドロキシベンゾチアゾール、５－メトキシ－２－メチルベンゾチアゾール、２－（２－ヒドロキシフェニル)ベンゾチアゾール、ベンゾチアゾール－６－カルボン酸等が好ましい。 Specific examples of the benzothiazole compound 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-benzothiazole, 5-methoxy-2-methyl-benzothiazole, 2- (2-hydroxyphenyl) benzothiazole, etc. benzothiazole-6-carboxylic acid.
　ベンゾトリアゾール系化合物としては１，２，３－ベンゾトリアゾール、４－メチルベンゾトリアゾール、１－クロロベンゾトリアゾール、５－クロロベンゾトリアゾール、１－メチル－１Ｈ－ベンゾトリアゾール、２－メチル－２Ｈ－ベンゾトリアゾール、５－メチル－１Ｈ－ベンゾトリアゾール１－（クロロメチル）－１Ｈ－ベンゾトリアゾール、４－ヒドロキシベンゾトリアゾール、１－（メトキシメチル）－１Ｈ－ベンゾトリアゾール、２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、１Ｈ－ベンゾトリアゾール－１－メタノール、１，２，３－ベンゾトリアゾール－５－カルボン酸メチル、１，２，４－ベンゾトリアゾール－３－カルボン酸メチル、４－メチル－２－フェニル－１，２，３－トリアゾール－５－カルボン酸、１－イソプロピルベンゾトリアゾール－５－カルボン酸、１－アミノベンゾトリアゾール等が好ましい。 As benzotriazole compounds, 1,2,3-benzotriazole, 4-methylbenzotriazole, 1-chlorobenzotriazole, 5-chlorobenzotriazole, 1-methyl-1H-benzotriazole, 2-methyl-2H-benzotriazole 5-methyl-1H-benzotriazole 1- (chloromethyl) -1H-benzotriazole 4-hydroxybenzotriazole 1- (methoxymethyl) -1H-benzotriazole 2- (2-hydroxy-5-methylphenyl) ) Benzotriazole, 1H-benzotriazole-1-methanol, methyl 1,2,3-benzotriazole-5-carboxylate, methyl 1,2,4-benzotriazole-3-carboxylate, 4-methyl-2-phenyl -1,2,3-Triazole- - carboxylic acid, 1-isopropyl-benzotriazole-5-carboxylic acid, 1-amino-benzotriazole and the like are preferable.
　ベンゾオキサジアゾール系化合物としては２，１，３－ベンゾオキサジアゾール、４－フルオロ－２，１，３－ベンゾオキサジアゾール、４－クロロ－２，１，３－ベンゾオキサジアゾール等が好ましい。 Examples of benzoxadiazole compounds include 2,1,3-benzoxadiazole, 4-fluoro-2,1,3-benzoxadiazole, 4-chloro-2,1,3-benzoxadiazole, etc. preferable.
　ベンゾチアジアゾール系化合物としては２，１，３－ベンゾチアジアゾール、４，７－ジブロモ－２，１，３－ベンゾチアジアゾール、５，６－ジブロモ－２，１，３－ベンゾチアジアゾール、２，１，３－ベンゾチアジアゾール－５－カルボン酸、２－メルカプトベンゾチアゾール、６－アミノ－２－メルカプトベンゾチアゾール等が好ましい。 Examples of 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.
　キナゾリン系化合物としては、キナゾリン、４－クロロキナゾリン、２，４－ジクロロキナゾリン、４－ヒドロキシキナゾリン、５－フルオロ－４－ヒドロキシキナゾリン等が好ましい。 Preferred quinazoline compounds are quinazoline, 4-chloroquinazoline, 2,4-dichloroquinazoline, 4-hydroxyquinazoline, 5-fluoro-4-hydroxyquinazoline and the like.
　フタラジン系化合物としては、フタラジン、６－メチルフタラジン、１－クロロフタラジン、１，４－ジクロロフタラジン等が好ましい。 As phthalazine-based compounds, phthalazine, 6-methyl phthalazine, 1-chlorophthalazine, 1,4-dichloro phthalazine and the like are preferable.
　フェナントロリン系化合物としては、１，１０－フェナントロリン、５－メチル－１，１０－フェナントロリン、２－クロロ－１，１０－フェナントロリン、５－クロロ－１，１０－フェナントロリン、３，８－ジメチル－１，１０－フェナントロリン、４，７－ジメチル－１，１０－フェナントロリン、５，６―ジメチル－１，１０－フェナントロリン、２，９－ジブチル－１，１０－フェナントロリン、４，７－ジフェニル－１，１０－フェナントロリン、４，７－ジクロロ－１，１０－フェナントロリン、３－ブロモ－１，１０－フェナントロリン、３，４，７，８－テトラメチル－１，１０－フェナントロリン、４，７－ジヒドロキシ－１，１０－フェナントロリン、１，１０－フェナントロリン－２，９－ジカルボン酸等が好ましい。 As phenanthroline compounds, 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.
　ビピリジン系化合物としては、２，２’－ビピリジン、２，４’－ビピリジン、４，４’－ビピリジン、５－フェニル－２，２’－ビピリジン、５－フェニル－２，３’－ビピリジン、５－フェニル－２，４’－ビピリジン、４，４’－ジメチル－２，２’－ビピリジン、５，５’－ジメチル－２，２’－ビピリジン、６，６’－ジメチル－２，２’－ビピリジン、４，４’－ジノニル－２，２’－ビピリジン、４，４’－ジブロモ－２，２’－ビピリジン、６，６’－ジブロモ－２，２’－ビピリジン、４，４’－ビス（クロロメチル）－２，２’－ビピリジン、５，５’－ジクロロ－２，２’－ビピリジン、５－ブロモ－２，２’－ビピリジン、５－ブロモ－２，３’－ビピリジン、５－ブロモ－２，４’－ビピリジン、６－ブロモ－２，２’－ビピリジン、４，４’－ビス（ヒドロキシメチル）－２，２’－ビピリジン、２，２’－ビピリジン－３，３’－ジカルボン酸、２，２’－ビピリジン－４，４’－ジカルボン酸、２，２’－ビピリジン－５，５’－ジカルボン酸、等が好ましい。 Examples of 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- Bromo-2,4'-bipyridine, 6-bromo- , 2′-bipyridine, 4,4′-bis (hydroxymethyl) -2,2′-bipyridine, 2,2′-bipyridine-3,3′-dicarboxylic acid, 2,2′-bipyridine-4,4 ′ -Dicarboxylic acid, 2,2'-bipyridine-5,5'-dicarboxylic acid, etc. are preferred.
　これらの中でも、芳香族複素環化合物としては、オキサゾール、２，４，５－トリメチルオキサゾール、イソオキサゾール、５－メチルイソオキサゾール、チアゾール、５－メチルチアゾール、イソチアゾール、１，２，３－トリアゾール、１，２，４－トリアゾール、１，２，３－オキサジアゾール、１，２，４－オキサジアゾール、１，３，４－オキサジアゾール、１，２，５－オキサジアゾール、１，２，３－チアジアゾール、１，２，４－チアジアゾール、１，３，４－チアジアゾール、１，２，５－チアジアゾール、ピリミジン、１，２，３－トリアジン、１，２，４－トリアジン、１，３，５－トリアジン、１，２－ベンゾピラゾール、ベンゾオキサゾール、５－メチルベンゾオキサゾール、１，２－ベンゾイソオキサゾール、ベンゾチアゾール、２，６－ジメチルベンゾチアゾール、２，１，３－ベンゾオキサジアゾール、２，１，３－ベンゾチアジアゾール、１，２，３－ベンゾトリアゾール、キナゾリン、フタラジン、１，１０－フェナントロリン、５－メチル－１，１０－フェナントロリン、２，２’－ビピリジン、４，４’－ビピリジン、５，５’－ジメチル－２，２’－ビピリジン、２－メルカプトベンゾチアゾール、１－アミノベンゾトリアゾール、６－アミノ－２－メルカプトベンゾチアゾールが好ましく、１，２，３－トリアゾール、１，２，４－トリアゾール、１，２，３－オキサジアゾール、１，２，４－オキサジアゾール、１，３，４－オキサジアゾール、１，２，５－オキサジアゾール、１，２，３－チアジアゾール、１，２，４－チアジアゾール、１，３，４－チアジアゾール、１，２，５－チアジアゾール、ピリミジン、１，２，３－トリアジン、１，２，４－トリアジン、１，３，５－トリアジン、１，２－ベンゾピラゾール、２，１，３－ベンゾオキサジアゾール、２，１，３－ベンゾチアジアゾール、１，２，３－ベンゾトリアゾール、キナゾリン、フタラジン、１，１０－フェナントロリン、５－メチル－１，１０－フェナントロリン、２，２’－ビピリジン、４，４’－ビピリジン、５，５’－ジメチル－２，２’－ビピリジンがより好ましい。 Among these, as the aromatic heterocyclic compound, 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. 2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, 1,2,5-thiadiazole, pyrimidine, 1,2,3-triazine, 1,2,4-triazine, 1, 3,5-Triazine, 1,2-benzopyrazole, benzoxazole, 5-methylbenzoxazole, 1,2-benzoisoxazole Benzothiazole, 2,6-dimethylbenzothiazole, 2,1,3-benzoxadiazole, 2,1,3-benzothiadiazole, 1,2,3-benzotriazole, quinazoline, phthalazine, 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,2'-bipyridine, 4,4'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 2-mercaptobenzothiazole, 1-aminobenzotriazole, 6-amino-2-mercaptobenzothiazole is preferred, 1,2,3-triazole, 1,2,4-triazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2. 3,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thia Azole, 1,3,4-thiadiazole, 1,2,5-thiadiazole, pyrimidine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 1,2- benzopyrazole 2,1,3-benzoxadiazole, 2,1,3-benzothiadiazole, 1,2,3-benzotriazole, quinazoline, phthalazine, 1,10-phenanthroline, 5-methyl-1,10-phenanthroline, More preferred are 2,2′-bipyridine, 4,4′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine.
　本発明の感光性樹脂組成物中における芳香族複素環化合物の添加量は、感光性樹脂組成物の全固形分１００質量部に対し、０．０１～１０質量部であることが好ましく、０．０１～８質量部であることがより好ましく、０．０１～５質量部であることがさらに好ましい。 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.
＜（Ｄ）溶剤＞
　本発明の感光性樹脂組成物は、（Ｄ）溶剤を含有する。本発明の感光性樹脂組成物は、本発明の必須成分と、さらに後述の任意の成分を（Ｄ）溶剤に溶解した溶液として調製されることが好ましい。
　本発明の感光性樹脂組成物に使用される（Ｄ）溶剤としては、公知の溶剤を用いることができ、エチレングリコールモノアルキルエーテル類、エチレングリコールジアルキルエーテル類、エチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールジアルキルエーテル類、プロピレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジアルキルエーテル類、ジエチレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、ジプロピレングリコールモノアルキルエーテルアセテート類、エステル類、ケトン類、アミド類、ラクトン類等が例示できる。また、本発明の感光性樹脂組成物に使用される（Ｄ）溶剤の具体例としては特開２０１１－２２１４９４号公報の段落番号０１７４～０１７８に記載の溶剤も挙げられ、これらの内容は本願明細書に組み込まれる。 <(D) Solvent>
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.
As the 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. Moreover, as a specific example of (D) solvent used for the photosensitive resin composition of this invention, the solvent as described in Paragraph No. 0174-0178 of Unexamined-Japanese-Patent No. 2011-221494 is also mentioned, These contents are this-application specification. Incorporated into the book.
　また、これらの溶剤にさらに必要に応じて、ベンジルエチルエーテル、ジヘキシルエーテル、エチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、イソホロン、カプロン酸、カプリル酸、１－オクタノール、１－ノナール、ベンジルアルコール、アニソール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、炭酸エチレン、炭酸プロピレン等の溶剤を添加することもできる。これら溶剤は、１種単独でまたは２種以上を混合して使用することができる。本発明に用いることができる溶剤は、１種単独、または、２種を併用することが好ましく、２種を併用することがより好ましく、プロピレングリコールモノアルキルエーテルアセテート類またはジアルキルエーテル類、ジアセテート類とジエチレングリコールジアルキルエーテル類、あるいは、エステル類とブチレングリコールアルキルエーテルアセテート類とを併用することがさらに好ましい。 In addition to these solvents, 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.
　また、成分Ｄとしては、沸点１３０℃以上１６０℃未満の溶剤、沸点１６０℃以上の溶剤、または、これらの混合物であることが好ましい。
　沸点１３０℃以上１６０℃未満の溶剤としては、プロピレングリコールモノメチルエーテルアセテート（沸点１４６℃）、プロピレングリコールモノエチルエーテルアセテート(沸点１５８℃)、プロピレングリコールメチル－ｎ－ブチルエーテル（沸点１５５℃）、プロピレングリコールメチル－ｎ－プロピルエーテル（沸点１３１℃）が例示できる。
　沸点１６０℃以上の溶剤としては、３－エトキシプロピオン酸エチル（沸点１７０℃）、ジエチレングリコールメチルエチルエーテル（沸点１７６℃）、プロピレングリコールモノメチルエーテルプロピオネート（沸点１６０℃）、ジプロピレングリコールメチルエーテルアセテート（沸点２１３℃）、３－メトキシブチルエーテルアセテート（沸点１７１℃）、ジエチレングリコールジエチエルエーテル（沸点１８９℃）、ジエチレングリコールジメチルエーテル（沸点１６２℃）、プロピレングリコールジアセテート（沸点１９０℃）、ジエチレングリコールモノエチルエーテルアセテート（沸点２２０℃）、ジプロピレングリコールジメチルエーテル（沸点１７５℃）、１，３－ブチレングリコールジアセテート（沸点２３２℃）が例示できる。 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.
As 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.).
As solvents having a boiling point of 160 ° C. or higher, ethyl 3-ethoxypropionate (boiling point 170 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), dipropylene glycol methyl ether acetate (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.
　本発明の感光性樹脂組成物における（Ｄ）溶剤の含有量は、感光性樹脂組成物中の全樹脂成分１００質量部当たり、５０～９５質量部であることが好ましく、６０～９０質量部であることがさらに好ましい。 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
＜その他の成分＞
　本発明の感光性樹脂組成物には、上記成分に加えて、必要に応じて、（Ｅ）アルコキシシラン化合物、（Ｆ）架橋剤、（Ｇ）増感剤、（Ｈ）塩基性化合物、（Ｉ）界面活性剤、（Ｊ）酸化防止剤、を好ましく加えることができる。さらに本発明の感光性樹脂組成物には、酸増殖剤、現像促進剤、可塑剤、熱ラジカル発生剤、熱酸発生剤、紫外線吸収剤、増粘剤、および、有機または無機の沈殿防止剤などの公知の添加剤を加えることができる。 <Other ingredients>
In 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.
（Ｅ）アルコキシシラン化合物
　本発明の感光性樹脂組成物は、（Ｅ）アルコキシシラン化合物（「（Ｅ）成分」ともいう）を含有することを特徴とする。アルコキシシラン化合物を用いると、本発明の感光性樹脂組成物により形成された膜と基板との密着性を向上できたり、本発明の感光性樹脂組成物により形成された膜の性質を調整することができる。アルコキシシラン化合物としては、ジアルコキシシラン化合物またはトリアルコキシシラン化合物が好ましく、トリアルコキシシラン化合物がより好ましい。アルコキシシラン化合物が有するアルコキシ基の炭素数は１～５が好ましい。
　本発明の感光性樹脂組成物に用いることができる（Ｅ）アルコキシシラン化合物は、基材となる無機物、例えば、シリコン、酸化シリコン、窒化シリコン等のシリコン化合物、金、銅、モリブデン、チタン、アルミニウム等の金属と絶縁膜との密着性を向上させる化合物であることが好ましい。具体的には、公知のシランカップリング剤等も有効である。
　シランカップリング剤としては、例えば、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－グリシドキシプロピルトリアルコキシシラン、γ－グリシドキシプロピルアルキルジアルコキシシラン、γ－メタクリロキシプロピルトリアルコキシシラン、γ－メタクリロキシプロピルアルキルジアルコキシシラン、γ－クロロプロピルトリアルコキシシラン、γ－メルカプトプロピルトリアルコキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリアルコキシシラン、ビニルトリアルコキシシランが挙げられる。これらのうち、γ－グリシドキシプロピルトリアルコキシシランやγ－メタクリロキシプロピルトリアルコキシシランがより好ましく、γ－グリシドキシプロピルトリアルコキシシランがさらに好ましく、３－グリシドキシプロピルトリメトキシシランがよりさらに好ましい。これらは１種単独または２種以上を組み合わせて使用することができる。 (E) Alkoxysilane Compound The photosensitive resin composition of the present invention is characterized by containing (E) an alkoxysilane compound (also referred to as “component (E)”). By using 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. Can. As 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. Specifically, known silane coupling agents are also effective.
As a silane coupling agent, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxy Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned. Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. More preferable. These can be used singly or in combination of two or more.
　また、下記の化合物も好ましく採用できる。
Figure JPOXMLDOC01-appb-C000021
 Further, the following compounds can also be preferably employed.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　上記において、Ｐｈはフェニル基である。 In the above, Ph is a phenyl group.
　本発明の感光性樹脂組成物における（Ｅ）アルコキシシラン化合物は、特にこれらに限定することなく、公知のものを使用することができる。
　本発明の感光性樹脂組成物における（Ｅ）アルコキシシラン化合物の含有量は、感光性組成物中の全固形分１００質量部に対して、０．１～３０質量部が好ましく、０．５～２０質量部がより好ましい。 As 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.
（Ｆ）架橋剤
　本発明の感光性樹脂組成物は、必要に応じ、架橋剤を含有することが好ましい。架橋剤を添加することにより、本発明の感光性樹脂組成物により得られる硬化膜をより強固な膜とすることができる。
　架橋剤としては、熱によって架橋反応が起こるものであれば制限は無い。（Ａ成分を除く）。例えば、以下に述べる分子内に２個以上のエポキシ基またはオキセタニル基を有する化合物、アルコキシメチル基含有架橋剤、または、少なくとも１個のエチレン性不飽和二重結合を有する化合物、ブロックイソシアネート化合物等を添加することができる。
　本発明の感光性樹脂組成物中における架橋剤の添加量は、感光性樹脂組成物の全固形分１００質量部に対し、０．０１～５０質量部であることが好ましく、０．１～３０質量部であることがより好ましく、０．５～２０質量部であることがさらに好ましい。この範囲で添加することにより、機械的強度および耐溶剤性に優れた硬化膜が得られる。架橋剤は複数を併用することもでき、その場合は架橋剤を全て合算して含有量を計算する。 (F) Crosslinking agent It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding the crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is not 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.
＜分子内に２個以上のエポキシ基またはオキセタニル基を有する化合物＞
　分子内に２個以上のエポキシ基を有する化合物の具体例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂肪族エポキシ樹脂等を挙げることができる。 <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.
　これらは市販品として入手できる。例えば、ＪＥＲ１５７Ｓ７０、ＪＥＲ１５７Ｓ６５（（株）三菱ケミカルホールディングス製）など、特開２０１１－２２１４９４号公報の段落番号０１８９に記載の市販品などが挙げられる。
　その他にも、ＡＤＥＫＡ　ＲＥＳＩＮ　ＥＰ－４０００Ｓ、同ＥＰ－４００３Ｓ、同ＥＰ－４０１０Ｓ、同ＥＰ－４０１１Ｓ（以上、（株）ＡＤＥＫＡ製）、ＮＣ－２０００、ＮＣ－３０００、ＮＣ－７３００、ＸＤ－１０００、ＥＰＰＮ－５０１、ＥＰＰＮ－５０２（以上、（株）ＡＤＥＫＡ製）、デナコール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－２１４Ｌ、ＥＸ－２１６Ｌ、ＥＸ－３２１Ｌ、ＥＸ－８５０Ｌ、ＤＬＣ－２０１、ＤＬＣ－２０３、ＤＬＣ－２０４、ＤＬＣ－２０５、ＤＬＣ－２０６、ＤＬＣ－３０１、ＤＬＣ－４０２（以上ナガセケムテック製）、ＹＨ－３００、ＹＨ－３０１、ＹＨ－３０２、ＹＨ－３１５、ＹＨ－３２４、ＹＨ－３２５（以上新日鐵化学製）セロキサイド２０２１Ｐ、２０８１、３０００、ＥＨＰＥ３１５０、エポリードＧＴ４００、セルビナースＢ０１３４、Ｂ０１７７（（株）ダイセル）、などが挙げられる。
これらは１種単独または２種以上を組み合わせて使用することができる。 These are commercially available. For example, 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.
In addition, 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, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase Chemtech Inc.), YH -300, YH-301, YH-302, YH-315, YH-324, YH-325 (all manufactured by Nippon Steel Chemical Co., Ltd.) Celoxide 2021 P, 2081, 3000, EHPE 3150, Epoide GT 400, Celliners B 0134, B 0177 Daicel), etc.
These can be used singly or in combination of two or more.
　これらの中でも、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂および脂肪族エポキシ、脂肪族エポキシ樹脂がより好ましく挙げられ、ビスフェノールＡ型エポキシ樹脂が特に好ましく挙げられる。 Among these, 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.
　分子内に２個以上のオキセタニル基を有する化合物の具体例としては、アロンオキセタンＯＸＴ－１２１、ＯＸＴ－２２１、ＯＸ－ＳＱ、ＰＮＯＸ（以上、東亞合成（株）製）を用いることができる。 As specific examples of the compound having two or more oxetanyl groups in the molecule, aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (all manufactured by Toagosei Co., Ltd.) can be used.
　また、オキセタニル基を含む化合物は、単独でまたはエポキシ基を含む化合物と混合して使用することが好ましい。 In addition, the compound containing an oxetanyl group is preferably used alone or in combination with a compound containing an epoxy group.
　また、その他の架橋剤としては特開２０１２－８２２３号公報の段落番号０１０７～０１０８に記載のアルコキシメチル基含有架橋剤、および少なくとも１個のエチレン性不飽和二重結合を有する化合物なども好ましく用いることができ、これらの内容は本願明細書に組み込まれる。アルコキシメチル基含有架橋剤としては、アルコキシメチル化グリコールウリルが好ましい。 In addition, as other crosslinking agents, 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. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.
＜ブロックイソシアネート化合物＞
　本発明の感光性樹脂組成物では、架橋剤として、ブロックイソシアネート系化合物も好ましく採用できる。ブロックイソシアネート化合物は、ブロックイソシアネート基を有する化合物であれば特に制限はないが、硬化性の観点から、１分子内に２以上のブロックイソシアネート基を有する化合物であることが好ましい。
　なお、本発明におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。また、前記ブロックイソシアネート基は、９０℃～２５０℃の熱によりイソシアネート基を生成することが可能な基であることが好ましい。
　また、ブロックイソシアネート化合物としては、その骨格は特に限定されるものではなく、１分子中にイソシアネート基を２個有するものであればどのようなものでもよく、脂肪族、脂環族または芳香族のポリイソシアネートであってよいが、例えば２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、イソホロンジイソシアネート、１，６－ヘキサメチレンジイソシアネート、１，３－トリメチレンジイソシアネート、１，４－テトラメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、１，９－ノナメチレンジイソシアネート、１，１０－デカメチレンジイソシアネート、１，４－シクロヘキサンジイソシアネート、２，２’－ジエチルエーテルジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ｏ－キシレンジイソシアネート、ｍ－キシレンジイソシアネート、ｐ－キシレンジイソシアネート、メチレンビス（シクロヘキシルイソシアネート）、シクロヘキサン－１，３－ジメチレンジイソシアネート、シクロヘキサン－１，４－ジメチレレンジイソシアネート、１，５－ナフタレンジイソシアネート、ｐ－フェニレンジイソシアネート、３，３’－メチレンジトリレン－４，４’－ジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート、テトラクロロフェニレンジイソシアネート、ノルボルナンジイソシアネート、水素化１，３－キシリレンジイソシアネート、水素化１，４－キシリレンジイソシアネート等のイソシアネート化合物およびこれらの化合物から派生するプレポリマー型の骨格の化合物を好適に用いることができる。これらの中でも、トリレンジイソシアネート（ＴＤＩ）やジフェニルメタンジイソシアネート（ＭＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）が特に好ましい。 <Blocked isocyanate compound>
In the photosensitive resin composition of the present invention, 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.
In addition, the block isocyanate group in this invention is group which can produce | generate an isocyanate group by heat, for example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can be illustrated preferably. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
The skeleton of the blocked isocyanate compound is not particularly limited, and may be any 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-dimethylene diisocyanate, cyclohexane-1 , 4-Dimethylenedi diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methyleneditrilene-4,4'-diisocyanate, 4,4'-diphenylether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate , Isocyanation of hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, etc. Compounds and prepolymer type skeleton compounds derived from these compounds can be suitably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are particularly preferable.
　本発明の感光性樹脂組成物におけるブロックイソシアネート化合物の母構造としては、ビウレット型、イソシアヌレート型、アダクト型、２官能プレポリマー型等を挙げることができる。
　前記ブロックイソシアネート化合物のブロック構造を形成するブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、イミド系化合物等を挙げることができる。これらの中でも、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物から選ばれるブロック剤が特に好ましい。 As a mother structure of the block isocyanate compound in the photosensitive resin composition of this invention, a biuret type, an isocyanurate type, an adduct type, a bifunctional prepolymer type etc. can be mentioned.
Examples of 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. Among these, blocking agents selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds and pyrazole compounds are particularly preferable.
　前記オキシム化合物としては、オキシム、および、ケトオキシムが挙げられ、具体的には、アセトキシム、ホルムアルドキシム、シクロヘキサンオキシム、メチルエチルケトンオキシム、シクロヘキサノンオキシム、ベンゾフェノンオキシム、アセトキシム等が例示できる。
　前記ラクタム化合物としてはε－カプロラクタム、γ－ブチロラクタム等が例示できる。
　前記フェノール化合物としては、フェノール、ナフトール、クレゾール、キシレノール、ハロゲン置換フェノール等が例示できる。
　前記アルコール化合物としては、メタノール、エタノール、プロパノール、ブタノール、シクロヘキサノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、乳酸アルキル等が例示できる。
　前記アミン化合物としては、１級アミンおよび２級アミンが上げられ、芳香族アミン、脂肪族アミン、脂環族アミンいずれでもよく、アニリン、ジフェニルアミン、エチレンイミン、ポリエチレンイミン等が例示できる。
　前記活性メチレン化合物としては、マロン酸ジエチル、マロン酸ジメチル、アセト酢酸エチル、アセト酢酸メチル等が例示できる。
　前記ピラゾール化合物としては、ピラゾール、メチルピラゾール、ジメチルピラゾール等が例示できる、
　前記メルカプタン化合物としては、アルキルメルカプタン、アリールメルカプタン等が例示できる。 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 ε-caprolactam, γ-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.
　本発明の感光性樹脂組成物に使用できるブロックイソシアネート化合物は、市販品として入手可能であり、例えば、コロネートＡＰステーブルＭ、コロネート２５０３、２５１５、２５０７、２５１３、２５５５、ミリオネートＭＳ－５０（以上、日本ポリウレタン工業（株）製）、タケネートＢ－８３０、Ｂ－８１５Ｎ、Ｂ－８２０ＮＳＵ、Ｂ－８４２Ｎ、Ｂ－８４６Ｎ、Ｂ－８７０Ｎ、Ｂ－８７４Ｎ、Ｂ－８８２Ｎ（以上、三井化学（株）製）、デュラネート１７Ｂ－６０ＰＸ、１７Ｂ－６０Ｐ、ＴＰＡ－Ｂ８０Ｘ、ＴＰＡ－Ｂ８０Ｅ、ＭＦ－Ｂ６０Ｘ、ＭＦ－Ｂ６０Ｂ、ＭＦ－Ｋ６０Ｘ、ＭＦ－Ｋ６０Ｂ、Ｅ４０２－Ｂ８０Ｂ、ＳＢＮ－７０Ｄ、ＳＢＢ－７０Ｐ、Ｋ６０００（以上、旭化成ケミカルズ（株）製）、デスモジュールＢＬ１１００、ＢＬ１２６５　ＭＰＡ／Ｘ、ＢＬ３５７５／１、ＢＬ３２７２ＭＰＡ、ＢＬ３３７０ＭＰＡ、ＢＬ３４７５ＢＡ／ＳＮ、ＢＬ５３７５ＭＰＡ、ＶＰＬＳ２０７８／２、ＢＬ４２６５ＳＮ、ＰＬ３４０、ＰＬ３５０、スミジュールＢＬ３１７５（以上、住化バイエルウレタン（株）製）等を好ましく使用することができる。 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, BL3575 / 1, BL3272 MPA, BL3370 MPA, BL3475 BA / SN, BL5375 MPA, VPLS2078 / 2, BL4265 SN, PL340, PL350, Semidur BL3175 (all manufactured by Sumika Bayer Urethane Co., Ltd.), etc. are preferably used can do.
（Ｇ）増感剤
　本発明の感光性樹脂組成物は、（Ｂ）光酸発生剤との組み合わせにおいて、その分解を促進させるために、増感剤を含有することが好ましい。増感剤は、活性光線または放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、光酸発生剤と接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより光酸発生剤は化学変化を起こして分解し、酸を生成する。好ましい増感剤の例としては、以下の化合物類に属しており、かつ３５０ｎｍから４５０ｎｍの波長域のいずれかに吸収波長を有する化合物を挙げることができる。 (G) Sensitizer 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. Thus, the photoacid generator chemically changes and decomposes to generate an acid. Examples of 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.
　多核芳香族類（例えば、ピレン、ペリレン、トリフェニレン、アントラセン、９，１０－ジブトキシアントラセン、９，１０－ジエトキシアントラセン，３，７－ジメトキシアントラセン、９，１０－ジプロピルオキシアントラセン）、キサンテン類（例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガル）、キサントン類（例えば、キサントン、チオキサントン、ジメチルチオキサントン、ジエチルチオキサントン）、シアニン類（例えばチアカルボシアニン、オキサカルボシアニン）、メロシアニン類（例えば、メロシアニン、カルボメロシアニン）、ローダシアニン類、オキソノール類、チアジン類（例えば、チオニン、メチレンブルー、トルイジンブルー）、アクリジン類（例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン）、アクリドン類（例えば、アクリドン、１０－ブチル－２－クロロアクリドン、１０－ブチルアクリドン）、アントラキノン類（例えば、アントラキノン）、スクアリウム類（例えば、スクアリウム）、スチリル類、ベーススチリル類（例えば、２－［２－［４－（ジメチルアミノ）フェニル］エテニル］ベンゾオキサゾール）、クマリン類（例えば、７－ジエチルアミノ４－メチルクマリン、７－ヒドロキシ４－メチルクマリン、２，３，６，７－テトラヒドロ－９－メチル－１Ｈ，５Ｈ，１１Ｈ［１］ベンゾピラノ［６，７，８－ｉｊ］キノリジン－１１－ノン）。
　これら増感剤の中でも、多核芳香族類、アクリドン類、スチリル類、ベーススチリル類、クマリン類が好ましく、多核芳香族類がより好ましい。多核芳香族類の中でもアントラセン誘導体が最も好ましい。 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, methylene blue, toluidine blue), acridines (eg, acridine olein) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone, 10-butylacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryl , Base styryls (eg, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (eg, 7-diethylamino 4-methyl coumarin, 7-hydroxy 4-methyl coumarin, 2 3,6,7-Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls and coumarins are preferable, and polynuclear aromatics are more preferable. Anthracene derivatives are most preferable among polynuclear aromatics.
　本発明の感光性樹脂組成物中における増感剤の添加量は、感光性樹脂組成物の光酸発生剤１００質量部に対し、０～１０００質量部であることが好ましく、１０～５００質量部であることがより好ましく、５０～２００質量部であることがさらに好ましい。
　２種以上を併用することもできる。 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.
（Ｈ）塩基性化合物
　本発明の感光性樹脂組成物は、（Ｈ）塩基性化合物を含有してもよい。（Ｈ）塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、カルボン酸の第四級アンモニウム塩等が挙げられる。これらの具体例としては、特開２０１１－２２１４９４号公報の段落番号０２０４～０２０７に記載の化合物が挙げられ、これらの内容は本願明細書に組み込まれる。また、Ｎ－シクロヘキシル－Ｎ’－［２－（４－モルホリニル）エチル］チオ尿素などのチオ尿素類を用いてもよい。 (H) Basic Compound The photosensitive resin composition of the present invention may contain (H) a basic compound. As the basic compound (H), any compound selected from those used in chemically amplified resists can be used. For example, 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. Also, thioureas such as N-cyclohexyl-N '-[2- (4-morpholinyl) ethyl] thiourea may be used.
　本発明に用いることができる塩基性化合物は、１種単独で使用しても、２種以上を併用してもよい。 The basic compounds that can be used in the present invention may be used alone or in combination of two or more.
　本発明の感光性樹脂組成物における（Ｈ）他の塩基性化合物の含有量は、他の塩基性化合物を含む場合、感光性樹脂組成物中の全固形分１００質量部に対して、０．００１～３質量部であることが好ましく、０．００５～１質量部であることがより好ましい。 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.
（Ｉ）界面活性剤
　本発明の感光性樹脂組成物は、（Ｉ）界面活性剤を含有してもよい。（Ｉ）界面活性剤としては、アニオン系、カチオン系、ノニオン系、または、両性のいずれでも使用することができるが、好ましい界面活性剤はノニオン界面活性剤である。
　ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、シリコーン系、フッ素系界面活性剤を挙げることができる。また、以下商品名で、ＫＰ（信越化学工業（株）製）、ポリフロー（共栄社化学（株）製）、エフトップ（ＪＥＭＣＯ社製）、メガファック（ＤＩＣ（株）製）、フロラード（住友スリーエム（株）製）、アサヒガード、サーフロン（旭硝子（株）製）、ＰｏｌｙＦｏｘ（ＯＭＮＯＶＡ社製）、ＳＨ－８４００（東レ・ダウコーニングシリコーン）等の各シリーズを挙げることができる。
　また、界面活性剤として、下記一般式（Ｉ－１）で表される構成単位Ａおよび構成単位Ｂを含み、テトラヒドロフラン（ＴＨＦ）を溶剤とした場合のゲルパーミエーションクロマトグラフィーで測定されるポリスチレン換算の重量平均分子量（Ｍｗ）が１，０００以上１０，０００以下である共重合体を好ましい例として挙げることができる。 (I) Surfactant The photosensitive resin composition of the present invention may contain (I) a surfactant. As the surfactant (I), any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. . In addition, 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 (Sumitomo 3M) under the following trade names. (Manufactured by Asahi Kasei Corp.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
Moreover, it is a polystyrene conversion measured by gel permeation chromatography at the time of using tetrahydrofuran (THF) as a solvent, containing the structural unit A and the structural unit B represented by following General formula (I-1) as surfactant. 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.
　一般式（Ｉ－１）
Figure JPOXMLDOC01-appb-C000023
  （式（Ｉ－１）中、Ｒ401およびＲ403はそれぞれ、水素原子またはメチル基を表し、Ｒ402は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ404は水素原子または炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐおよびｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。） General formula (I-1)
Figure JPOXMLDOC01-appb-C000023
 (In formula (I-1), 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, and 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, and 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).
　上記Ｌは、下記一般式（Ｉ－２）で表される分岐アルキレン基であることが好ましい。一般式（Ｉ－２）におけるＲ405は、炭素数１以上４以下のアルキル基を表し、相溶性と被塗布面に対する濡れ性の点で、炭素数１以上３以下のアルキル基が好ましく、炭素数２または３のアルキル基がより好ましい。ｐとｑとの和（ｐ＋ｑ）は、ｐ＋ｑ＝１００、すなわち、１００質量％であることが好ましい。 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 sum of p and q (p + q) is preferably p + q = 100, that is, 100% by mass.
　一般式（Ｉ－２）
Figure JPOXMLDOC01-appb-C000024
 General formula (I-2)
Figure JPOXMLDOC01-appb-C000024
　上記共重合体の重量平均分子量（Ｍｗ）は、１，５００以上５，０００以下がより好ましい。 The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.
　これらの界面活性剤は、１種単独でまたは２種以上を混合して使用することができる。
　本発明の感光性樹脂組成物における（Ｉ）界面活性剤の添加量は、感光性樹脂組成物中の全固形分１００質量部に対して、１０質量部以下であることが好ましく、０．００１～１０質量部であることがより好ましく、０．０１～３質量部であることがさらに好ましい。 These surfactants can be used singly or in combination of two or more.
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.
（Ｊ）酸化防止剤
　本発明の感光性樹脂組成物は、酸化防止剤を含有してもよい。酸化防止剤としては、公知の酸化防止剤を含有することができる。酸化防止剤を添加することにより、硬化膜の着色を防止できる、または、分解による膜厚減少を低減でき、また、耐熱透明性に優れるという利点がある。
　このような酸化防止剤としては、例えば、リン系酸化防止剤、アミド類、ヒドラジド類、ヒンダードアミン系酸化防止剤、イオウ系酸化防止剤、フェノール系酸化防止剤、アスコルビン酸類、硫酸亜鉛、糖類、亜硝酸塩、亜硫酸塩、チオ硫酸塩、ヒドロキシルアミン誘導体などを挙げることができる。これらの中では、硬化膜の着色、膜厚減少の観点から特にフェノール系酸化防止剤、アミド系酸化防止剤、ヒドラジド系酸化防止剤、イオウ系酸化防止剤が好ましい。これらは１種単独で用いてもよいし、２種以上を混合してもよい。
　フェノール系酸化防止剤の市販品としては、例えば、アデカスタブＡＯ－１５、アデカスタブＡＯ－１８、アデカスタブＡＯ－２０、アデカスタブＡＯ－２３、アデカスタブＡＯ－３０、アデカスタブＡＯ－３７、アデカスタブＡＯ－４０、アデカスタブＡＯ－５０、アデカスタブＡＯ－５１、アデカスタブＡＯ－６０、アデカスタブＡＯ－７０、アデカスタブＡＯ－８０、アデカスタブＡＯ－３３０、アデカスタブＡＯ－４１２Ｓ、アデカスタブＡＯ－５０３、アデカスタブＡ－６１１、アデカスタブＡ－６１２、アデカスタブＡ－６１３、アデカスタブＰＥＰ－４Ｃ、アデカスタブＰＥＰ－８、アデカスタブＰＥＰ－８Ｗ、アデカスタブＰＥＰ－２４Ｇ、アデカスタブＰＥＰ－３６、アデカスタブＰＥＰ－３６Ｚ、アデカスタブＨＰ－１０、アデカスタブ２１１２、アデカスタブ２６０、アデカスタブ５２２Ａ、アデカスタブ１１７８、アデカスタブ１５００、アデカスタブＣ、アデカスタブ１３５Ａ、アデカスタブ３０１０、アデカスタブＴＰＰ、アデカスタブＣＤＡ－１、アデカスタブＣＤＡ－６、アデカスタブＺＳ－２７、アデカスタブＺＳ－９０、アデカスタブＺＳ－９１（以上、（株）ＡＤＥＫＡ製）、イルガノックス２４５ＦＦ、イルガノックス１０１０ＦＦ、イルガノックス１０１０、イルガノックスＭＤ１０２４、イルガノックス１０３５ＦＦ、イルガノックス１０３５、イルガノックス１０９８、イルガノックス１３３０、イルガノックス１５２０Ｌ、イルガノックス３１１４、イルガノックス１７２６、イルガフォス１６８、イルガモッド２９５（ＢＡＳＦ（株）製）などが挙げられる。中でも、アデカスタブＡＯ－６０、アデカスタブＡＯ－８０、イルガノックス１７２６、イルガノックス１０３５、イルガノックス１０９８を好適に使用することができる。 (J) Antioxidant The photosensitive resin composition of the present invention may contain an antioxidant. As 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. Among these, 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.
As a commercial item of a phenol type antioxidant, for example, 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 stub 522A, Adeka stub 1178, Adeka stub 1500, Adeka stub C, Adeka stub 135A, Adeka stub 3010, Adeka stub TPP, Adeka stub CDA-1, Adeka stub CDA-6, Adeka stub ZS-27, Adeka stub ZS-90, Adeka stub ZS -91 (all available from ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD 1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520 L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Co., Ltd.), and the like. Among them, Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035 and Irganox 1098 can be suitably used.
　酸化防止剤の含有量は、感光性樹脂組成物の全固形分に対して、０．１～１０質量％であることが好ましく、０．２～５質量％であることがより好ましく、０．５～４質量％であることが特に好ましい。この範囲にすることで、形成された膜の十分な透明性が得られ、且つ、パターン形成時の感度も良好となる。
　また、酸化防止剤以外の添加剤として、“高分子添加剤の新展開（（株）日刊工業新聞社）”に記載の各種紫外線吸収剤や、金属不活性化剤等を本発明の感光性樹脂組成物に添加してもよい。 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.
In addition, as 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.
〔酸増殖剤〕
　本発明の感光性樹脂組成物は、感度向上を目的に、酸増殖剤を用いることができる。
　本発明に用いることができる酸増殖剤は、酸触媒反応によってさらに酸を発生して反応系内の酸濃度を上昇させることができる化合物であり、酸が存在しない状態では安定に存在する化合物である。このような化合物は、１回の反応で１つ以上の酸が増えるため、反応の進行に伴って加速的に反応が進むが、発生した酸自体が自己分解を誘起するため、ここで発生する酸の強度は、酸解離定数、ｐＫａとして３以下であるのが好ましく、特に２以下であるのが好ましい。
　酸増殖剤の具体例としては、特開平１０－１５０８号公報の段落番号０２０３～０２２３、特開平１０－２８２６４２号公報の段落番号００１６～００５５、および、特表平９－５１２４９８号公報第３９頁１２行目～第４７頁２行目に記載の化合物を挙げることができ、これらの内容は本願明細書に組み込まれる。
　本発明で用いることができる酸増殖剤としては、酸発生剤から発生した酸によって分解し、ジクロロ酢酸、トリクロロ酢酸、メタンスルホン酸、ベンゼンスルホン酸、トリフルオロメタンスルホン酸、フェニルホスホン酸などのｐＫａが３以下の酸を発生させる化合物を挙げることができる。
　具体的には
Figure JPOXMLDOC01-appb-C000025
  等を挙げることができる。
　酸増殖剤の感光性組成物への含有量は、光酸発生剤１００質量部に対して、１０～１，０００質量部とするのが、露光部と未露光部との溶解コントラストの観点から好ましく、２０～５００質量部とするのがさらに好ましい。 [Acid multiplication agent]
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. 0203 to 0223 of JP-A No. 10-1508, paragraph Nos. 0016 to 0055 of JP-A No. 10-282642, and page 39 of JP-A No. 9-512498. The compounds described in line 12 to page 47 line 2 can be mentioned, the contents of which are incorporated herein.
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
Figure JPOXMLDOC01-appb-C000025
 Etc. can be mentioned.
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.
〔現像促進剤〕
　本発明の感光性樹脂組成物は、現像促進剤を含有することができる。
　現像促進剤としては、特開２０１２－０４２８３７号公報の段落番号０１７１～０１７２の記載を参酌でき、かかる内容は本願明細書に組み込まれる。 [Development accelerator]
The photosensitive resin composition of the present invention can contain a development accelerator.
As the 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.
　現像促進剤は、１種を単独で用いてもよいし、２種以上を併用することも可能である。
　本発明の感光性樹脂組成物における現像促進剤の添加量は、感度と残膜率の観点から、感光性組成物の全固形分１００質量部に対し、０～３０質量部が好ましく、０．１～２０質量部がより好ましく、０．５～１０質量部であることが最も好ましい。
　また、その他の添加剤としては特開２０１２－８２２３号公報の段落番号０１２０～０１２１に記載の熱ラジカル発生剤、ＷＯ２０１１／１３６０７４Ａ１に記載の窒素含有化合物および熱酸発生剤も用いることができ、これらの内容は本願明細書に組み込まれる。 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.
Further, as other additives, 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.
＜感光性樹脂組成物の調製方法＞
　各成分を所定の割合でかつ任意の方法で混合し、撹拌溶解して感光性樹脂組成物を調製する。例えば、成分を、それぞれ予め溶剤に溶解させた溶液とした後、これらを所定の割合で混合して樹脂組成物を調製することもできる。以上のように調製した組成物溶液は、孔径０．２μｍのフィルター等を用いてろ過した後に、使用に供することもできる。 <Method of Preparing Photosensitive Resin Composition>
The components are mixed in a predetermined ratio and in an arbitrary method, and dissolved by stirring to prepare a photosensitive resin composition. For example, 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 μm or the like.
［硬化膜の製造方法］
　次に、本発明の硬化膜の製造方法を説明する。
　本発明の硬化膜の製造方法は、以下の（１）～（５）の工程を含むことが好ましい。
　（１）本発明の感光性樹脂組成物を基板上に塗布する工程；
　（２）塗布された感光性樹脂組成物から溶剤を除去する工程；
　（３）溶剤が除去された感光性樹脂組成物を活性光線により露光する工程；
　（４）露光された感光性樹脂組成物を水性現像液により現像する工程；
　（５）現像された感光性樹脂組成物を熱硬化するポストベーク工程。
　以下に各工程を順に説明する。 [Method of producing a cured film]
Next, the manufacturing method of the cured film of this invention is demonstrated.
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.
　（１）の塗布工程では、本発明の感光性樹脂組成物を基板上に塗布して溶剤を含む湿潤膜とすることが好ましい。感光性樹樹脂組成物を基板へ塗布する前にアルカリ洗浄やプラズマ洗浄といった基板の洗浄を行うことが好ましく、さらに基板洗浄後にヘキサメチルジシラザンで基板表面を処理することがより好ましい。この処理を行うことにより、感光性樹脂組成物の基板への密着性が向上する傾向にある。ヘキサメチルジシラザンで基板表面を処理する方法としては、特に限定されないが、例えば、ヘキサメチルジシラザン蒸気に中に基板を晒しておく方法等が挙げられる。
　上記の基板としては、無機基板、樹脂、樹脂複合材料などが挙げられる。
　無機基板としては、例えばガラス、石英、シリコーン、シリコンナイトライド、および、それらのような基板上にモリブデン、チタン、アルミ、銅などを蒸着した複合基板が挙げられる。
　樹脂としては、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリスチレン、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリアリレート、アリルジグリコールカーボネート、ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリベンズアゾール、ポリフェニレンサルファイド、ポリシクロオレフィン、ノルボルネン樹脂、ポリクロロトリフルオロエチレン等のフッ素樹脂、液晶ポリマー、アクリル樹脂、エポキシ樹脂、シリコーン樹脂、アイオノマー樹脂、シアネート樹脂、架橋フマル酸ジエステル、環状ポリオレフィン、芳香族エーテル、マレイミドーオレフィン、セルロース、エピスルフィド化合物等の合成樹脂からなる基板が挙げられる
　これらの基板は、上記の形態のまま用いられる場合は少なく、通常、最終製品の形態によって、例えばＴＦＴ素子のような多層積層構造が形成されている。
　基板への塗布方法は特に限定されず、例えば、スリットコート法、スプレー法、ロールコート法、回転塗布法、流延塗布法、スリットアンドスピン法等の方法を用いることができる。さらに、特開２００９－１４５３９５号公報に記載されているような、所謂プリウェット法を適用することも可能である。
　塗布したときのウエット膜厚は特に限定されるものではなく、用途に応じた膜厚で塗布することができるが、通常は０．５～１０μｍの範囲で使用される。 In the application step of (1), 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.
Examples of 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.
As the resin, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, 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 These 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-layered structure such as a TFT element is formed.
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 μm.
　（２）の溶剤除去工程では、塗布された上記の膜から、減圧（バキューム）および／または加熱により、溶剤を除去して基板上に乾燥塗膜を形成させる。溶剤除去工程の加熱条件は、好ましくは７０～１３０℃で３０～３００秒間程度である。温度と時間が上記範囲である場合、パターンの密着性がより良好で、且つ残渣もより低減できる傾向にある。 In the solvent removal step of (2), 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.
　（３）の露光工程では、塗膜を設けた基板に所定のパターンを有するマスクを介して、活性光線を照射する。この工程では、光酸発生剤が分解し酸が発生する。発生した酸の触媒作用により、塗膜成分中に含まれる酸分解性基が加水分解されて、カルボキシル基またはフェノール性水酸基が生成する。
　活性光線による露光光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ＬＥＤ光源、エキシマレーザー発生装置などを用いることができ、ｇ線（４３６ｎｍ）、ｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）などの波長３００ｎｍ以上４５０ｎｍ以下の波長を有する活性光線が好ましく使用できる。また、必要に応じて長波長カットフィルター、短波長カットフィルター、バンドパスフィルターのような分光フィルターを通して照射光を調整することもできる。
　露光装置としては、ミラープロジェクションアライナー、ステッパー、スキャナー、プロキシミティ、コンタクト、マイクロレンズアレイ、レーザー露光、など各種方式の露光機を用いることができる。
　酸触媒の生成した領域において、上記の加水分解反応を加速させるために、露光後加熱処理：Ｐｏｓｔ　Ｅｘｐｏｓｕｒｅ　Ｂａｋｅ（以下、「ＰＥＢ」ともいう。）を行うことができる。ＰＥＢにより、酸分解性基からのカルボキシル基またはフェノール性水酸基の生成を促進させることができる。ＰＥＢを行う場合の温度は、３０℃以上１３０℃以下であることが好ましく、４０℃以上１１０℃以下がより好ましく、５０℃以上１００℃以下が特に好ましい。
　ただし、本発明における酸分解性基は、酸分解の活性化エネルギーが低く、露光による酸発生剤由来の酸により容易に分解し、カルボキシル基またはフェノール性水酸基を生じるため、必ずしもＰＥＢを行うことなく、現像によりポジ画像を形成することもできる。 In the exposure step (3), the substrate provided with the coating film is irradiated with an actinic ray through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated 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. In addition, it is also possible to adjust the irradiation light through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a laser exposure, and the like can be used.
In the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter, also referred to as “PEB”) can be performed in order to accelerate the above-mentioned hydrolysis reaction. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-degradable group. The temperature for PEB is preferably 30 ° C. or more and 130 ° C. or less, more preferably 40 ° C. or more and 110 ° C. or less, and particularly preferably 50 ° C. or more and 100 ° C. or less.
However, 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.
　（４）の現像工程では、遊離したカルボキシル基またはフェノール性水酸基を有する重合体を、アルカリ性現像液を用いて現像する。アルカリ性現像液に溶解しやすいカルボキシル基またはフェノール性水酸基を有する樹脂組成物を含む露光部領域を除去することにより、ポジ画像が形成する。
　現像工程で使用する現像液には、塩基性化合物が含まれることが好ましい。塩基性化合物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物類；炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭酸塩類；重炭酸ナトリウム、重炭酸カリウムなどのアルカリ金属重炭酸塩類；テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリンヒドロキシド等のアンモニウムヒドロキシド類；ケイ酸ナトリウム、メタケイ酸ナトリウムなどの水溶液を使用することができる。また、上記アルカリ類の水溶液にメタノールやエタノールなどの水溶性有機溶剤や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。
　好ましい現像液として、テトラエチルアンモニウムヒドロキシドの０．４％水溶液、０．５％水溶液、０．７％水溶液、２．３８％水溶液を挙げる事ができる。
　現像液のｐＨは、好ましくは１０．０～１４．０である。
　現像時間は、好ましくは３０～５００秒間であり、また、現像の手法は液盛り法、ディップ法等の何れでもよい。現像後は、流水洗浄を、通常、３０～３００秒間行い、所望のパターンを形成させることができる。
　現像の後に、リンス工程を行うこともできる。リンス工程では、現像後の基板を純水などで洗うことで、付着している現像液除去、現像残渣除去を行う。リンス方法は公知の方法を用いることができる。例えばシャワーリンスやディップリンスなどを挙げる事ができる。 In the development step (4), 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.
As a preferable developing solution, 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.
　（５）のポストベーク工程では、得られたポジ画像を加熱することにより、酸分解性基を熱分解しカルボキシル基またはフェノール性水酸基を生成させ、架橋性基、架橋剤等と架橋させることにより、硬化膜を形成することができる。この加熱は、ホットプレートやオーブン等の加熱装置を用いて、所定の温度、例えば１８０～２５０℃で所定の時間、例えばホットプレート上なら５～９０分間、オーブンならば３０～１２０分間、加熱処理をすることが好ましい。このような架橋反応を進行させることにより、耐熱性、硬度等により優れた保護膜や層間絶縁膜を形成することができる。また、加熱処理を行う際は窒素雰囲気下で行うことにより、透明性をより向上させることもできる。
　ポストベークの前に、比較的低温でベークを行った後にポストベークすることもできる（ミドルベーク工程の追加）。ミドルベークを行う場合は、９０～１５０℃で１～６０分加熱した後に、２００℃以上の高温でポストベークすることが好ましい。また、ミドルベーク、ポストベークを３段階以上の多段階に分けて加熱する事もできる。このようなミドルベーク、ポストベークの工夫により、パターンのテーパー角を調整することができる。これらの加熱は、ホットプレート、オーブン、赤外線ヒーターなど、公知の加熱方法を使用することができる。
　なお、ポストベークに先立ち、パターンを形成した基板に活性光線により全面再露光（ポスト露光）した後、ポストベークすることにより未露光部分に存在する光酸発生剤から酸を発生させ、架橋工程を促進する触媒として機能させることができ、膜の硬化反応を促進することができる。ポスト露光工程を含む場合の好ましい露光量としては、１００～３，０００ｍＪ／ｃｍ2が好ましく、１００～５００ｍＪ／ｃｍ2が特に好ましい。
　一方で、硬化膜としての特性（透過率、耐薬品性、比誘電率、下地基板との密着性、ドライエッチング耐性など）が、全面再露光を行った場合よりも優れる場合には、全面再露光工程を省略することも可能である。全面再露光工程を省略することで、生産性を向上させることも可能である。 In the post-baking step (5), 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. It is preferable to By promoting such a crosslinking reaction, a protective film or an interlayer insulating film can be formed which is more excellent in heat resistance, hardness, and the like. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Before post-baking, post-baking can also be performed after baking at a relatively low temperature (addition of a middle-baking step). When middle baking is performed, 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. Further, 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.
It should be noted that prior to post-baking, 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.
On the other hand, when the properties as a cured film (transmittance, chemical resistance, relative dielectric constant, adhesion to the base substrate, dry etching resistance, etc.) are superior to the case where the entire surface is re-exposed, It is also possible to omit the exposure step. It is also possible to improve the productivity by omitting the entire surface re-exposure step.
　さらに、本発明の感光性樹脂組成物より得られた硬化膜は、ドライエッチングレジストとして使用することもできる。ポストベーク工程により熱硬化して得られた硬化膜をドライエッチングレジストとして使用する場合、エッチング処理としてはアッシング、プラズマエッチング、オゾンエッチングなどのドライエッチング処理を行うことができる。 Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. When a cured film obtained by heat curing in the post-baking step is used as a dry etching resist, dry etching such as ashing, plasma etching, or ozone etching can be performed as the etching treatment.
［硬化膜］
　本発明の硬化膜は、本発明の感光性樹脂組成物を硬化して得られた硬化膜である。
　本発明の硬化膜は、層間絶縁膜として好適に用いることができる。また、本発明の硬化膜は、本発明の硬化膜の形成方法により得られた硬化膜であることが好ましい。
　本発明の感光性樹脂組成物により、絶縁性に優れ、高温でベークされた場合においても高い透明性を有する層間絶縁膜が得られる。本発明の感光性樹脂組成物を用いてなる層間絶縁膜は、高い透明性を有し、硬化膜物性に優れるため、有機ＥＬ表示装置や液晶表示装置の用途に有用である。 [Cured film]
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. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
By the photosensitive resin composition of the present 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.
［液晶表示装置］
　本発明の液晶表示装置は、本発明の硬化膜を具備することを特徴とする。
　本発明の液晶表示装置としては、上記本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の液晶表示装置を挙げることができる。
　例えば、本発明の液晶表示装置が具備するＴＦＴ（Ｔｈｉｎ－Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）の具体例としては、アモルファスシリコン－ＴＦＴ、低温ポリシリコンーＴＦＴ、酸化物半導体ＴＦＴ等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのＴＦＴに組み合わせて好ましく用いることができる。
　また、本発明の液晶表示装置が取りうる液晶駆動方式としてはＴＮ（ＴｗｉｓｔｅｄＮｅｍａｔｉｃ）方式、ＶＡ（Ｖｉｒｔｉｃａｌ　Ａｌｉｇｎｍｅｎｔ）方式、ＩＰＳ（Ｉｎ－Ｐｌａｃｅ－Ｓｗｉｔｃｈｉｎｇ）方式、ＦＦＳ（Ｆｒｉｎｇｓ　Ｆｉｅｌｄ　Ｓｗｉｔｃｈｉｎｇ）方式、ＯＣＢ（Ｏｐｔｉｃａｌ　Ｃｏｍｐｅｎｓａｔｅｄ　Ｂｅｎｄ）方式などが挙げられる。
　パネル構成においては、ＣＯＡ（Ｃｏｌｏｒ　Ｆｉｌｔｅｒ　ｏｎ　Ａｌｌａｙ）方式の液晶表示装置でも本発明の硬化膜を用いることができ、例えば、特開２００５－２８４２９１号公報の有機絶縁膜（１１５）や、特開２００５－３４６０５４号公報の有機絶縁膜（２１２）として用いることができる。
　また、本発明の液晶表示装置が取りうる液晶配向膜の具体的な配向方式としてはラビング配向法、光配向方などが挙げられる。また、特開２００３－１４９６４７号公報や特開２０１１－２５７７３４号公報に記載のＰＳＡ（Ｐｏｌｙｍｅｒ　Ｓｕｓｔａｉｎｅｄ　Ａｌｉｇｎｍｅｎｔ）技術によってポリマー配向支持されていてもよい。
　また、本発明の感光性樹脂組成物および本発明の硬化膜は、上記用途に限定されず種々の用途に使用することができる。例えば、平坦化膜や層間絶縁膜以外にも、カラーフィルターの保護膜や、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや固体撮像素子においてカラーフィルター上に設けられるマイクロレンズ等に好適に用いることができる。
　図１は、アクティブマトリックス方式の液晶表示装置１０の一例を示す概念的断面図である。このカラー液晶表示装置１０は、背面にバックライトユニット１２を有する液晶パネルであって、液晶パネルは、偏光フィルムが貼り付けられた２枚のガラス基板１４，１５の間に配置されたすべての画素に対応するＴＦＴ１６の素子が配置されている。ガラス基板上に形成された各素子には、硬化膜１７中に形成されたコンタクトホール１８を通して、画素電極を形成するＩＴＯ透明電極１９が配線されている。ＩＴＯ透明電極１９の上には、液晶２０の層とブラックマトリックスを配置したＲＧＢカラーフィルター２２が設けられている。
　バックライトの光源としては、特に限定されず公知の光源を用いることができる。例えば白色ＬＥＤ、青色・赤色・緑色などの多色ＬＥＤ、蛍光灯（冷陰極管）、有機ＥＬなどを挙げる事ができる。
　また、液晶表示装置は、３Ｄ（立体視）型のものとしたり、タッチパネル型のものとしたりすることも可能である。さらにフレキシブル型にすることも可能であり、特開２０１１－１４５６８６号公報の第２相間絶縁膜（４８）や、特開２００９－２５８７５８号公報の相間絶縁膜（５２０）として用いることができる。 [Liquid crystal display device]
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.
For example, 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.
In addition, as a liquid crystal drive system that can be used for the liquid crystal display device of the present invention, a TN (Twisted Nematic) system, a VA (Virtical Alignment) system, an IPS (In-Place-Switching) system, an FFS (Frings Field Switching) system, an OCB (Optical) And the like.
In the panel configuration, 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.
Moreover, as a specific orientation system of the liquid crystal aligning film which the liquid crystal display device of this invention can take, the rubbing orientation method, the optical orientation method, etc. are mentioned. In addition, the polymer orientation may be supported by the PSA (Polymer Sustained Alignment) technology described in JP-A-2003-149647 and JP-A-2011-257734.
Moreover, 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. For example, besides a planarizing film and an interlayer insulating film, a protective film for a color filter, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a micro lens provided on a color filter in a solid imaging device Can be suitably used.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. As shown in FIG. 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. Elements of the TFT 16 corresponding to In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, 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.
In addition, the liquid crystal display device may be a 3D (stereoscopic) type or a touch panel type. Furthermore, it is possible to use a flexible type, and it can be used as the second interphase insulating film (48) of JP2011-145686A or the interphase insulating film (520) of JP2009-258758A.
［有機ＥＬ表示装置］
　本発明の有機ＥＬ表示装置は、本発明の硬化膜を具備することを特徴とする。
　本発明の有機ＥＬ表示装置としては、上記本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の各種有機ＥＬ表示装置や液晶表示装置を挙げることができる。
　例えば、本発明の有機ＥＬ表示装置が具備するＴＦＴ（Ｔｈｉｎ－Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）の具体例としては、アモルファスシリコン－ＴＦＴ、低温ポリシリコンーＴＦＴ、酸化物半導体ＴＦＴ等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのＴＦＴに組み合わせて好ましく用いることができる。
　図２は、有機ＥＬ表示装置の一例の構成概念図である。ボトムエミッション型の有機ＥＬ表示装置における基板の模式的断面図を示し、平坦化膜４を有している。
　ガラス基板６上にボトムゲート型のＴＦＴ１を形成し、このＴＦＴ１を覆う状態でＳｉ3Ｎ4から成る絶縁膜３が形成されている。絶縁膜３に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してＴＦＴ１に接続される配線２（高さ１．０μｍ）が絶縁膜３上に形成されている。配線２は、ＴＦＴ１間または、後の工程で形成される有機ＥＬ素子とＴＦＴ１とを接続するためのものである。
　さらに、配線２の形成による凹凸を平坦化するために、配線２による凹凸を埋め込む状態で絶縁膜３上に平坦化層４が形成されている。
　平坦化膜４上には、ボトムエミッション型の有機ＥＬ素子が形成されている。すなわち、平坦化膜４上に、ＩＴＯからなる第一電極５が、コンタクトホール７を介して配線２に接続させて形成されている。また、第一電極５は、有機ＥＬ素子の陽極に相当する。
　第一電極５の周縁を覆う形状の絶縁膜８が形成されており、この絶縁膜８を設けることによって、第一電極５とこの後の工程で形成する第二電極との間のショートを防止することができる。
　さらに、図２には図示していないが、所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設け、次いで、基板上方の全面にＡｌから成る第二電極を形成し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止し、各有機ＥＬ素子にこれを駆動するためのＴＦＴ１が接続されてなるアクティブマトリックス型の有機ＥＬ表示装置が得られる。 [Organic EL Display Device]
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.
For example, 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. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
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. After forming a contact hole (not shown) in the insulating film 3, a wire 2 (height 1.0 μm) 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.
　本発明の感光性樹脂組成物は、硬化性および硬化膜特性に優れるため、ＭＥＭＳデバイスの構造部材として、本発明の感光性樹脂組成物を用いて形成されたレジストパターンを隔壁としたり、機械駆動部品の一部として組み込んで使用される。このようなＭＥＭＳ用デバイスとしては、例えばＳＡＷフィルター、ＢＡＷフィルター、ジャイロセンサー、ディスプレイ用マイクロシャッター、イメージセンサー、電子ペーパー、インクジェットヘッド、バイオチップ、封止剤等の部品が挙げられる。より具体的な例は、特表２００７－５２２５３１号公報、特開２００８－２５０２００号公報、特開２００９－２６３５４４号公報等に例示されている。 Since the photosensitive resin composition of the present invention is excellent in curability and cured film characteristics, 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. Examples of such 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.
　本発明の感光性樹脂組成物は、平坦性や透明性に優れるため、例えば特開２０１１－１０７４７６号公報の図２に記載のバンク層（１６）および平坦化膜（５７）、特開２０１０－９７９３号公報の図４（ａ）に記載の隔壁（１２）および平坦化膜（１０２）、特開２０１０－２７５９１号公報の図１０に記載のバンク層（２２１）および第３層間絶縁膜（２１６ｂ）、特開２００９－１２８５７７号公報の図４（ａ）に記載の第２層間絶縁膜（１２５）および第３層間絶縁膜（１２６）、特開２０１０－１８２６３８号公報の図３に記載の平坦化膜（１２）および画素分離絶縁膜（１４）などの形成に用いることもできる。 Since 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- The barrier rib (12) and the flattening film (102) described in FIG. 4 (a) of 9793, and the bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of JP 2010-27591A. , The second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4 (a) of JP 2009-128857 A, and the flat described in FIG. 3 of JP 2010-182638 A. It can also be used to form a chemical conversion film (12) and a pixel isolation insulating film (14).
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。なお、特に断りのない限り、「部」、「％」は質量基準である。 Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references.
　以下の合成例において、以下の符号はそれぞれ以下の化合物を表す。
　ＭＡＴＨＦ：メタクリル酸テトラヒドロフラン－２－イル（合成品）
　ＭＡＥＶＥ：メタクリル酸１－エトキシエチル（和光純薬工業社製）
　ＭＡＣＨＯＥ：１－（シクロヘキシルオキシ）エチルメタクリレート（合成品）
　ＭＡＴＨＰ：メタクリル酸テトラヒドロ－２Ｈ－ピラン－２－イル（新中村化学工業（株）製）
　ＧＭＡ：グリシジルメタクリレート（和光純薬工業（株）製）
　ＯＸＥ－３０：メタクリル酸（３－エチルオキセタン－３－イル）メチル（大阪有機化学工業（株）製）
　ＮＢＭＡ：ｎ－ブトキシメチルアクリルアミド（三菱レイヨン（株）製）
　ＭＡＡ：メタクリル酸（和光純薬工業（株）製）
　ＨＥＭＡ：メタクリル酸２－ヒドロキシエチル（和光純薬工業（株）製）
　ＭＭＡ：メタクリル酸メチル（和光純薬工業（株）製）
　Ｓｔ：スチレン（和光純薬工業（株）製）
　ＤＣＰＭ：ジシクロペンタニルメタクリレート（日立化成工業（株）製）
　Ｖ－６０１：ジメチル－２，２’－アゾビス（２－メチルプロピオネート）（和光純薬工業（株）製）
　Ｖ－６５：２，２’－アゾビス（２，４－ジメチルバレロニトリル）（和光純薬工業（株）製）
　ＭＥＤＧ：ジエチレングリコールエチルメチルエーテル（東邦化学工業（株）製、ハイソルブＥＤＭ）
　ＰＧＭＥＡ：メトキシプロピルアセテート（昭和電工社製） In the following synthesis examples, the following symbols represent the following compounds, respectively.
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. product)
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 ethyl methyl ether (manufactured by Toho Chemical Industry Co., Ltd., Hysorb EDM)
PGMEA: methoxypropyl acetate (made by Showa Denko)
＜ＭＡＴＨＦの合成＞
　メタクリル酸（８６ｇ、１ｍｏｌ）を１５℃に冷却しておき、カンファースルホン酸（４．６ｇ，０．０２ｍｏｌ）添加した。その溶液に、２－ジヒドロフラン（７１ｇ、１ｍｏｌ、１．０当量）を滴下した。１時間撹拌した後に、飽和炭酸水素ナトリウム（５００ｍＬ）を加え、酢酸エチル（５００ｍＬ）で抽出し、硫酸マグネシウムで乾燥後、不溶物を濾過後４０℃以下で減圧濃縮し、残渣の黄色油状物を減圧蒸留して沸点（ｂｐ．）５４～５６℃／３．５ｍｍＨｇ留分のメタクリル酸テトラヒドロ－２Ｈ－フラン－２－イル（ＭＡＴＨＦ）１２５ｇを無色油状物として得た（収率８０％）。 <Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C. and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution was added dropwise 2-dihydrofuran (71 g, 1 mol, 1.0 eq). After stirring for 1 hour, saturated sodium hydrogen carbonate (500 mL) is added, extraction is performed with ethyl acetate (500 mL), drying is performed with magnesium sulfate, insolubles are filtered and concentrated under reduced pressure at 40 ° C. or less. Distillation under reduced pressure gave 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54-56 ° C./3.5 mmHg fraction as a colorless oil (yield 80%).
　なお、ＭＡＣＨＯＥは、２－ジヒドロフランを対応する化合物に変更した以外、前記ＭＡＴＨＦと同様の方法で合成した。 MACHOE was synthesized in the same manner as the aforementioned MATHF except that 2-dihydrofuran was changed to the corresponding compound.
〔重合体Ａ１の合成〕
　３つ口フラスコにＭＥＤＧ（８９ｇ）を入れ、窒素雰囲気下において９０℃に昇温した。その溶液にＭＡＡ（全単量体成分中の９．５ｍｏｌ％となる量）、ＭＡＴＨＦ（全単量体成分中の４３ｍｏｌ％となる量）、ＧＭＡ（全単量体成分中の４７．５ｍｏｌ％に相当）、Ｖ－６５（全単量体成分の合計１００ｍｏｌ％に対して４ｍｏｌ％に相当）を溶解させ、２時間かけて滴下した。滴下終了後２時間攪拌し、反応を終了させた。それにより重合体Ａ１を得た。なお、ＭＥＤＧとその他の成分の合計量の比を６０：４０とした。即ち、固形分濃度４０％の重合体溶液を調製した。
　使用するモノマーの種類、重合開始剤等を下記表に示す通りに変更し、他の重合体を合成した。 [Synthesis of Polymer A1]
A three-necked flask was charged with MEDG (89 g), and the temperature was raised to 90 ° C. under a nitrogen atmosphere. In the solution, MAA (amount to become 9.5 mol% in all monomer components), MATHF (amount to become 43 mol% in all monomer components), GMA (47.5 mol% in all monomer components) And V-65 (corresponding to 4 mol% relative to a total of 100 mol% of all the monomer components) were dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the reaction was stirred for 2 hours to complete the reaction. Thus, a polymer A1 was obtained. The ratio of the total amount of MEDG and the other components was 60:40. That is, a polymer solution having a solid concentration of 40% was prepared.
The kind of monomer to be used, the polymerization initiator, etc. were changed as shown in the following table, and another polymer was synthesized.
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
　上記表中の特に単位を付していない数値は、ｍｏｌ％を単位とする。また、重合開始剤の数値は、単量体成分を１００ｍｏｌ％とした場合の、ｍｏｌ％である。
　固形分濃度は、以下の式により算出できる。
　固形分濃度：モノマー重量／（モノマー重量＋溶剤重量）×１００（単位：質量％）
　また、開始剤として、Ｖ－６０１を用いた場合は反応温度を９０℃とし、Ｖ－６５を用いた場合は反応温度を７０℃とした。 In the above table, numerical values not particularly attached are in units of mol%. The numerical value of the polymerization initiator is mol% when the monomer component is 100 mol%.
The solid content concentration can be calculated by the following equation.
Solid content concentration: monomer weight / (monomer weight + solvent weight) × 100 (unit: mass%)
When V-601 was used as the initiator, the reaction temperature was 90 ° C., and when V-65 was used, the reaction temperature was 70 ° C.
＜実施例および比較例＞
（１）感光性樹脂組成物の調製
　下記表２、３に示す各成分を溶剤（ＰＧＭＥＡ）に固形分濃度３２％になるまで溶解混合し均一な溶液とした後、０．１μｍのポアサイズを有するポリテトラフルオロエチレン製フィルタを用いて濾過して、実施例および比較例の感光性樹脂組成物の溶液をそれぞれ調製した。なお、表２、３における各成分量の添加量は質量部を表す。 <Example and Comparative Example>
(1) Preparation of Photosensitive Resin Composition Each component shown in Tables 2 and 3 below is dissolved and mixed in a solvent (PGMEA) to a solid content concentration of 32% to obtain a uniform solution, and has a pore size of 0.1 μm. The solution was filtered using a polytetrafluoroethylene filter to prepare solutions of photosensitive resin compositions of Examples and Comparative Examples. In addition, the addition amount of each component amount in Table 2, 3 represents a mass part.
　実施例および比較例に用いた各化合物を示す略号の詳細は、以下の通りである。
＜重合体＞
Ａ１～Ａ１０：上記合成例に従って合成した重合体
Ａ１１：Ｊｏｎｃｒｙｌ６７（ＢＡＳＦ社製） The detail of the symbol which shows each compound used for the Example and the comparative example is as follows.
<Polymer>
A1 to A10: Polymer A11 synthesized according to the above synthesis example: Joncryl 67 (manufactured by BASF)
＜光酸発生剤＞
Ｂ１：下記構造の化合物（合成品）
Ｂ２：下記構造の化合物（合成品）
Ｂ３：下記構造の化合物（合成品）
Ｂ４：ＣＧＩ－１３９７（ＢＡＳＦ社製）
Ｂ５：下記構造の化合物（特表２００２－５２８４５１号公報の段落０１０８に記載の方法に従って合成した）
Figure JPOXMLDOC01-appb-C000027
 <Photo acid generator>
B1: Compound of the following structure (synthetic product)
B2: Compound of the following structure (synthetic product)
B3: Compound of the following structure (synthetic product)
B4: CGI-1397 (manufactured by BASF)
B5: Compound of the following structure (synthesized according to the method described in paragraph 0108 of JP-A-2002-528451)
Figure JPOXMLDOC01-appb-C000027
＜Ｂ１の合成＞
　２－ナフトール（１０ｇ）、クロロベンゼン（３０ｍＬ）の懸濁溶液に塩化アルミニウム（１０．６ｇ）、２－クロロプロピオニルクロリド（１０．１ｇ）を添加し、混合液を４０℃に加熱して２時間反応させた。氷冷下、反応液に４Ｎ ＨＣｌ水溶液（６０ｍＬ）を滴下し、酢酸エチル（５０ｍＬ）を添加して分液した。有機層に炭酸カリウム（１９．２ｇ）を加え、４０℃で１時間反応させた後、２Ｎ ＨＣｌ水溶液（６０ｍＬ）を添加して分液し、有機層を濃縮後、結晶をジイソプロピルエーテル（１０ｍＬ）でリスラリーし、ろ過、乾燥してケトン化合物（６．５ｇ）を得た。
　得られたケトン化合物（３．０ｇ）、メタノール（１８ｍＬ）の懸濁溶液に酢酸（７．３ｇ）、５０重量％ヒドロキシルアミン水溶液（８．０ｇ）を添加し、１０時間加熱還流した。放冷後、水（５０ｍＬ）を加え、析出した結晶をろ過、冷メタノール洗浄後、乾燥してオキシム化合物（２．４ｇ）を得た。
　得られたオキシム化合物（１．８ｇ）をアセトン（２０ｍＬ）に溶解させ、氷冷下トリエチルアミン（１．５ｇ）、ｐ－トルエンスルホニルクロリド（２．４ｇ）を添加し、室温に昇温して１時間反応させた。反応液に水（５０ｍＬ）を添加し、析出した結晶をろ過後、メタノール（２０ｍＬ）でリスラリーし、ろ過、乾燥してＢ１（２．３ｇ）を得た。
　なお、Ｂ１の1Ｈ－ＮＭＲスペクトル（３００ＭＨｚ、ＣＤＣｌ3）は、δ＝８．３（ｄ，１Ｈ），８．０（ｄ，２Ｈ），７．９（ｄ，１Ｈ），７．８（ｄ，１Ｈ），７．６（ｄｄ，１Ｈ），７．４（ｄｄ，１Ｈ）７．３（ｄ，２Ｈ），７．１（ｄ．１Ｈ），５．６（ｑ，１Ｈ），２．４（ｓ，３Ｈ），１．７（ｄ，３Ｈ）であった。 <Composition of B1>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) are added to a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture is heated to 40 ° C. and reacted for 2 hours I did. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added to separate the layers. Potassium carbonate (19.2 g) is added to the organic layer and allowed to react at 40 ° C. for 1 hour, then 2 N HCl aqueous solution (60 mL) is added for phase separation, and the organic layer is concentrated, and then the crystals are diisopropyl ether (10 mL) The resultant was re-slurryed, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50 wt% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (18 mL), and the mixture was heated under reflux for 10 hours. 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).
Note that the 1 H-NMR spectrum (300 MHz, CDCl 3) of B 1 is δ = 8.3 (d, 1 H), 8.0 (d, 2 H), 7.9 (d, 1 H), 7.8 (d , 1 H), 7.6 (dd, 1 H), 7.4 (dd, 1 H), 7.3 (d, 2 H), 7.1 (d. 1 H), 5.6 (q, 1 H), 2. It was 4 (s, 3 H) and 1.7 (d, 3 H).
＜Ｂ２の合成＞
　２－ナフトール（２０ｇ）をＮ，Ｎ－ジメチルアセトアミド（１５０ｍＬ）に溶解させ、炭酸カリウム（２８．７ｇ）、２－ブロモオクタン酸エチル（５２．２ｇ）を添加して１００℃で２時間反応させた。反応液に水（３００ｍＬ）、酢酸エチル（２００ｍＬ）を添加して分液し、有機層を濃縮後、４８重量％水酸化ナトリウム水溶液（２３ｇ）、エタノール（５０ｍＬ）、水（５０ｍＬ）を添加し、２時間反応させた。反応液を１Ｎ ＨＣｌ水溶液（５００ｍＬ）にあけ、析出した結晶をろ過、水洗してカルボン酸粗体を得た後、ポリリン酸３０ｇを添加して１７０℃で３０分反応させた。反応液を水（３００ｍＬ）にあけ、酢酸エチル（３００ｍＬ）を添加して分液し、有機層を濃縮した後シリカゲルカラムクロマトグラフィーで精製し、ケトン化合物（１０ｇ）を得た。
　得られたケトン化合物（１０．０ｇ）、メタノール（１００ｍＬ）の懸濁溶液に酢酸ナトリウム（３０．６ｇ）、塩酸ヒドロキシルアミン（２５．９ｇ）、硫酸マグネシウム（４．５ｇ）を添加し、２４時間加熱還流した。放冷後、水（１５０ｍＬ）、酢酸エチル（１５０ｍL）添加して分液し、有機層を水８０ｍＬで４回分液し、濃縮した後シリカゲルカラムクロマトグラフィーで精製してオキシム化合物（５．８ｇ）を得た。
　得られたオキシム（３．１ｇ）に対し、Ｂ１と同様にスルホネート化を行い、Ｂ２（３．２ｇ）を得た。
　なお、Ｂ２の1Ｈ－ＮＭＲスペクトル（３００ＭＨｚ、ＣＤＣｌ3）は、δ＝８．３（ｄ，１Ｈ），８．０（ｄ，２Ｈ），７．９（ｄ，１Ｈ），７．８（ｄ，１Ｈ），７．６（ｄｄ，１Ｈ），７．５（ｄｄ，１Ｈ）７．３（ｄ，２Ｈ），７．１（ｄ．１Ｈ），５．６（ｄｄ，１Ｈ），２．４（ｓ，３Ｈ），２．２（ｄｄｔ，１Ｈ），１．９（ｄｄｔ，１Ｈ），１．４～１．２（ｍ，８Ｈ），０．８（ｔ，３Ｈ）であった。 <Composition of B2>
Dissolve 2-naphthol (20 g) in N, N-dimethylacetamide (150 mL), add potassium carbonate (28.7 g) and ethyl 2-bromooctanoate (52.2 g), and react at 100 ° C. for 2 hours The Water (300 mL) and ethyl acetate (200 mL) are added to the reaction liquid and the phases are separated, and the organic layer is concentrated, and a 48 wt% aqueous sodium hydroxide solution (23 g), ethanol (50 mL) and water (50 mL) are added. Let react for 2 hours. 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).
Note that the 1 H-NMR spectrum (300 MHz, CDCl 3 ) of B2 is δ = 8.3 (d, 1 H), 8.0 (d, 2 H), 7.9 (d, 1 H), 7.8 ( d, 1 H), 7.6 (dd, 1 H), 7.5 (dd, 1 H) 7.3 (d, 2 H), 7.1 (d. 1 H), 5.6 (dd, 1 H), 2 .4 (s, 3 H), 2.2 (ddt, 1 H), 1.9 (dd t, 1 H), 1.4 to 1.2 (m, 8 H), 0.8 (t, 3 H) .
＜Ｂ３の合成＞
　Ｂ１におけるｐ－トルエンスルホニルクロリドの代わりにベンゼンスルホニルクロリドを用いた以外は、Ｂ１と同様にしてＢ３を合成した。
　なお、Ｂ３の1Ｈ－ＮＭＲスペクトル（３００ＭＨｚ、ＣＤＣｌ3）は、δ＝８．３（ｄ，１Ｈ），８．１（ｄ，２Ｈ），７．９（ｄ，１Ｈ），７．８（ｄ，１Ｈ），７．７－７．５（ｍ，４Ｈ），７．４（ｄｄ，１Ｈ），７．１（ｄ．１Ｈ），５．６（ｑ，１Ｈ），１．７（ｄ，３Ｈ）であった。 <Composition of B3>
B3 was synthesized in the same manner as B1, except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in B1.
Note that the 1 H-NMR spectrum (300 MHz, CDCl 3 ) of B3 is δ = 8.3 (d, 1 H), 8.1 (d, 2 H), 7.9 (d, 1 H), 7.8 ( d, 1 H), 7.7-7.5 (m, 4 H), 7.4 (dd, 1 H), 7.1 (d. 1 H), 5.6 (q, 1 H), 1.7 (d , 3H).
＜芳香族複素環化合物＞
Ｃ１：オキサゾール（和光純薬工業（株）製）
Ｃ２：２，４，５－トリメチルオキサゾール（和光純薬工業（株）製）
Ｃ３：イソオキサゾール（和光純薬工業（株）製）
Ｃ４：５－メチルイソオキサゾール（和光純薬工業（株）製）
Ｃ５：チアゾール（和光純薬工業（株）製）
Ｃ６：５－メチルチアゾール（和光純薬工業（株）製）
Ｃ７：イソチアゾール（和光純薬工業（株）製）
Ｃ８：１，２，３－トリアゾール（和光純薬工業（株）製）
Ｃ９：１，２，４－トリアゾール（和光純薬工業（株）製）
Ｃ１０：１，２，３－オキサジアゾール（和光純薬工業（株）製）
Ｃ１１：１，２，４－オキサジアゾール（和光純薬工業（株）製）
Ｃ１２：１，３，４－オキサジアゾール（和光純薬工業（株）製）
Ｃ１３：１，２，５－オキサジアゾール（和光純薬工業（株）製）
Ｃ１４：１，２，３－チアジアゾール（和光純薬工業（株）製）
Ｃ１５：１，２，４－チアジアゾール（和光純薬工業（株）製）
Ｃ１６：１，３，４－チアジアゾール（和光純薬工業（株）製）
Ｃ１７：１，２，５－チアジアゾール（和光純薬工業（株）製）
Ｃ１８：ピリミジン（和光純薬工業（株）製）
Ｃ１９：１，２，３－トリアジン（和光純薬工業（株）製）
Ｃ２０：１，２，４－トリアジン（和光純薬工業（株）製）
Ｃ２１：１，３，５－トリアジン（和光純薬工業（株）製）
Ｃ２２：１，２－ベンゾピラゾール（和光純薬工業（株）製）
Ｃ２３：ベンゾオキサゾール（和光純薬工業（株）製）
Ｃ２４：５－メチルベンゾオキサゾール（和光純薬工業（株）製）
Ｃ２５：１，２－ベンゾイソオキサゾール（和光純薬工業（株）製）
Ｃ２６：ベンゾチアゾール（和光純薬工業（株）製）
Ｃ２７：２，６－ジメチルベンゾチアゾール（和光純薬工業（株）製）
Ｃ２８：２，１，３－ベンゾオキサジアゾール（和光純薬工業（株）製）
Ｃ２９：２，１，３－ベンゾチアジアゾール（和光純薬工業（株）製）
Ｃ３０：１，２，３－ベンゾトリアゾール（和光純薬工業（株）製）
Ｃ３１：キナゾリン（和光純薬工業（株）製）
Ｃ３２：フタラジン（和光純薬工業（株）製）
Ｃ３３：１，１０－フェナントロリン（和光純薬工業（株）製）
Ｃ３４：５－メチル－１，１０－フェナントロリン（和光純薬工業（株）製）
Ｃ３５：２，２’－ビピリジン（和光純薬工業（株）製）
Ｃ３６：４，４’－ビピリジン（和光純薬工業（株）製）
Ｃ３７：５，５’－ジメチル－２，２’－ビピリジン（和光純薬工業（株）製）
Ｃ３８：２－メルカプトベンゾチアゾール（和光純薬工業（株）製）
Ｃ３９：１－アミノベンゾトリアゾール（和光純薬工業（株）製）
Ｃ４０：６－アミノ－２－メルカプトベンゾチアゾール（和光純薬工業（株）製）
Ｃ４１：ピロール（和光純薬工業（株）製）
Ｃ４２：ピリジン（和光純薬工業（株）製）
Ｃ４３：インドール（和光純薬工業（株）製）
Ｃ４４：イソインドール（和光純薬工業（株）製）
　以下に、Ｃ１～Ｃ４４の構造を示す。 <Aromatic heterocyclic compound>
C1: Oxazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C2: 2,4,5-trimethyloxazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C3: Isoxazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C4: 5-methylisoxazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C5: Thiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C6: 5-methylthiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C7: Isothiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C8: 1,2,3-Triazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C 9: 1,2,4-triazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C10: 1,2,3-oxadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C11: 1,2,4-oxadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C12: 1,3,4-oxadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C13: 1,2,5-oxadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C14: 1,2,3-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C15: 1,2,4-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C16: 1,3,4-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C17: 1,2,5-thiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C18: Pyrimidine (manufactured by Wako Pure Chemical Industries, Ltd.)
C19: 1,2,3-Triazine (manufactured by Wako Pure Chemical Industries, Ltd.)
C20: 1,2,4-triazine (manufactured by Wako Pure Chemical Industries, Ltd.)
C21: 1,3,5-Triazine (manufactured by Wako Pure Chemical Industries, Ltd.)
C22: 1,2-benzopyrazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C23: benzoxazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C24: 5-methylbenzoxazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C25: 1,2-benzoisoxazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C26: benzothiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C27: 2, 6-dimethylbenzothiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C28: 2,1,3-benzoxadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C29: 2,1,3-benzothiadiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C30: 1,2,3-benzotriazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C31: quinazoline (manufactured by Wako Pure Chemical Industries, Ltd.)
C32: Phthalazine (manufactured by Wako Pure Chemical Industries, Ltd.)
C33: 1, 10-phenanthroline (manufactured by Wako Pure Chemical Industries, Ltd.)
C34: 5-methyl-1,10-phenanthroline (manufactured by Wako Pure Chemical Industries, Ltd.)
C35: 2, 2'-bipyridine (manufactured by Wako Pure Chemical Industries, Ltd.)
C36: 4, 4'-bipyridine (manufactured by Wako Pure Chemical Industries, Ltd.)
C37: 5,5'-dimethyl-2,2'-bipyridine (manufactured by Wako Pure Chemical Industries, Ltd.)
C38: 2-mercaptobenzothiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C39: 1-aminobenzotriazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C40: 6-amino-2-mercaptobenzothiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
C41: Pyrrole (manufactured by Wako Pure Chemical Industries, Ltd.)
C42: Pyridine (manufactured by Wako Pure Chemical Industries, Ltd.)
C43: Indole (manufactured by Wako Pure Chemical Industries, Ltd.)
C44: Isoindole (manufactured by Wako Pure Chemical Industries, Ltd.)
The structures of C1 to C44 are shown below.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
＜シラン化合物＞
Ｅ１：３－グリシドキシプロピルトリメトキシシラン（ＫＢＭ－４０３（信越化学工業（株）製））
Ｅ２：ビス（トリエトキシシリルプロピル）テトラスルフィド（ＫＢＥ－８４６（信越化学工業（株）製））
Ｅ３：デシルトリメトキシシラン（ＫＢＭ－３１０３（信越化学工業（株）製）） <Silane compound>
E1: 3-glycidoxypropyl trimethoxysilane (KBM-403 (Shin-Etsu Chemical Co., Ltd. product))
E2: Bis (triethoxysilylpropyl) tetrasulfide (KBE-846 (Shin-Etsu Chemical Co., Ltd. product))
E3: decyltrimethoxysilane (KBM-3103 (Shin-Etsu Chemical Co., Ltd. product))
＜増感剤＞
Ｇ１：ＤＢＡ（９，１０－ジブトキシアントラセン、川崎化成工業（株）製） <Sensitizer>
G1: DBA (9, 10-dibutoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
＜塩基性化合物＞
Ｈ１：１，５－ジアザビシクロ［４，３，０］－５－ノネン（東京化成工業（株）製）
Ｈ２：下記構造の化合物 <Basic compound>
H1: 1,5-Diazabicyclo [4,3,0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)
H2: compound of the following structure
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
＜界面活性剤＞
Ｉ１：下記構造の化合物 <Surfactant>
I1: Compound of the following structure
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
＜架橋剤＞
Ｆ１：ＪＥＲ１５７Ｓ６５（三菱化学（株）製）
Ｆ２：デュラネート１７Ｂ－６０Ｐ（旭化成ケミカルズ（株）製）
Ｆ３：デスモジュールＢＬ４２６５ＳＮ（住化バイエルウレタン（株）製） <Crosslinking agent>
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.)
＜酸化防止剤＞
Ｊ１：イルガノックス１０３５ＦＦ（酸化防止剤、ＢＡＳＦ社製）
Ｊ２：イルガノックス１０９８（酸化防止剤、ＢＡＳＦ社製）
Ｊ３：アデカスタブＡＯ－６０（酸化防止剤、（株）ＡＤＥＫＡ製） <Antioxidant>
J1: Irganox 1035FF (antioxidant, manufactured by BASF)
J2: Irganox 1098 (antioxidant, manufactured by BASF)
J3: Adekastab AO-60 (antioxidant, manufactured by ADEKA Co., Ltd.)
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
（２）感光性樹脂組成物の評価
（２－１）感度の評価
　ガラス基板（ＥＡＧＬＥ　ＸＧ、０．７ｍｍ厚（コーニング社製））を、ヘキサメチルジシラザン（ＨＭＤＳ）蒸気下に３０秒曝し、各感光性樹脂組成物をスピンコート塗布した後、９０℃／１２０秒ホットプレート上でプリベークして溶剤を揮発させ、膜厚３．０μｍの感光性樹脂組成物層を形成した。
　次に、得られた感光性樹脂組成物層を、キヤノン（株）製　ＭＰＡ　５５００ＣＦ（高圧水銀灯）を用いて、所定のマスクを介して露光した。そして、露光後の感光性樹脂組成物層を、アルカリ現像液（０．４％のテトラメチルアンモニウムヒドロキシド水溶液）で２３℃／６０秒間現像した後、超純水で２０秒リンスした。これらの操作により５μｍのホールを解像する時の最適ｉ線露光量（Ｅｏｐｔ）を感度とした。
　Ａ：２０ｍＪ／ｃｍ2未満
　Ｂ：２０ｍＪ／ｃｍ2以上、４０ｍＪ／ｃｍ2未満
　Ｃ：４０ｍＪ／ｃｍ2以上、８０ｍＪ／ｃｍ2未満
　Ｄ：８０ｍＪ／ｃｍ2以上、１６０ｍＪ／ｃｍ2未満
　Ｅ：１６０ｍＪ／ｃｍ2以上 (2) Evaluation of photosensitive resin composition (2-1) Evaluation of sensitivity A glass substrate (EAGLE XG, 0.7 mm thickness (manufactured by Corning)) is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, After spin-coating each photosensitive resin composition, it was prebaked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3.0 μm.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using Canon Inc. MPA 5500CF (high pressure mercury lamp). Then, 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 μm hole by these operations was taken as the sensitivity.
A: 20mJ / cm 2 less B: 20mJ / cm 2 or more, 40 mJ / cm 2 less than C: 40mJ / cm 2 or more, 80 mJ / cm 2 less than D: 80mJ / cm 2 or more, 160 mJ / cm 2 less than E: 160 mJ / cm 2 or more
（２－２）耐薬品性の評価
　ガラス基板を、ヘキサメチルジシラザン（ＨＭＤＳ）蒸気下に３０秒曝し、該基板に各感光性樹脂組成物をスピンコート塗布した後、９０℃／１２０秒ホットプレート上でプリベークして溶剤を揮発させ、膜厚３．０μｍの感光性樹脂組成物層を形成した。続いて超高圧水銀灯を用いて積算照射量が３００ｍＪ／ｃｍ2（エネルギー強度：２０ｍＷ／ｃｍ2、ｉ線）となるように露光し、この基板をオーブンにて２３０℃／６０分間加熱した後、さらにオーブンにて２３０℃／２時間加熱した。
　得られた硬化膜の膜厚（Ｔ1）を測定した。そして、この硬化膜が形成された基板を６０℃に温度制御されたジメチルスルホキシド：モノエタノールアミン＝７：３溶液中に１０分間浸漬させた後、浸漬後の硬化膜の膜厚（ｔ1）を測定し、浸漬による膜厚変化率｛｜ｔ1－Ｔ1｜／Ｔ1｝×１００〔％〕を算出した。
　小さいほど好ましく、Ａ、Ｂが実用上問題のないレベルである。
　Ａ：２％未満
　Ｂ：２％以上３％未満
　Ｃ：３％以上４％未満
　Ｄ：４％以上６％未満
　Ｅ：６％以上 (2-2) Evaluation of chemical resistance A glass substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and after spin-coating each photosensitive resin composition on the substrate, it is hot at 90 ° C./120 seconds. The solvent was evaporated by prebaking on a plate to form a photosensitive resin composition layer having a thickness of 3.0 μm. Subsequently, using an ultra-high pressure mercury lamp, exposure is performed so that the cumulative irradiation dose is 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and this substrate is heated at 230 ° C./60 minutes in an oven. Furthermore, it heated at 230 degreeC / 2 hours in oven.
The film thickness (T1) of the obtained cured film was measured. Then, after immersing the substrate on which this cured film is formed in a solution of dimethylsulfoxide: monoethanolamine = 7: 3 temperature-controlled at 60 ° C. for 10 minutes, the thickness (t1) of the cured film after immersion is It measured and calculated the film thickness change rate {| t1-T1 | / T1} x 100 [%] by immersion.
The smaller, the better, and A and B are levels that cause no problem in practical use.
A: less than 2% B: 2% or more and less than 3% C: 3% or more and less than 4% D: 4% or more and less than 6% E: 6% or more
（２－３）表示装置における表示ムラ（パネル表示ムラ）の評価
　薄膜トランジスタ（ＴＦＴ）を用いた液晶表示装置を以下の方法で作製した（図２参照）。特許第３３２１００３号公報の図１および図２に記載のアクティブマトリクス型液晶表示装置において、層間絶縁膜として硬化膜１７を以下のようにして形成し、液晶表示装置を得た。
　すなわち、ガラス基板６上にボトムゲート型のＴＦＴ１を形成し、このＴＦＴ１を覆う状態でＳｉ3Ｎ4から成る絶縁膜３を形成した。次に、この絶縁膜３に、コンタクトホールを形成した後、このコンタクトホールを介してＴＦＴ１に接続される配線２（高さ１．０μｍ）を絶縁膜３上に形成した。 (2-3) Evaluation of display unevenness (panel display unevenness) in display device A liquid crystal display device using a thin film transistor (TFT) was manufactured by the following method (see FIG. 2). In the active matrix liquid crystal display device shown in FIG. 1 and FIG. 2 of Japanese Patent No. 3321003, 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 μm) connected to the TFT 1 via the contact hole was formed on the insulating film 3.
　さらに、配線２の形成による凹凸を平坦化するために、配線２による凹凸を埋め込む状態で絶縁膜３上へ平坦化膜４を形成した。絶縁膜３上への平坦化膜４の形成は、実施例および比較例の各感光性樹脂組成物を基板上にスピン塗布し、ホットプレート上でプリベーク（９０℃×２分）した後、マスク上から高圧水銀灯を用いてｉ線（３６５ｎｍ）を２５ｍＪ／ｃｍ2（エネルギー強度２０ｍＷ／ｃｍ2）照射した後、アルカリ水溶液にて現像してパターンを形成し、２３０℃で６０分間の加熱処理を行った。前記感光性樹脂組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。さらに、配線２の平均段差は５００ｎｍ、作製した平坦化膜４の膜厚は２，０００ｎｍであった。 Furthermore, in order to planarize the unevenness due to the formation of the wiring 2, 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. From above, 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. 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.
　得られた液晶表示装置に対して駆動電圧を印加し、グレイのテスト信号を入力させ、６０℃、９０％の環境でパネルを連続点灯させ、１０００時間点灯後のグレイ表示を目視にて観察し、表示ムラの発生の有無を下記評価基準にしたがって評価した。
　Ａ：まったくムラがみられない（非常に良い）
　Ｂ：ガラス基板の縁部分にかすかにムラが見られるが、表示部に問題なし（良い）
　Ｃ：表示部にかすかにムラが見られるが実用レベル（普通）
　Ｄ：表示部にムラがある（やや悪い）
　Ｅ：表示部に強いムラがある（非常に悪い） 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.
A: There is no unevenness at all (very good)
B: Slight unevenness appears on the edge of the glass substrate, but there is no problem with the display (good)
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)
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　上記結果から明らかなとおり本発明の感光性樹脂組成物は、感度が高く、硬化膜の耐薬品性に優れ、パネル信頼性試験においてパネル表示ムラの発生が抑制されていることがわかった。これに対し、比較例の感光性樹脂組成物は、感度、耐薬品性およびパネル表示ムラの全ての項目を満足するものがないことがわかった。 As is clear from the above results, it was found that 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. On the other hand, it was found that the photosensitive resin composition of the comparative example did not satisfy all the items of sensitivity, chemical resistance and panel display unevenness.
＜実施例７４＞
　実施例７４は、実施例１において、露光機を、キヤノン（株）製　ＭＰＡ　５５００ＣＦから、Ｎｉｋｏｎ（株）製ＦＸ－８０３Ｍ（ｇｈ－Ｌｉｎｅ　ステッパ）に変更した以外は同様に行った。感度、耐薬品性およびパネル表示ムラの評価は実施例１と同レベルであった。 Example 74
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.
＜実施例７５＞
　実施例７５は、実施例１において、露光機を、キヤノン（株）製　ＭＰＡ　５５００ＣＦから、３５５ｎｍレーザー露光機に変更して３５５ｎｍレーザー露光を行った以外は同様に行った。ここで、３５５ｎｍレーザー露光機としては、株式会社ブイテクノロジー社製の「ＡＥＧＩＳ」を使用し（波長３５５ｎｍ、パルス幅６ｎｓｅｃ）、露光量はＯＰＨＩＲ社製の「ＰＥ１０Ｂ－Ｖ２」を用いて測定した。
　感度、耐薬品性およびパネル表示ムラの評価は実施例１と同レベルであった。 Example 75
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. Here, as 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.
＜実施例７６＞
　実施例７６は、実施例１において、露光機を、キヤノン（株）製　ＭＰＡ　５５００ＣＦから、ＵＶ－ＬＥＤ光源露光機に変更した以外は同様に行った。感度、耐薬品性およびパネル表示ムラの評価は実施例１と同レベルであった。 Example 76
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.
＜実施例７７＞
　実施例１と以下の塗布プロセスのみ変更して、同様の液晶表示装置を得た。すなわち、実施例１の感光性樹脂組成物をスリットコート法にて塗布した後、９０℃／１２０秒ホットプレート上で加熱により溶剤を除去し、膜厚３．０μｍの感光性樹脂組成物層を形成した。得られた塗膜は、平坦でムラの無い良好な面状であった。また液晶表示装置としての性能も実施例１と同様に良好であった。 <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 μm 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.
　上記のとおり、実施例の感光性樹脂組成物は、露光機や塗布方法の如何に拘らず、感度、耐薬品性に優れ、パネル信頼性の高い液晶表示装置が得られることがわかった。 As mentioned above, it turned out that 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.
＜実施例７８＞
　薄膜トランジスター（ＴＦＴ）を用いた有機ＥＬ表示装置を以下の方法で作製した（図２参照）。
　ガラス基板６上にボトムゲート型のＴＦＴ１を形成し、このＴＦＴ１を覆う状態でＳｉ3Ｎ4から成る絶縁膜３を形成した。次に、この絶縁膜３に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してＴＦＴ１に接続される配線２（高さ１．０μｍ）を絶縁膜３上に形成した。この配線２は、ＴＦＴ１間または、後の工程で形成される有機ＥＬ素子とＴＦＴ１とを接続するためのものである。 <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. Next, after forming a contact hole (not shown) in the insulating film 3, a wire 2 (height 1.0 μm) 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.
　さらに、配線２の形成による凹凸を平坦化するために、配線２による凹凸を埋め込む状態で絶縁膜３上へ平坦化膜４を形成した。絶縁膜３上への平坦化膜４の形成は、実施例１６の感光性樹脂組成物を基板上にスピン塗布し、ホットプレート上でプリベーク（９０℃／１２０秒）した後、マスク上から高圧水銀灯を用いてｉ線（３６５ｎｍ）を４５ｍＪ／ｃｍ2（エネルギー強度２０ｍＷ／ｃｍ2）照射した後、アルカリ水溶液にて現像してパターンを形成し、２３０℃／３０分間の加熱処理を行った。
　感光性樹脂組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。さらに、配線２の平均段差は５００ｎｍ、作製した平坦化膜４の膜厚は２，０００ｎｍであった。 Furthermore, in order to planarize the unevenness due to the formation of the wiring 2, 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. After forming the planarizing film 4 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.
　次に、得られた平坦化膜４上に、ボトムエミッション型の有機ＥＬ素子を形成した。まず、平坦化膜４上に、ＩＴＯからなる第一電極５を、コンタクトホール７を介して配線２に接続させて形成した。その後、レジストを塗布、プリベークし、所望のパターンのマスクを介して露光し、現像した。このレジストパターンをマスクとして、ＩＴＯエッチャント用いたウエットエッチングによりパターン加工を行った。その後、レジスト剥離液（リムーバ１００、ＡＺエレクトロニックマテリアルズ社製）を用いて上記レジストパターンを５０℃で剥離した。こうして得られた第一電極５は、有機ＥＬ素子の陽極に相当する。 Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, 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. Thereafter, 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.
　次に、第一電極５の周縁を覆う形状の絶縁膜８を形成した。絶縁膜８には、実施例１の感光性樹脂組成物を用い、上記と同様の方法で絶縁膜８を形成した。この絶縁膜８を設けることによって、第一電極５とこの後の工程で形成する第二電極との間のショートを防止することができる。 Next, 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.
　さらに、真空蒸着装置内で所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設けた。次いで、基板上方の全面にＡｌから成る第二電極を形成した。得られた上記基板を蒸着機から取り出し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止した。 Furthermore, 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.
　以上のようにして、各有機ＥＬ素子にこれを駆動するためのＴＦＴ１が接続してなるアクティブマトリックス型の有機ＥＬ表示装置が得られた。駆動回路を介して電圧を印加したところ、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 As described above, 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. When 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.

Claims (16)

  1. （Ａ）下記（１）および（２）の少なくとも一方を満たす重合体を含む重合体成分、
    （１）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位、および（ａ２）架橋性基を有する構成単位、を有する重合体、
    （２）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位を有する重合体、および（ａ２）架橋性基を有する構成単位を有する重合体、
    （Ｂ）光酸発生剤、
    （Ｃ）芳香族複素環化合物、および、
    （Ｄ）溶剤、
    を含み、前記（Ｃ）芳香族複素環化合物が、分子量が１０００以下であり、芳香環中に少なくとも１つの窒素原子を含み、且つ芳香環中に少なくとも２つの配位原子を含むことを特徴とする感光性樹脂組成物。     (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 (C) the 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. Photosensitive resin composition.
  2. 前記（Ｃ）の芳香族複素環化合物が、５員環芳香族複素環化合物、６員環芳香族複素環化合物、５員環芳香族複素環構造および６員環芳香族複素環構造の少なくとも一方を含む多環式芳香族複素環化合物のいずれかであることを特徴とする、請求項１に記載の感光性樹脂組成物。 The aromatic heterocyclic compound (C) is at least one of 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 claim 1, which is any one of polycyclic aromatic heterocyclic compounds containing
  3. 前記配位原子が窒素原子、硫黄原子、酸素原子のいずれかである、請求項１または２に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the coordinating atom is any one of a nitrogen atom, a sulfur atom, and an oxygen atom.
  4. 前記（Ａ）の重合体において、（ａ２）架橋性基を有する構成単位に含まれる架橋性基が、エポキシ基、オキセタニル基、および－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは水素原子または炭素数１～２０のアルキル基）で表される基から選ばれる少なくとも１種である、請求項１～３のいずれか１項に記載の感光性樹脂組成物。 In the polymer (A), the crosslinkable group contained in the structural unit having a crosslinkable group (a2) is an epoxy group, an oxetanyl group, and -NH-CH 2 -O-R (R represents a hydrogen atom or carbon The photosensitive resin composition according to any one of claims 1 to 3, which is at least one selected from the groups represented by the alkyl groups of 1 to 20).
  5. 前記酸分解性基がアセタールの形で保護された構造を有する基である、請求項１～４のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the acid-degradable group is a group having a protected structure in the form of acetal.
  6. 前記（Ａ）の重合体成分のいずれかが、さらに、酸基を含有する重合体である、請求項１～５のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 5, wherein any of the polymer components (A) is a polymer further containing an acid group.
  7. 前記（Ｂ）の光酸発生剤が、オキシムスルホネート化合物である、請求項１～６のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 6, wherein the photoacid generator (B) is an oxime sulfonate compound.
  8. 前記（Ｃ）の芳香族複素環化合物が、芳香環中に２～３つの配位原子を含む、請求項１～７のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 7, wherein the aromatic heterocyclic compound (C) contains two to three coordinating atoms in the aromatic ring.
  9. 前記（Ｃ）の芳香族複素環化合物が、芳香環中に少なくとも２つの窒素原子を含む、請求項１～８のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 8, wherein the aromatic heterocyclic compound (C) contains at least two nitrogen atoms in the aromatic ring.
  10. 前記（Ｃ）芳香族複素環化合物が有する環が、単環、ならびに／または、２つもしくは３つの環の縮合環である、請求項１～９のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 9, wherein the ring of the (C) aromatic heterocyclic compound is a single ring and / or a fused ring of two or three rings. object.
  11. 前記（Ｃ）芳香族複素環化合物における芳香環が有する置換基としてアミノ基を含まないことを特徴とする、請求項１～１０のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 10, which does not contain an amino group as a substituent that the aromatic ring of the (C) aromatic heterocyclic compound has.
  12. 　（１）請求項１～１１のいずれか１項に記載の感光性樹脂組成物を基板上に塗布する塗布工程、
    　（２）塗布された感光性樹脂組成物から溶剤を除去する溶剤除去工程、
    　（３）溶剤が除去された感光性樹脂組成物を活性光線により露光する露光工程、
    　（４）露光された感光性樹脂組成物を水性現像液により現像する現像工程、および、
    　（５）現像された感光性樹脂組成物を熱硬化するポストベーク工程、
    を含む硬化膜の形成方法。     (1) A coating step of coating the photosensitive resin composition according to any one of claims 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.
  13. 前記現像工程後、前記ポストベーク工程前に、現像された感光性樹脂組成物を全面露光する工程を含む、請求項１２に記載の硬化膜の形成方法。 The method for forming a cured film according to claim 12, comprising the step of exposing the entire surface of the developed photosensitive resin composition after the development step and before the post-baking step.
  14. 請求項１２または１３に記載の方法により形成された硬化膜。 A cured film formed by the method according to claim 12 or 13.
  15. 層間絶縁膜である、請求項１４に記載の硬化膜。 The cured film according to claim 14, which is an interlayer insulating film.
  16. 請求項１４または１５に記載の硬化膜を具備する有機ＥＬ表示装置または液晶表示装置。 An organic EL display device or a liquid crystal display device comprising the cured film according to claim 14 or 15.
PCT/JP2013/074977 2012-09-28 2013-09-17 Photosensitive resin composition, method for forming cured film using same, cured film, liquid crystal display device, and organic el display device WO2014050627A1 (en)

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