WO2016052389A1 - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic electroluminescent display device, and touch panel - Google Patents

Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic electroluminescent display device, and touch panel Download PDF

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Publication number
WO2016052389A1
WO2016052389A1 PCT/JP2015/077287 JP2015077287W WO2016052389A1 WO 2016052389 A1 WO2016052389 A1 WO 2016052389A1 JP 2015077287 W JP2015077287 W JP 2015077287W WO 2016052389 A1 WO2016052389 A1 WO 2016052389A1
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group
resin composition
photosensitive resin
structural unit
polysiloxane
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PCT/JP2015/077287
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French (fr)
Japanese (ja)
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豪 安藤
大助 柏木
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富士フイルム株式会社
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Publication of WO2016052389A1 publication Critical patent/WO2016052389A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers

Definitions

  • the present invention relates to a photosensitive resin composition. More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film, an interlayer insulating film, and the like of electronic components such as a liquid crystal display device, an organic electroluminescence display device, a touch panel, an integrated circuit element, and a solid-state imaging element About.
  • the present invention also relates to a method for producing a cured film, a cured film obtained by curing a photosensitive resin composition, a liquid crystal display device using the cured film, an image display device such as an organic electroluminescence display device, and an input device such as a touch panel.
  • An image display device such as an organic electroluminescence display device and a liquid crystal display device, and an input device such as a touch panel are provided with a patterned interlayer insulating film.
  • a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained. As a characteristic of the photosensitive resin composition, good sensitivity is required.
  • Patent Document 1 discloses a photosensitive resin composition containing an alkali-soluble siloxane polymer and a photosensitive compound having a 1,2-naphthoquinone diad group.
  • Patent Document 2 polysiloxane containing a structural unit having a carboxylic acid protected with an acid-decomposable group as component (A), a photoacid generator as component (B), an organic solvent as component (C), A photosensitive resin composition containing an epoxy group-containing siloxane compound as component (D) is disclosed.
  • Patent Document 3 discloses a photosensitive resin composition containing polysiloxane containing a structural unit having a protected silanol group and a structural unit having an epoxy group.
  • Patent Document 4 discloses a photosensitive resin composition containing an acrylic resin, a photoacid generator, and an alicyclic epoxy compound.
  • Patent Document 4 in a photosensitive resin composition using an acrylic resin, a uniform contact call is formed while maintaining sensitivity and transparency after heating by including an alicyclic epoxy compound.
  • Patent Document 4 there is no description regarding suppression of pattern defects and development residues.
  • an object of the present invention is to provide a photosensitive resin composition having good sensitivity and having suppressed pattern defects and development residues. Moreover, it is providing the manufacturing method of a cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel.
  • a polysiloxane component a photoacid generator that generates an acid having a pKa of 3 or less, a solvent, and an alicyclic epoxy compound described later are included. It has been found that a photosensitive resin composition having a good sensitivity and having suppressed pattern defects and development residues can be obtained by the photosensitive resin composition, and the present invention has been completed.
  • the present invention provides the following.
  • a polysiloxane component comprising a polysiloxane having a structural unit having a crosslinkable group as the structural unit a2.
  • a photoacid generator that generates an acid having a pKa of 3 or less as component B;
  • a solvent as component C and
  • a photosensitive resin composition comprising, as component S, an alicyclic epoxy compound having a molecular weight of 150 to 1000 represented by the following formula EP;
  • R EP1 represents an alkyl group
  • p represents an integer of 0 to 7
  • A represents a q-valent hydrocarbon group which may have an oxygen atom
  • q represents an integer of 1 to 4.
  • ⁇ 3> The photosensitive resin composition according to ⁇ 1> or ⁇ 2>, wherein the alicyclic epoxy compound has a molecular weight of 200 to 400.
  • ⁇ 4> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the alicyclic epoxy compound is a compound represented by the following formula EP1:
  • R EP2 and R EP3 each independently represent an alkyl group
  • p represents an integer of 0 to 7
  • the plurality of R EP2 and R EP3 may be the same or different
  • a 1 represents a divalent hydrocarbon group containing at least one selected from —O—, —COO—, and —OCO—.
  • the structural unit a1 is at least one selected from a structural unit represented by the following general formula a1-1 and a structural unit represented by the following general formula a1-2.
  • a 0 or 1
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 represents an alkyl group or an aryl group
  • R 3 represents an alkyl group or an aryl group.
  • R 1 or R 2 and R 3 may be linked to form a cyclic ether
  • R 4 represents an alkyl group, an aryl group, or an aralkyl group
  • L 1 represents a single bond or a divalent linking group
  • L 2 represents a single bond or a divalent linking group
  • R x represents an alkyl group or a halogen atom
  • m1 represents an integer of 0 to 4.
  • ⁇ 8> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the polysiloxane further includes a structural unit having at least one group selected from a carboxy group and a phenolic hydroxyl group.
  • the photoacid generator is at least one selected from an onium salt compound, an oxime sulfonate compound, and an imide sulfonate compound.
  • a method for producing a cured film comprising: exposing the exposed photosensitive resin composition; developing the exposed photosensitive resin composition; and thermally curing the developed photosensitive resin composition.
  • a cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 9>.
  • the cured film according to ⁇ 11> which is an interlayer insulating film.
  • a liquid crystal display device having the cured film according to ⁇ 11> or ⁇ 12>.
  • An organic electroluminescence display device having the cured film according to ⁇ 11> or ⁇ 12>.
  • a touch panel having the cured film according to ⁇ 11> or ⁇ 12>.
  • composition conceptual diagram of an example of a liquid crystal display It is a composition conceptual diagram of other examples of a liquid crystal display.
  • 1 shows a conceptual diagram of a configuration of an example of an organic EL display device. It is sectional drawing which shows the structural example of a capacitive touch panel. It is explanatory drawing which shows an example of a front plate. It is explanatory drawing which shows an example of a 1st transparent electrode pattern and a 2nd transparent electrode pattern.
  • the solid content concentration in this specification refers to the solid content concentration at 25 ° C.
  • the viscosity in this specification refers to a viscosity at 25 ° C.
  • a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by a gel permeation chromatography (GPC) measurement.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, using HLC-8120 (manufactured by Tosoh Corp.) and using TSK gel Multipore HXL-M (manufactured by Tosoh Corp.) as a column. 7.8 mm ID ⁇ 30.0 cm can be determined by using THF (tetrahydrofuran) as the eluent.
  • the photosensitive resin composition of the present invention comprises (A) a polysiloxane component described later, (B) a photoacid generator that generates an acid having a pKa of 3 or less, (C) a solvent, (D) a molecular weight of 150 to 1000 cycloaliphatic epoxy compounds represented by the formula (EP) described later. Since the photosensitive resin composition of this invention contains the polysiloxane component mentioned later and a photo-acid generator, a sensitivity is favorable. Moreover, the cured film excellent in heat resistance can also be formed by including a polysiloxane component.
  • the photosensitive resin composition of the present invention can be preferably used as a chemically amplified positive photosensitive resin composition.
  • each component of the photosensitive resin composition of the present invention will be described in more detail.
  • the polysiloxane component satisfies at least one of the following (1) and (2).
  • (1) a1 a structural unit having at least one group selected from a group in which a carboxy group is protected with an acid-decomposable group and a group in which a phenolic hydroxyl group is protected with an acid-decomposable group;
  • a polysiloxane component comprising a polysiloxane (A1) having a structural unit having a crosslinkable group.
  • a polysiloxane component comprising (A2) and (a2) polysiloxane (A3) having a structural unit having a crosslinkable group.
  • a polysiloxane component means what included other polysiloxane added as needed in addition to the said polysiloxane.
  • At least one polysiloxane (A1) is contained, and the polysiloxane (A1) has the structural unit (a1) and the structural unit (a2).
  • Each of the structural unit (a1) and the structural unit (a2) may contain two or more types.
  • the structural unit (a3) which has an acid group mentioned later, and the structural unit (a4) may be included.
  • the proportion of the structural unit (a1) of the polysiloxane (A1) is preferably 10 to 90 mol% with respect to the total structural units of the polysiloxane (A1) from the viewpoint of sensitivity.
  • the lower limit is preferably 15 mol% or more, and more preferably 20 mol% or more.
  • the upper limit is preferably 80 mol% or less, and more preferably 60 mol% or less.
  • the proportion of the structural unit (a2) is preferably 10 to 90 mol% with respect to all the structural units of the polysiloxane (A1) from the viewpoint of cured film characteristics.
  • the lower limit is preferably 20 mol% or more, and more preferably 30 mol% or more.
  • the upper limit is preferably 80 mol% or less, and more preferably 70 mol% or less.
  • the proportion of the structural unit (a3) is preferably 0 to 50 mol% with respect to all the structural units of the polysiloxane (A1) from the viewpoint of sensitivity.
  • the lower limit is preferably 1 mol% or more, more preferably 5 mol% or more.
  • the upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
  • the proportion of the structural unit (a4) is preferably 0 to 40 mol% with respect to all the structural units of the polysiloxane (A1) from the viewpoints of developability and cured film characteristics.
  • the lower limit is preferably 1 mol% or more, more preferably 5 mol% or more.
  • the upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
  • the polysiloxane (A2) having the structural unit (a1) and the polysiloxane (A3) having the structural unit (a2) are included.
  • the polysiloxane (A2) containing the structural unit (a1) may further contain the structural unit (a2).
  • the polysiloxane (A3) containing the structural unit (a2) may contain the structural unit (a1).
  • the aspect satisfies both (1) and (2).
  • polysiloxane (A2) and polysiloxane (A3) may contain the structural unit (a3) which has the acid group mentioned later, and a structural unit (a4).
  • the proportion of the structural unit (a1) of the polysiloxane (A2) is preferably 10 to 90 mol% with respect to all the structural units of the polysiloxane (A2).
  • the lower limit is preferably 30 mol% or more, and more preferably 40 mol% or more.
  • the upper limit is preferably 90 mol% or less, and more preferably 80 mol% or less.
  • the proportion of the structural unit (a3) is preferably 0 to 50 mol% with respect to all the structural units of the polysiloxane (A2).
  • the lower limit is preferably 1 mol% or more, more preferably 5 mol% or more.
  • the upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
  • the proportion of the structural unit (a4) is preferably 0 to 40 mol% with respect to all the structural units of the polysiloxane (A2).
  • the lower limit is preferably 1 mol% or more, more preferably 5 mol% or more.
  • the upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
  • the proportion of the structural unit (a2) of the polysiloxane (A3) is preferably 10 to 90 mol% with respect to all the structural units of the polysiloxane (A3).
  • the lower limit is preferably 30 mol% or more, and more preferably 50 mol% or more.
  • the upper limit is preferably 90 mol% or less, and more preferably 80 mol% or less.
  • the proportion of the structural unit (a4) is preferably 0 to 40 mol% with respect to all the structural units of the polysiloxane (A3).
  • the lower limit is preferably 1 mol% or more, more preferably 5 mol% or more.
  • the upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
  • the mass ratio of the polysiloxane (A2) having the structural unit (a1) and the polysiloxane (A3) having the structural unit (a2) is 95: 5 to 5:95. Is preferable, 80:20 to 20:80 is more preferable, and 70:30 to 30:70 is more preferable.
  • the structure of the polysiloxane used in the present invention is not particularly limited. Any of a straight chain shape, a ring shape, a ladder shape, and a mesh shape may be used, and a structure in which these are connected to each other may be used. It is preferable in terms of hardness of the cured film that a ladder-like or network-like structure is included.
  • the weight average molecular weight of the polysiloxane contained in the polysiloxane component is preferably 1,000 to 200,000, and more preferably 2,000 to 50,000. Various characteristics are favorable in the said range.
  • the ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
  • the polysiloxane used in the present invention is a structural unit (a1) having at least one group selected from a group in which a carboxy group is protected with an acid-decomposable group and a group in which a phenolic hydroxyl group is protected with an acid-decomposable group.
  • the polysiloxane used in the present invention is a structural unit (a1) having at least one group selected from a group in which a carboxy group is protected with an acid-decomposable group and a group in which a phenolic hydroxyl group is protected with an acid-decomposable group. ).
  • the carboxy group and the phenolic hydroxyl group are also referred to as an acid group.
  • a group in which a carboxy group is protected with an acid-decomposable group and “a group in which a phenolic hydroxyl group is protected with an acid-decomposable group” are used for deprotection reaction using an acid as a catalyst (or an initiator). It means a group which is raised and produces the above-described acid group, regenerated acid, and decomposed structure.
  • the acid group is preferably a carboxy group.
  • An acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group described later) or a group that is relatively difficult to decompose by an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group) can be used. Among these groups, an acetal group is preferable.
  • the structural unit (a1) preferably has a protected carboxy group in which a carboxy group is protected with an acetal group, or a protected phenol group in which a phenolic hydroxyl group is protected with an acetal group, and the carboxy group is protected with an acetal group. It is more preferable to have a protected carboxy group. According to this aspect, it is preferable from the viewpoints of basic physical properties of the photosensitive resin composition, particularly sensitivity, pattern shape, contact hole formability, and storage stability of the photosensitive resin composition.
  • the structural unit (a1) is preferably a structural unit represented by the following general formula (a1-1) and / or a structural unit represented by the following general formula (a1-2).
  • a represents 0 or 1;
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 represents an alkyl group or an aryl group, and
  • R 3 represents an alkyl group or an aryl group.
  • R 1 or R 2 and R 3 may be linked to form a cyclic ether,
  • R 4 represents an alkyl group, an aryl group, or an aralkyl group,
  • L 1 represents a single bond or a divalent linking group,
  • L 2 represents a single bond or a divalent linking group,
  • R x represents an alkyl group or a halogen atom,
  • m1 represents an integer of 0 to 4.
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1 and R 2 is an alkyl group or an aryl group.
  • the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • the alkyl group may be unsubstituted or may have a substituent.
  • the alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.
  • substituents that the alkyl group may have include an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, and a halogen atom (fluorine atom, chlorine atom, bromine atom). , Iodine atom) and the like. These substituents may further have a substituent.
  • an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable.
  • the aryl group may be unsubstituted or may have a substituent.
  • Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the substituent include those described above.
  • an alkyl group having 1 to 10 carbon atoms can be used as a substituent.
  • R 1 and R 2 are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and one of R 1 and R 2 is a methyl group.
  • the other is particularly preferably a hydrogen atom.
  • R 3 represents an alkyl group or an aryl group.
  • the alkyl group and aryl group represented by R 3 have the same meanings as the alkyl group and aryl group in R 1 and R 2 .
  • R 3 is preferably a methyl group, an ethyl group, or a propyl group, and more preferably an ethyl group or a propyl group.
  • R 3 may be linked to R 1 or R 2 to form a cyclic ether.
  • the cyclic ether formed by linking with R 1 or R 2 is preferably a 3- to 6-membered cyclic ether, and more preferably a 5- to 6-membered cyclic ether.
  • R 4 represents an alkyl group, an aryl group, or an aralkyl group.
  • an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • the alkyl group may have a substituent.
  • the alkyl group may be linear, branched or cyclic.
  • an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable.
  • the aryl group may have a substituent.
  • the aryl group examples include a phenyl group, a naphthyl group, and an anthracenyl group.
  • the aralkyl group a group in which a part of hydrogen atoms of an alkyl group having 1 to 10 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms is preferable.
  • the aralkyl group may have a substituent.
  • the alkyl group constituting the aralkyl group may be linear, branched or cyclic.
  • the substituents that the alkyl group, aryl group, and aralkyl group may have are the same as the substituents described for R 1 and R 2 .
  • R 4 is preferably a methyl group, a phenyl group, a propyl group, a butyl group, or a hexyl group from the viewpoint of solvent resistance or heat resistance, and more preferably a methyl group or a phenyl group.
  • R x represents an alkyl group or a halogen atom.
  • the alkyl group an alkyl group having 1 to 4 carbon atoms is preferable.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.
  • L 1 and L 2 represent a single bond or a divalent linking group.
  • the divalent linking group include an alkylene group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 12 carbon atoms, and an arylene group having 6 to 12 carbon atoms.
  • the alkylene oxide group and the alkylene oxide group may be linear, branched or cyclic.
  • the alkylene group, alkylene oxide group, and arylene group may have a substituent. Examples of the substituent are the same as those described for R 1 and R 2 .
  • m1 represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and most preferably 0.
  • the structural unit represented by the general formula (a1-2) is preferably a structural unit represented by the following general formula (a1-2-1).
  • a 0 or 1
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and at least one of R 1 and R 2 is Represents an alkyl group or an aryl group
  • R 3 represents an alkyl group or an aryl group
  • R 1 or R 2 and R 3 may be linked to form a cyclic ether
  • R 4 represents an alkyl group
  • An aryl group or an aralkyl group is represented
  • L 2 represents a single bond or a divalent linking group
  • R x represents an alkyl group or a halogen atom
  • m1 represents an integer of 0 to 4.
  • silane compound that can be used for obtaining the structural unit (a1) include the following silane compounds.
  • the structural unit (a2) has a crosslinkable group.
  • the crosslinkable group means a group capable of causing a crosslinking reaction by heat.
  • the crosslinkable group is not particularly limited as long as it is a group having a crosslinking reaction starting temperature of 100 ° C. or higher during heat treatment at 1 atm.
  • the initiation temperature of the cross-linking reaction can be analyzed using a known method, for example, by a method using DSC measurement (Differential scanning calorimetry).
  • Examples of the crosslinkable group include a cyclic ether, a group having an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, and an amino group.
  • the crosslinkable group may be bonded via a linking group or the like.
  • Examples of the cyclic ether include an epoxy group and an oxetanyl group.
  • Examples of the group having an ethylenically unsaturated bond include vinyl group, allyl group, methallyl group, methacryloyl group, acryloyl group, allyloxycarbonyl group, and methallyloxycarbonyl group.
  • Examples of the alkoxymethyl group include a group represented by “—CH 2 OR”.
  • R represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear.
  • the amino group may be an amino group having a substituent or an unsubstituted amino group.
  • the crosslinkable group is preferably a cyclic ether or a group having an ethylenically unsaturated bond, more preferably a cyclic ether, still more preferably an epoxy group or an oxetanyl group, and particularly preferably an epoxy group. Cyclic ethers can consume unreacted acid groups to form a strong cured film.
  • crosslinkable group examples include the following, but are not limited thereto.
  • * represents a connecting portion with another group.
  • the structural unit (a2) may have at least one crosslinkable group in one structural unit, preferably 1 to 3 and more preferably 1.
  • the structural unit (a2) may all be of the same type or different types.
  • a plurality of crosslinkable groups are included, the same kind is preferable.
  • Examples of the structural unit (a2) include structural units represented by the following general formula (a2 ′).
  • a represents 0 or 1
  • R 5 represents an alkyl group, an aryl group or an aralkyl group
  • L 3 represents a single bond or a divalent linking group
  • X represents Represents a crosslinkable group.
  • the structural unit (a2) is a structural unit represented by the following general formula (a2-1) and / or a structural unit represented by the following general formula (a2-2) from the viewpoint of cured film properties. Is preferred.
  • a represents 0 or 1
  • R 5 represents an alkyl group, an aryl group or an aralkyl group
  • R y represents an alkyl group or a halogen atom
  • L 3 represents a single bond or a divalent linking group
  • n represents 0 or 1
  • m 2 represents an integer of 0 to 2 when n is 0, and 0 when n is 1.
  • m3 represents an integer from 0 to 6.
  • R 5 represents an alkyl group, an aryl group, or an aralkyl group.
  • the alkyl group, aryl group and aralkyl group are the same as the ranges described for R 4 in the above (a1-1) and (a1-2), and the preferred ranges are also the same.
  • L 3 represents a single bond or a divalent linking group.
  • the divalent linking group is the same as the range described for L 1 of (a1-1) and L 2 of (a1-2), and the preferred range is also the same.
  • R y represents an alkyl group or a halogen atom.
  • the alkyl group and the halogen atom are the same as the range described for R x in (a1-2) described above, and the preferred range is also the same.
  • n 0 or 1, and 0 is preferable.
  • m2 represents an integer of 0 to 2 when n is 0, and represents an integer of 0 to 3 when n is 1.
  • m2 is preferably 0.
  • m3 represents an integer of 0 to 6, and 0 is preferable.
  • silanes that can be used to obtain the structural unit (a2) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxy. Mention may be made of propyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. . Moreover, the silane compound shown below can also be used.
  • the polysiloxane component may contain the structural unit (a3) having an acid group.
  • the structural unit (a3) may contain a polysiloxane having at least one structural unit selected from the structural unit (a1) and the structural unit (a2).
  • the polysiloxane which does not contain a structural unit (a1) and a structural unit (a2) substantially may be contained.
  • Specific examples of the acid group include a carboxy group, a sulfonamide group, a phosphonyl group, a sulfonyl group, a phenolic hydroxyl group, a sulfonamide group, and a sulfonylimide group.
  • Preferred acid groups include a carboxy group and a phenolic hydroxyl group.
  • the structural unit (a3) having an acid group for example, a structure represented by the following general formula (a3-1) and / or a structure represented by the general formula (a3-2) are preferable specific examples. Can be mentioned.
  • a 0 or 1
  • R 6 represents an alkyl group, an aryl group, or an aralkyl group
  • L 4 represents a single bond or a divalent group
  • L 5 represents a single bond or a divalent linking group
  • R z represents an alkyl group or a halogen atom
  • m4 represents an integer of 0 to 4.
  • R 6 represents an alkyl group, an aryl group, or an aralkyl group.
  • the alkyl group, aryl group and aralkyl group are the same as the ranges described for R 4 in the above (a1-1) and (a1-2), and the preferred ranges are also the same.
  • L 4 represents a single bond or a divalent linking group.
  • the divalent linking group is the same as the range described for L 1 in (a1-1), and the preferred range is also the same.
  • L 5 represents a single bond or a divalent linking group.
  • the divalent linking group is the same as the range described for L 2 in (a1-2), and the preferred range is also the same.
  • R z represents an alkyl group or a halogen atom.
  • alkyl group and the halogen atom are the same as the range described for R x in (a1-2) described above, and the preferred range is also the same.
  • m4 represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and most preferably 0.
  • the structural unit represented by the general formula (a3-2) is preferably a structural unit represented by the following general formula (a3-2-1).
  • a 0 or 1
  • R 6 represents an alkyl group, an aryl group, or an aralkyl group
  • L 5 represents a single bond or a divalent linking group.
  • R z represents an alkyl group or a halogen atom
  • m4 represents an integer of 0-4.
  • silane compound that can be used to obtain the structural unit (a3) the same silane compound that can be used to obtain the structural unit (a1) can be used.
  • the polysiloxane component can contain a structural unit (a4) other than the structural units (a1) to (a3) described above.
  • a structural unit (a4) for example, a structure represented by general formula (a4-1) shown below is preferred.
  • a represents an integer of 0 to 3
  • b represents an integer of 0 to 3.
  • R 7 and R 8 each independently represents an alkyl group, an aryl group, or an aralkyl group.
  • the alkyl group, aryl group and aralkyl group represented by R 7 and R 8 are the same as the ranges described for R 4 in (a1-1) and (a1-2) described above, and the preferred ranges are also the same.
  • the polysiloxane component is the total number of moles of the structural unit (a1) and the moles of the structural unit (a3) and the number of moles of the structural unit (a2) in the total amount of polysiloxane contained in the photosensitive resin composition.
  • the ratio is preferably 10:90 to 90:10, more preferably 30:70 to 70:30, and still more preferably 40:60 to 60:40. If the ratio between the total number of moles of the structural unit (a1) and the moles of the structural unit (a3) and the mole number of the structural unit (a2) is in the above range, a cured film having excellent solvent resistance can be formed.
  • the polysiloxane contained in the polysiloxane component may contain silanol groups remaining during polymerization of the polysiloxane.
  • the number of silanol groups in the total amount of polysiloxane is preferably 0 to 0.5 times, more preferably 0 to 0.2 times, and most preferably 0 to 0.05 times the number of Si atoms in the polysiloxane. When the number of silanol groups is in the above range, the storage stability of the photosensitive resin composition is good.
  • the number of silanol groups in the total amount of polysiloxane here means the total number of silanol groups of the polysiloxane contained in the polysiloxane component. The same applies to the number of Si atoms.
  • the polysiloxane can be obtained by mixing and reacting a silane compound corresponding to each structural unit or oligosiloxane.
  • a silane compound corresponding to each structural unit or oligosiloxane For example, it can be obtained by hydrolysis and condensation of the corresponding trimethoxysilane or dimethoxysilane. Hydrolysis and condensation can be appropriately performed by known methods and conditions.
  • Japanese Patent Application Laid-Open No. 10-324748 especially 0085 paragraph to 0087 paragraph
  • Japanese Patent Application Laid-Open No. 2005-283939 particularly 0052 paragraph to 054 paragraph
  • Japanese Patent Application Laid-Open No. 2006-276598 particularly 0009 paragraph to 0030 paragraph
  • the procedures and conditions described in can be referred to.
  • the acid-decomposable group of the structural unit (a1) described above may be introduced using a protected silane compound or may be introduced by a polymer reaction.
  • a structural unit containing a carboxy group is introduced into (A) polysiloxane
  • the corresponding alkyl ester of carboxylic acid is used. It is preferable to synthesize a polysiloxane using a silane having an alkyl group and hydrolyze the alkyl ester by a general method to obtain a structural unit having a carboxy group.
  • an acid-decomposable group is formed by a so-called polymer reaction. It is preferable to introduce carboxy to protect the carboxy group.
  • a so-called polymer reaction is performed to produce an acid-decomposable group. It is preferable to protect the phenolic hydroxyl group by introducing.
  • the polysiloxane (A1) having the structural unit (a1) and the structural unit (a2) further has the structural unit (a3) and / or the structural unit (a4).
  • the polysiloxane (A2) having the structural unit (a1) further has the structural unit (a3) and / or the structural unit (a4).
  • the polysiloxane (A3) having the structural unit (a2) further has the structural unit (a3) and / or the structural unit (a4).
  • the structural unit (a1) and / or the structural unit (a4) substantially free of the structural unit (a1) and the structural unit (a2) the structural unit (a1) and / or The total amount of the polysiloxane having the structural unit (a2) and the polysiloxane having the structural unit (a3) and / or the structural unit (a4) substantially not including the structural unit (a1) and the structural unit (a2)
  • the mass ratio with respect to the total amount is preferably 99: 1 to 5:95, more preferably 97: 3 to 30:70, and still more preferably 95: 5 to 50:50.
  • the total content of the polysiloxane having the structural unit (a1) and / or the structural unit (a2) is preferably 60% by mass or more, preferably 70% by mass or more, and 90% by mass with respect to the total content of the polysiloxane. % Or more is most preferable.
  • the content of the (A) polysiloxane component in the photosensitive resin composition of the present invention is preferably 60 to 99% by mass with respect to the total solid content of the photosensitive resin composition.
  • the upper limit is more preferably 98% by mass or less, for example.
  • the lower limit is more preferably 65% by mass or more, and still more preferably 70% by mass or more.
  • the photosensitive resin composition of the present invention contains a photoacid generator that generates an acid having a pKa of 3 or less.
  • the photoacid generator is preferably one that generates an acid having a pKa of 2 or less.
  • pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to.
  • the acid having a pKa of 3 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.
  • the photoacid generator is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • Examples of the photoacid generator include onium salt compounds, trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and imide sulfonate compounds.
  • onium salt compounds trichloromethyl-s-triazines
  • diazomethane compounds imide sulfonate compounds
  • oxime sulfonate compounds oxime sulfonate compounds
  • imide sulfonate compounds imide sulfonate compounds.
  • a photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
  • trichloromethyl-s-triazines diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-212494A. It can be illustrated.
  • onium salt compounds examples include diphenyliodonium salts, triarylsulfonium salts, sulfonium salts, benzothiazonium salts, tetrahydrothiophenium salts, and the like.
  • Compounds represented by the following general formula (1) and / or general formula (2) are preferred.
  • R 5 , R 6 and R 7 each independently represents an alkyl group or an aryl group, and in the case of representing an alkyl group, they may be linked together to form a ring, R 8 and R 9 each independently represents an aryl group, and X ⁇ represents a conjugate base.
  • R 5 , R 6 and R 7 each independently represents an alkyl group or an aryl group, and the alkyl group or aryl group may have a substituent.
  • substituents include an aryl group having 1 to 10 carbon atoms, a thioaryl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a thioalkoxy group having 1 to 10 carbon atoms. , Hydroxyl group, cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. These substituents may further have a substituent.
  • the alkyl groups represented by R 5 , R 6 and R 7 are each preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and 1 to More preferred is an alkyl group of 4.
  • Examples of the alkyl group include a methyl group, an ethyl group, and a t-butyl group.
  • the two or more alkyl groups may be linked to each other to form a ring, and a hetero atom A ring may be formed via (for example, an oxygen atom, a sulfur atom, etc.).
  • Such a ring form is preferably a 5-membered ring (thiacyclopentane) or a 6-membered ring (thiacyclohexane) containing a sulfur atom.
  • the alkyl group may have a substituent.
  • the aryl group represented by R 5 , R 6 and R 7 is preferably an aryl group having 6 to 15 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.
  • the aryl group may have a substituent.
  • Aryl groups include phenyl, naphthyl, 4-methoxyphenyl, 4-chlorophenyl, 4-methylphenyl, 4-tertiarybutylphenyl, 4-phenylthiophenyl, 2,4,6-trimethyl. Examples thereof include a phenyl group and a 4-methoxy-1-naphthyl group. Of these, a phenyl group, a 4-methoxyphenyl group, and a 4-chlorophenyl group are preferable.
  • R 5 , R 6 and R 7 are preferably aryl groups, and preferably represent the same group.
  • X ⁇ represents a conjugate base.
  • the conjugate base represents a conjugate base of an alkyl sulfonic acid, a conjugate base of an aryl sulfonic acid, or a conjugate base of a bisperfluorosulfonylamide, and a conjugate base of an alkyl sulfonic acid or an aryl sulfonic acid is particularly preferable.
  • a conjugate base a conjugate base of an alkyl sulfonic acid having 1 to 7 carbon atoms is preferable, and a conjugate base having 1 to 4 carbon atoms is more preferable.
  • sulfonic acid When expressed in the form of an acid, for example, methanesulfonic acid, trifluoromethane Particularly preferred are sulfonic acid, n-propanesulfonic acid and heptanesulfonic acid.
  • conjugate base of the aryl sulfonic acid for example, benzene sulfonic acid, chlorobenzene sulfonic acid, and paratoluene sulfonic acid are particularly preferable when expressed in an acid form.
  • the aryl groups independently represented by R 8 and R 9 are the same as the aryl groups represented by R 5 , R 6 and R 7 in general formula (1), and the preferred ranges are also the same. is there. Specifically, R 8 and R 9 are particularly preferably a phenyl group, a 4-methoxyphenyl group, and a 4-chlorophenyl group. R 8 and R 9 preferably represent the same group.
  • the conjugate base represented by X ⁇ has the same meaning as X ⁇ in general formula (1), and the preferred range is also the same.
  • onium salt compound examples include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate.
  • the following compounds and the compounds described in JP-A-2011-232648, paragraphs 0083 to 0085 can be exemplified.
  • Preferred examples of the oxime sulfonate compound that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1).
  • R 21 represents an alkyl group or an aryl group.
  • a wavy line represents a bond with another group.
  • the alkyl group in R 21 may be linear, branched or cyclic.
  • the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group represented by R 21 may be substituted with a halogen atom, an aryl group having 6 to 11 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • the aryl group for 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 with an alkyl group, an alkoxy group, or a halogen atom.
  • a preferred embodiment of the compound containing the oxime sulfonate structure represented by the general formula (B1) is an oxime sulfonate compound represented by the following general formula (B1-1).
  • R 42 represents an optionally substituted alkyl group or aryl group
  • X represents an alkyl group, an alkoxy group, or a halogen atom
  • m4 represents 0-3. Represents an integer, and when m4 is 2 or 3, a plurality of Xs may be the same or different.
  • the alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • the halogen atom as X is preferably a chlorine atom or a fluorine atom.
  • m4 is preferably 0 or 1.
  • m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound which is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
  • oxime sulfonate compound represented by the general formula (B1-1) include the following compounds.
  • Another preferred embodiment of the compound containing an oxime sulfonate structure represented by the above general formula (B1) is an oxime sulfonate compound represented by the following general formula (B1-2).
  • R 43 has the same meaning as R 42 in the formula (B1-1), and X 1 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.
  • R 43 in the above general formula (B1-2) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n- A propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
  • X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
  • n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
  • Another preferred embodiment of the compound containing an oxime sulfonate structure represented by the above general formula (B1) is 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 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups.
  • R 121 to R 124 each independently represents 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 amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R 121 to R 124 may be bonded to each other to form a ring.
  • R 121 to R 124 are preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which 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.
  • the compound containing the oxime sulfonate structure represented by the general formula (B1) As another preferred embodiment of the compound containing the oxime sulfonate structure represented by the general formula (B1), the following general formula (OS-3), the following general formula (OS-4) or the following general formula (OS-5) It is an oxime sulfonate compound represented by these.
  • R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group
  • R 23 , R 26 and R 29 are Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom
  • R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group.
  • X 1 to X 3 each independently represents an oxygen atom or a sulfur atom
  • n 1 to n 3 each independently represents 1 or 2
  • m 1 to m 3 each independently represents an integer of 0 to 6 To express.
  • the compound having an oxime sulfonate structure represented by the general formula (B1) is, for example, the general formulas (OS-6) to (OS-) described in paragraph No. 0117 of JP2012-163937A. It is particularly preferable that the compound is represented by any one of 11), the contents of which are incorporated herein.
  • Preferred ranges in the general formulas (OS-6) to (OS-11) are the preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. It is the same.
  • oxime sulfonate compounds represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. The present invention is not limited to these.
  • Another preferred embodiment of the compound containing an oxime sulfonate structure represented by the general formula (B1) is an oxime sulfonate compound represented by the following general formula (B1-3).
  • R 1 represents an alkyl group or an aryl group
  • R 2 represents an alkyl group, an aryl group, or a heteroaryl group
  • R 3 to R 6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom.
  • R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may be bonded to form an alicyclic ring or an aromatic ring.
  • X represents —O— or —S—.
  • R 1 represents an alkyl group or an aryl group.
  • the alkyl group include linear, branched, and cyclic groups, and branched or cyclic groups are preferable.
  • the alkyl group preferably has 3 to 10 carbon atoms. In the case of a branched alkyl group, the number of carbon atoms is preferably 3-6. In the case of a cyclic alkyl group, the number of carbon atoms is preferably 5 to 7.
  • alkyl group examples include, for example, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group.
  • Hexyl group, 2-ethylhexyl group, cyclohexyl group, octyl group and the like preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
  • the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms.
  • Specific examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
  • the alkyl group and aryl group represented by R 1 may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chloro atom, bromine atom, iodine atom), linear, branched or cyclic alkyl group (eg, methyl group, ethyl group, propyl group), alkenyl group, alkynyl group.
  • R 1 is preferably an alkyl group from the viewpoint of transparency, and R 1 is a branched alkyl group having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity.
  • R 1 is a branched alkyl group having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity.
  • a cyclic alkyl group having 5 to 7 carbon atoms, or a phenyl group is preferable, and a branched alkyl group having 3 to 6 carbon atoms or a cyclic alkyl group having 5 to 7 carbon atoms is more preferable.
  • an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.
  • R 2 represents an alkyl group, an aryl group, or a heteroaryl group.
  • the alkyl group represented by R 2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group, preferably a methyl group.
  • the aryl group an aryl group having 6 to 10 carbon atoms is preferable.
  • Examples of the aryl group include a phenyl group, a naphthyl group, and a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
  • Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
  • the alkyl group, aryl group, and heteroaryl group represented by R 2 may have a substituent. Examples of the substituent include an alkyl group and an aryl group R 1 represents is same as the substituents which may be possessed.
  • R 2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group.
  • As the substituent for the phenyl group a methyl group is preferred.
  • R 3 to R 6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom).
  • the alkyl group represented by R 3 to R 6 has the same meaning as the alkyl group represented by R 2 , and the preferred range is also the same.
  • the aryl group represented by R 3 to R 6 has the same meaning as the aryl group represented by R 1 , and the preferred range is also the same.
  • R 3 to R 6 , R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form a ring, and the ring forms an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
  • R 3 to R 6 are a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 It preferably constitutes a benzene ring, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are bonded to form a benzene ring Is more preferable.
  • Preferred embodiments of R 3 to R 6 are as follows. (Aspect 1) At least two are hydrogen atoms.
  • Ts represents a tosyl group (p-toluenesulfonyl group)
  • Me represents a methyl group
  • Bu represents an n-butyl group
  • Ph represents a phenyl group.
  • an imide sulfonate compound having a structure represented by the following general formula (B2) can be preferably used.
  • R 200 represents a monovalent organic group having 16 or less carbon atoms.
  • the wavy line represents a bond with another group.
  • R 200 represents a monovalent organic group having 16 or less carbon atoms.
  • R 200 preferably does not contain other than C, H, O, and F.
  • examples of R 200 include a methyl group, a trifluoromethyl group, a propyl group, a phenyl group, and a tosyl group.
  • a preferred embodiment of the compound containing the structure represented by the general formula (B2) is an imide sulfonate compound represented by the following general formula (I).
  • R 1 and R 2 each represent a group represented by the following general formula (A) or a hydrogen atom.
  • R 3 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group, a halogen atom, an alkylthio group, an alkyl group and an acyl
  • B represents the group represented by the following general formula (B).
  • X 1 represents an oxygen atom or a sulfur atom
  • Y 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms
  • R 4 represents a hydrocarbon group having 1 to 12 carbon atoms.
  • R 5 represents an alkylene group having 1 to 4 carbon atoms
  • R 6 represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic carbon atom having 3 to 10 carbon atoms. Represents a hydrogen group, a heterocyclic group, or a hydroxyl group.
  • n represents an integer of 0 to 5. When n is 2 to 5, a plurality of R 5 may be the same or different.
  • X 1 represents an oxygen atom or a sulfur atom
  • Y 1 represents a single bond or an alkanediyl group having 1 to 4 carbon atoms
  • R 11 represents a hydrocarbon group having 1 to 12 carbon atoms
  • R 12 represents an alkanediyl group having 1 to 4 carbon atoms
  • R 13 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a branch or an alicyclic hydrocarbon having 3 to 10 carbon atoms.
  • m represents 0 to 5, and when m is 2 to 5, a plurality of R 12 may be the same or different.
  • Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms
  • R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms
  • carbon Represents an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms
  • R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms
  • R 9 represents an alkyl group having 1 to 18 carbon atoms which may be branched, or 1 to 1 carbon atoms which may be branched.
  • a and b each independently represents 0 or 1, and at least one of a and b is 1.
  • the content of the (B) photoacid generator in the photosensitive resin composition of the present invention is preferably 0.1 to 10% by mass, and preferably 0.5 to 10% by mass with respect to the total solid content of the photosensitive resin composition. Is more preferable, and 1 to 5% by mass is even more preferable.
  • the (B) photoacid generator is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the (A) polysiloxane component. Part by mass is more preferable.
  • Only 1 type may be sufficient as a photo-acid generator, and it can also use 2 or more types together. When using 2 or more types together, it is preferable that the total amount becomes the said range.
  • the photosensitive resin composition of the present invention contains a solvent.
  • the photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent.
  • a solvent a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
  • a known solvent can be used as the solvent.
  • 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 Examples thereof include monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Further, the solvent described in paragraph Nos.
  • the solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.
  • the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
  • Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
  • Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
  • the content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition. 55 mass% or more is more preferable, and 60 mass parts or more is further more preferable.
  • the upper limit is more preferably 90 parts by mass or less. Only one type of solvent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.
  • the photosensitive resin composition of the present invention contains an alicyclic epoxy compound having a molecular weight of 150 to 1000 represented by the formula (EP) (hereinafter sometimes simply referred to as “alicyclic epoxy compound”).
  • (S) alicyclic epoxy compound” is a compound different from the polysiloxane described in the above (A) polysiloxane component.
  • R EP1 represents an alkyl group
  • p represents an integer of 0 to 7
  • A represents a q-valent hydrocarbon group that may contain an oxygen atom
  • q represents an integer of 1 to 4.
  • R EP1 represents an alkyl group.
  • Examples of the alkyl group include linear, branched and cyclic.
  • the alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • p represents an integer of 0 to 7, preferably 0 to 3, more preferably 0 or 1.
  • A represents a q-valent hydrocarbon group that may contain an oxygen atom.
  • the monovalent hydrocarbon group include an alkyl group and an aryl group, and an alkyl group is preferable.
  • the alkyl group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear.
  • the alkyl group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, an aryl group, and an aryloxy group.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
  • Examples of the divalent hydrocarbon group include an alkylene group and an arylene group, and an alkylene group is more preferable.
  • the alkylene group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear.
  • the alkylene group may be unsubstituted or may have a substituent.
  • Examples of the substituent include a halogen atom, an alkoxy group, an aryl group, and an aryloxy group.
  • the carbon number of the arylene group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12.
  • the arylene group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
  • Examples of the trivalent hydrocarbon group and the tetravalent hydrocarbon group include groups obtained by removing one or two hydrogen atoms from the above-described divalent hydrocarbon group.
  • hydrocarbon group containing an oxygen atom examples include a group formed by combining the above-described hydrocarbon group and at least one group selected from —O—, —CO—, —COO—, and —OCO—, A group formed by combining the above-described hydrocarbon group and at least one selected from —O—, —COO—, and —OCO— is more preferable, and the above-described hydrocarbon group and —COO— or —OCO— are combined.
  • the alicyclic epoxy compound is preferably a compound represented by the following formula (EP1).
  • R EP2 and R EP3 each independently represent an alkyl group
  • p represents an integer of 0 to 7
  • the plurality of R EP2 and R EP3 may be the same or different
  • a 1 represents a divalent hydrocarbon group containing at least one selected from —O—, —COO—, and —OCO—.
  • R EP2, R EP3, p has the same meaning as R EP, p in the general formula (EP), and preferred ranges are also the same.
  • a 1 represents a divalent hydrocarbon group containing at least one selected from —O—, —COO—, and —OCO—.
  • An alkylene group is preferable.
  • the alkylene group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear.
  • the alkylene group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
  • the alicyclic epoxy compound is preferably a compound represented by the following formula (EP2).
  • R EP2 and R EP3 each independently represent an alkyl group
  • p represents an integer of 0 to 7
  • a 2 represents an alkylene group.
  • R EP2, R EP3, p has the same meaning as R EP, p in the general formula (EP), and preferred ranges are also the same.
  • a 2 represents an alkylene group.
  • the alkylene group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear.
  • the alkylene group may have a substituent, but is preferably unsubstituted.
  • the production method of the alicyclic epoxy compound used in the present invention is not limited.
  • Maruzen KK Publishing, 4th Edition Experimental Chemistry Course 20 Organic Synthesis II, 213-, 1992, Ed. by Alfred Hasfner The chemistry of heterocyclic compounds-Small Ring Heterocycles part3 oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, adhesive, Vol. 29 No. 12, 32,1985, Yoshimura, adhesive, Vol. 30, No. 5 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, JP-A-1-100388, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.
  • the molecular weight of the alicyclic epoxy compound used in the present invention is 150 to 1000, preferably 200 to 400, and most preferably 200 to 300. By setting it as such a range, the effect of this invention is exhibited more effectively.
  • the molecular weight of an alicyclic epoxy compound is a theoretical value calculated from the structural formula, and when the molecular weight cannot be calculated from the structural formula, it is a weight average molecular weight based on a polystyrene conversion value by GPC measurement.
  • the content of the alicyclic epoxy compound in the photosensitive resin composition of the present invention is preferably 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • As for an upper limit 8 mass% or less is more preferable, and 5 mass% or less is still more preferable. Only one type of alicyclic epoxy compound may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.
  • the photosensitive resin composition of the present invention can contain a sensitizer in order to promote the decomposition of the photoacid generator in combination with the photoacid generator.
  • the sensitizer absorbs actinic rays or radiation and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur.
  • a photo-acid generator raise
  • preferable sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges of 350 to 450 nm.
  • Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene
  • xanthenes Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone
  • cyanines eg, thiacarbocyanine, oxacarbocyanine
  • merocyanines For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, to
  • polynuclear aromatics polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
  • polynuclear aromatics anthracene derivatives are most preferred.
  • the content of the sensitizer is preferably 0 to 1000 parts by weight, more preferably 10 to 500 parts by weight, and more preferably 50 to 200 parts by weight with respect to 100 parts by weight of the photoacid generator. Further preferred. Only one type of sensitizer may be used, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount is the said range.
  • the photosensitive resin composition of this invention can contain a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
  • the crosslinking agent is a compound containing at least two crosslinking groups in the molecule.
  • the cross-linking group means a group that reacts with one or more kinds selected from a cross-linkable group, a benzene ring, a hydroxy group, and a carboxy group of polysiloxane by heat.
  • a methylol group, an epoxy group, an oxetanyl group, an alkoxymethyl group, a methacryloyl group and an acryloyl group are preferable, and a methylol group, an epoxy group, an alkoxymethyl group, a methacryloyl group and an acryloyl group are more preferable.
  • the number of crosslinking groups in one molecule of the crosslinking agent is preferably 3 or more, and more preferably 4 or more.
  • the cross-linking group may have two or more of the same type of cross-linking group in the molecule, or may have two or more different types of cross-linking groups in the molecule.
  • the molecular weight of the crosslinking agent is preferably from 150 to 30,000, more preferably from 200 to 10,000. By setting it as such a range, the effect of this invention is exhibited more effectively.
  • the content of the crosslinking agent is 0.01 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition.
  • the amount is 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass. If it is the said range, the cured film excellent in mechanical strength and solvent tolerance will be obtained. Only one type of crosslinking agent may be used, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount is the said range.
  • the photosensitive resin composition of this invention can also be set as the structure which does not contain a crosslinking agent substantially. The configuration that is not practically used means that the crosslinking agent is, for example, 1% by mass or less of the solid content of the photosensitive resin composition.
  • ⁇ Compound having two or more epoxy groups in the molecule >>>
  • the crosslinking agent a compound that is different from the above-described (S) alicyclic epoxy compound and has two or more epoxy groups in the molecule can be used.
  • Specific examples of compounds having two or more epoxy groups in the molecule used as a crosslinking agent include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins, and aliphatic epoxy resins. And an acrylic resin having an epoxy group-containing structural unit. These are available as commercial products.
  • JER152, JER157S70, JER157S65, JER806, JER828, JER1007 are commercially available products described in paragraph No. 0189 of JP2011-212494, etc.
  • Crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule a crosslinking agent containing an alkoxymethyl group or a methylol group can be used as the crosslinking agent.
  • the crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule is a crosslinking agent having two or more structures represented by the following general formula (1) or general formula (2) in the molecule. , One or both of an alkoxymethyl group and a methylol group are contained in the molecule in a total of two or more.
  • —CH 2 OR 1 (1) (Wherein R 1 represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.) —CH 2 OH (2)
  • the alkoxymethyl group or methylol group is preferably bonded to a nitrogen atom or a carbon atom forming an aromatic ring.
  • Alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, and alkoxymethylated urea convert methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylol group of methylolated urea to alkoxymethyl group, respectively.
  • Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group, and the methoxymethyl group is particularly preferable from the viewpoint of outgas generation amount.
  • alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril are preferred, and from the viewpoint of transparency, alkoxymethylated glycoluril and methylol Glycoluril is particularly preferred.
  • an alkoxymethyl group-containing crosslinking agent described in paragraph No. 0107 of JP2012-8223A can be used, and the contents thereof are incorporated herein.
  • Preferred structures of the crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule include compounds represented by the following formulas (8-1) to (8-4).
  • R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 8 to R 11 each independently represents a hydrogen atom
  • a hydroxyl group, an alkyl group or an alkoxyl group is represented
  • X 2 represents a single bond, a methylene group or an oxygen atom.
  • the alkyl group represented by R 7 has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • the alkyl group represented by R 8 to R 11 preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • the alkoxyl group represented by R 8 to R 11 preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group.
  • X 2 is preferably a single bond or a methylene group.
  • R 7 to R 11 and X 2 may be substituted with an alkyl group such as a methyl group or an ethyl group, or a halogen atom.
  • the plurality of R 7 and R 8 to R 11 may be the same or different.
  • Crosslinkers containing two or more alkoxymethyl groups or methylol groups in the molecule are also available as commercial products, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalac MX-750, -032, -706, -708, -40,- 31, -270, -280, -290, -750LM, Nicarak MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used. These can be used alone or in combination of two or more.
  • a compound containing two or more methacryloyl groups or acryloyl groups in the molecule may be used as a crosslinking agent.
  • the compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. It is preferable that the acryloyl group and the methacryloyl group are compounds having two or more, more preferably trifunctional or more in one molecule.
  • bifunctional (meth) acrylate examples include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
  • Examples of the tri- or more functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
  • Preferable commercially available products are KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., NK ester series manufactured by Shin-Nakamura Chemical Co., Ltd., bifunctional A-200, A-400, A-600, A-1000, ABE-300, A- BPE-4, A-BPE-10, A-BPE-20, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A- B1206PE, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, BD, HD- N, NOD, IND, BPE-100, BPE-200, BPE-300, BPE-500, BPE-900, BPE-1300N, NPG, DCP, 1206PE, 701, 3 G, 9PG, tri
  • a compound containing an oxetanyl group may be used as a crosslinking agent. It is preferable that there are two or more oxetanyl groups in the molecule.
  • the compound having two or more oxetanyl groups in the molecule include the compounds described in paragraphs 0134 to 0145 of JP-A-2008-224970, the contents of which are incorporated herein.
  • Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.
  • the photosensitive resin composition of the present invention can contain a basic compound.
  • the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
  • aliphatic amine for example, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tributylamine, di-n-pentylamine, tri-n-pentylamine, Examples include diethanolamine, triethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
  • the content of the basic compound is preferably 0.001 to 3 parts by mass and more preferably 0.005 to 1 part by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition.
  • a basic compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.
  • the photosensitive resin composition of the present invention can contain a surfactant.
  • a surfactant any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • examples of the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
  • trade names are FA-630, KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No.
  • the surfactant is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and tetrahydrofuran (THF) as a solvent.
  • a preferred example is a copolymer having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.
  • R 401 and R 403 each independently represent a hydrogen atom or a methyl group
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 404 represents hydrogen.
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is 10 mass% to 80 mass%.
  • the following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.
  • L is preferably a branched alkylene group represented by the following general formula (I-1-2).
  • R 405 in formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • the content of the surfactant is preferably 10 parts by mass or less, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, the content is 0.01 to 3 parts by mass.
  • Surfactant may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.
  • the photosensitive resin composition of the present invention may contain an antioxidant.
  • an antioxidant a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
  • antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives.
  • phenolic antioxidants hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur antioxidants from the viewpoint of coloring the cured film and reducing film thickness Agents are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types. Specific examples include compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515, and compounds described in paragraph numbers 0106 to 0116 of JP-A-2011-227106. It is incorporated herein.
  • Preferred commercially available products are ADK STAB AO-20, ADK STAB AO-60, ADK STAB AO-80, ADK STAB LA-52, ADK STAB LA-81, ADK STAB AO-412S, ADK STAB PEP-36, IRGANOX 1035, IRGANOX 1098, and Tinuvin 144.
  • the content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, it is easy to form a film having excellent transparency. Furthermore, the sensitivity at the time of pattern formation is also good.
  • an acid proliferating agent can be used for the purpose of improving sensitivity.
  • the acid proliferating agent is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid.
  • Specific examples of the acid proliferating agent include acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-212494A, the contents of which are incorporated herein.
  • the photosensitive resin composition of the present invention can contain a development accelerator.
  • a development accelerator those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated herein.
  • the content 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 resin composition from the viewpoint of sensitivity and residual film ratio. More preferably, it is 1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass.
  • a development accelerator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.
  • the photosensitive resin composition of the present invention can contain an alkoxysilane compound.
  • an alkoxysilane compound a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable.
  • the alkoxy group contained in the alkoxysilane compound preferably has 1 to 5 carbon atoms.
  • the alkoxysilane compound is a compound that improves the adhesion between an insulating material and an inorganic material serving as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. It is preferable. Specifically, a known silane coupling agent or the like is also effective.
  • the photosensitive resin composition of the present invention is a known additive such as a plasticizer, a thermal radical generator, a thermal acid generator, a thermal radical generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor.
  • An agent can be added.
  • these compounds for example, the description of paragraph numbers 0201 to 0224 of JP2012-88459A can be referred to, and the contents thereof are incorporated in the present specification.
  • the photosensitive resin composition of the present invention can be prepared by mixing each component at a predetermined ratio and by any method, stirring and dissolving.
  • the photosensitive resin composition of the present invention can also be prepared by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent.
  • the composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 ⁇ m.
  • the solid content concentration of the photosensitive resin composition of the present invention at 25 ° C. is preferably 1 to 60% by mass, more preferably 3 to 40% by mass, further preferably 5 to 30% by mass, and particularly preferably 5 to 17% by mass. preferable.
  • the viscosity is preferably 1 to 100 mPa ⁇ s, more preferably 2 to 60 mPa ⁇ s, and most preferably 3 to 40 mPa ⁇ s.
  • Viscosity can be measured, for example, using a viscometer RE85L (rotor: 1 ° 34 ′ ⁇ R24 measurement range 0.6 to 1200 mPa ⁇ s) manufactured by Toki Sangyo Co., Ltd., with the temperature adjusted to 25 ° C. .
  • the photosensitive resin composition of this invention can also be preserve
  • the method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
  • substrate application
  • the substrate may be subjected to cleaning such as alkali cleaning or plasma cleaning. Further, the substrate surface may be treated with hexamethyldisilazane or the like with respect to the cleaned substrate.
  • the method of treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldisilazane vapor. Examples of the substrate include inorganic substrates, resins, and resin composite materials.
  • the inorganic substrate examples include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
  • the resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide
  • the method for applying the photosensitive resin composition to the substrate is not particularly limited.
  • an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, etc. Can be used.
  • the relative movement speed between the substrate and the slit die is preferably 50 to 120 mm / sec.
  • the wet film thickness when the photosensitive resin composition is applied is not particularly limited, and can be applied with a film thickness according to the application. For example, 0.5 to 10 ⁇ m is preferable.
  • pre-wet method as described in JP-A-2009-145395.
  • the solvent is removed from the wet film formed by applying the photosensitive resin composition by vacuum (vacuum) and / or heating to form a dry film on the substrate.
  • the heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.
  • the substrate provided with the dry film is irradiated with actinic rays having a predetermined pattern.
  • the photoacid generator is decomposed to generate an acid.
  • the acid-decomposable group contained in the coating film component is hydrolyzed to generate a carboxy group, a phenolic hydroxyl group, and the like.
  • a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, i-line (365 nm), h-line (405 nm), g-line ( Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used.
  • irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • the exposure amount is preferably 1 to 500 mJ / cm 2 .
  • various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
  • exposure using so-called super-resolution technology can also be performed.
  • the super-resolution technique include multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, a deformation proof method represented by an annular illumination method, and the like.
  • PEB Post Exposure Bake
  • the temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
  • a copolymer having a free carboxy group and a phenolic hydroxyl group is developed using a developer to form a positive image.
  • the developer used in the development step preferably contains an aqueous solution of 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, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; Alcoholamines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo- [5.4.0] -7-unde
  • sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
  • An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
  • the pH of the developer is preferably 10.0 to 14.0.
  • the development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
  • a rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like.
  • a known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
  • the acid-decomposable group is thermally decomposed to generate a carboxy group and a phenolic hydroxyl group, and crosslinked with a crosslinking group, a crosslinking agent, etc.
  • a cured film can be formed.
  • This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 400 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed.
  • post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process).
  • middle baking it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 180 ° C. for 1 to 60 minutes.
  • middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking.
  • These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
  • the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film.
  • the preferred exposure amount in the case of including a post-exposure step preferably 100 ⁇ 3,000mJ / cm 2, particularly preferably 100 ⁇ 500mJ / cm 2.
  • the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
  • dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
  • the cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention. 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 mentioned above.
  • the cured film of the present invention can be suitably used as an interlayer insulating film. It is preferable to use at least a part of the cured film in contact with the metal part, and it can be particularly preferably used as an insulating substrate for metal wiring.
  • the photosensitive resin composition of the present invention can provide an interlayer insulating film having high transparency even when baked at a high temperature.
  • the interlayer insulation film formed using the photosensitive resin composition of the present invention has high transparency and is useful for applications such as a liquid crystal display device, an organic electroluminescence display device, and a touch panel.
  • the liquid crystal display device of the present invention has 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 planarizing film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures. Can be mentioned.
  • specific examples of TFTs included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • the liquid crystal driving methods that can be adopted by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
  • the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device.
  • the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method.
  • the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
  • the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses.
  • a protective film for the color filter in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc.
  • FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10.
  • the 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 disposed on all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
  • Corresponding TFT 16 elements are arranged.
  • Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
  • an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
  • the light source of the backlight is not particularly limited, and a known light source can be used.
  • the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, a flexible type can also be used.
  • the second interlayer insulating film (48) described in JP2011-145686A, the interlayer insulating film (520) described in JP2009-258758A, JP It can be used as an organic insulating film (PAS) described in FIG. 1 of 2007-328210.
  • PAS organic insulating film
  • the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A-2001-125086.
  • reference numeral SUB1 denotes a glass substrate, which has a plurality of scanning signal lines and a plurality of video signal lines intersecting with the plurality of scanning signal lines.
  • a TFT is provided in the vicinity of each intersection.
  • a base film UC On the glass substrate SUB1, a base film UC, a semiconductor film PS such as silicon, a gate insulating film GI, a TFT gate electrode GT, and a first interlayer insulating film IN1 are formed in this order from the bottom.
  • a drain electrode SD1 of the TFT and a source electrode SD2 of the TFT are formed on the first interlayer insulating film IN1.
  • the drain electrode SD1 is connected to the drain region of the TFT through a contact hole formed in the gate insulating film GI and the first interlayer insulating film IN1.
  • the source electrode SD2 is connected to the source region of the TFT through a contact hole formed in the gate insulating film GI and the first interlayer insulating film IN1.
  • a second interlayer insulating film IN2 is formed on the drain electrode SD1 and the source electrode SD2.
  • An organic insulating film PAS is formed on the second interlayer insulating film IN2.
  • the organic insulating film PAS can be formed using the photosensitive resin composition of the present invention.
  • a counter electrode CT and a reflective film RAL are formed on the organic insulating film PAS.
  • a third interlayer insulating film IN3 is formed on the counter electrode CT and the reflective film RAL.
  • a pixel electrode PX is formed on the third interlayer insulating film IN3.
  • the pixel electrode PX is connected to the source electrode SD2 of the TFT through a contact hole formed in the second interlayer insulating film IN2 and the third interlayer insulating film IN3.
  • the organic insulating film PAS is formed using the photosensitive resin composition of the present invention, since the heat resistance of the organic insulating film PAS is excellent, the film forming temperature of the third interlayer insulating film IN3 is increased. And a denser film can be formed.
  • first interlayer insulating film IN1, the second interlayer insulating film IN2, and the third interlayer insulating film IN3 can also be formed using the photosensitive resin composition of the present invention.
  • the details of the liquid crystal display device shown in FIG. 2 can be referred to the description in Japanese Patent Application Laid-Open No. 2007-328210, and the contents thereof are incorporated in this specification.
  • the organic electroluminescence (organic EL) display device of the present invention has the cured film of the present invention.
  • the organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic materials having various structures.
  • An EL display device and a liquid crystal display device can be given.
  • specific examples of TFTs included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • FIG. 3 is a conceptual diagram of a configuration of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • a bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3.
  • the wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
  • the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
  • a bottom emission type organic EL element is formed on the planarizing film 4. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • the first electrode 5 corresponds to the anode of the organic EL element.
  • An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. be able to. Further, although not shown in FIG.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate.
  • An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it.
  • An EL display device is obtained.
  • the photosensitive resin composition of the present invention Since the photosensitive resin composition of the present invention has good sensitivity and excellent pattern adhesion during development, it is formed using the photosensitive resin composition of the present invention as a structural member of a MEMS (Micro Electro Mechanical Systems) device.
  • the resist pattern thus formed is used as a partition wall or incorporated as a part of a mechanical drive component.
  • MEMS devices include parts such as SAW (Surface Acoustic Wave) filters, BAW (Bulk Acoustic Wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, biochips, and sealants. It is done. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
  • the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010-
  • spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.
  • the touch panel of the present invention is a touch panel in which all or part of the insulating layer and / or protective layer is made of a cured product of the photosensitive resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an electrode, an insulating layer, and / or a protective layer at least.
  • the touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention.
  • any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, and an electromagnetic induction method may be used. Among these, the electrostatic capacity method is preferable.
  • Examples of the capacitive touch panel include those disclosed in JP 2010-28115 A and those disclosed in International Publication No. 2012/057165.
  • a touch panel display device As a touch panel display device, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7 and FIG. 8 of JP-A-2012-517051), a so-called on-cell type (for example, FIG. 19 of JP2013-168125A). , OGS type, TOL type, and other configurations (for example, FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164877).
  • the capacitive touch panel has at least a front plate and a non-contact side of the front plate.
  • the insulating layer (4) is preferably a cured film using the photosensitive resin composition of the present invention.
  • Frame layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) First transparent electrode pattern and electrical And a plurality of second transparent electrode patterns comprising a plurality of pad portions formed extending in a direction crossing the first direction.
  • First transparent electrode pattern and second transparent electrode pattern (5) The first transparent electrode pattern and the second transparent electrode pattern are electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern.
  • a transparent protective layer is further provided so as to cover all or a part of the elements (1) to (5).
  • the cured film of the present invention is more preferable. There.
  • FIG. 4 is a cross-sectional view illustrating a configuration example of a capacitive touch panel.
  • the capacitive touch panel 30 includes a front plate 31, a frame layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, and a conductive element 36. And a transparent protective layer 37.
  • the front plate 31 is made of a transparent substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used.
  • a transparent substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc.
  • a transparent substrate a glass substrate, a quartz substrate, a transparent resin substrate, etc. are mentioned preferably.
  • the side in which each element of the front plate 31 is provided is called a non-contact surface.
  • input is performed by bringing a finger or the like into contact with the contact surface of the front plate 31 (the surface opposite to the non-contact surface).
  • the front plate may be referred to as a “base material”.
  • a frame layer 32 is provided on the non-contact surface of the front plate 31.
  • the frame layer 32 is a frame-like pattern around the display area formed on the non-contact side of the front panel of the touch panel, and is formed so as not to show the lead wiring and the like.
  • the capacitive touch panel may be provided with a frame layer 32 so as to cover a part of the front plate 31 (a region other than the input surface in FIG. 5).
  • the front plate 31 can be provided with an opening 38 in part as shown in FIG. A mechanical switch by pressing can be installed in the opening 38.
  • a plurality of first transparent electrode patterns 33 formed with a plurality of pad portions extending in the first direction via the connection portions, A plurality of second transparent electrode patterns consisting of a plurality of pad portions that are electrically insulated from the first transparent electrode pattern 33 and extend in a direction crossing the first direction; An insulating layer 35 that electrically insulates the transparent electrode pattern 33 and the second transparent electrode pattern 34 is formed.
  • the 1st transparent electrode pattern 33, the 2nd transparent electrode pattern 34, and the electroconductive element 36 mentioned later can be produced with a metal film, for example.
  • the film thickness of each element can be 10 to 200 nm.
  • the amorphous ITO film can be crystallized into a polycrystalline ITO film by firing, and the electrical resistance can be reduced.
  • the 1st transparent electrode pattern 33, the 2nd transparent electrode pattern 34, and the electroconductive element 36 mentioned later are manufactured using the photosensitive transfer material which has the photosensitive resin composition using a conductive fiber. You can also In addition, when the first conductive pattern or the like is formed of ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to, and the contents thereof are incorporated in this specification.
  • At least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 extends over both the non-contact surface of the front plate 31 and the region of the frame layer 32 opposite to the front plate 31. Can be installed.
  • FIG. 4 a diagram is shown in which the second transparent electrode pattern is installed across both areas of the non-contact surface of the front plate 31 and the surface opposite to the front plate 31 of the frame layer 32. Yes.
  • FIG. 6 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern.
  • the first transparent electrode pattern 33 is formed such that the pad portion 33a extends in the first direction via the connection portion 33b.
  • the second transparent electrode pattern 34 is electrically insulated by the first transparent electrode pattern 33 and the insulating layer 35, and extends in a direction intersecting the first direction (second direction in FIG. 6). It is constituted by a plurality of pad portions that are formed.
  • the pad portion 33a and the connection portion 33b may be manufactured integrally, or only the connection portion 33b is manufactured, and the pad portion 33a and the second transparent electrode pattern 33 are formed.
  • the electrode pattern 34 may be integrally formed (patterned).
  • the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 6, a part of the connection part 33b and a part of the pad part 33a are connected and an insulating layer is formed. Each layer is formed so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by 35.
  • a conductive element 36 is installed on the surface side of the frame layer 32 opposite to the front plate 31.
  • the conductive element 36 is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34, and is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34. Is another element.
  • FIG. 4 a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.
  • the transparent protective layer 37 is installed so that all of each component may be covered.
  • the transparent protective layer 37 may be configured to cover only a part of each component.
  • the insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.
  • the touch panel display device including the capacitive touch panel and the capacitive touch panel as a constituent element is “Latest Touch Panel Technology” (Techno Times, issued July 6, 2009), supervised by Yuji Mitani, “Touch Panel The configurations disclosed in “Technology and Development” CMC Publishing (2004, 12), “FPD International 2009 Forum T-11 Lecture Textbook”, “Cypress Semiconductor Corporation Application Note AN2292” and the like can be applied.
  • the touch panel of the present invention can be manufactured, for example, as follows. That is, the photosensitive resin composition of the present invention is applied by various methods such as an inkjet coating method so as to be in contact with the ITO electrode, and an opening pattern having a predetermined shape is formed on the photosensitive resin composition applied to the ITO electrode. It can be manufactured through Step 2 in which a mask is placed and exposed by irradiation with active energy rays, Step 3 in which the exposed photosensitive resin composition is developed, and Step 4 in which the photosensitive resin composition after development is heated. .
  • Step 1 when the photosensitive resin composition is applied so as to be in contact with the ITO electrode, it is sufficient that at least a part of the applied photosensitive resin composition of the present invention is in contact with the ITO electrode.
  • Step 2 can be performed in the same manner as the exposure step described above, and the preferred embodiment is also the same.
  • Step 3 can be performed in the same manner as the development step described above, and the preferred embodiment is also the same.
  • Step 4 can be performed in the same manner as the post-baking step described above, and the preferred embodiment is also the same.
  • the ITO electrode pattern in the touch panel of this invention the pattern shown in FIG. 6 mentioned above is mentioned preferably.
  • NMR is an abbreviation for nuclear magnetic resonance.
  • A1-1 precursor polymer in which the carboxyl group of A1-1 was not protected with tetrahydrofuranyl.
  • 100 g of the resulting A1-1 precursor was dissolved in 400 mL of tetrahydrofuran, and after adding a catalytic amount of p-toluenesulfonic acid, a solution in which 30 g of dihydrofuran was dissolved in 30 g of tetrahydrofuran was added dropwise with stirring at 20 ° C. .
  • A1-1 was a polysiloxane having a carboxy group, a carboxy group, an epoxy group, a methyl group, and a phenyl group protected by a tetrahydrofuranyl group in the side chain.
  • Analysis by 1 H-NMR revealed that 78 mol% of the carboxy group was tetrahydrofuranylated in A1-1.
  • the types and molar ratios of the silane compounds used for the synthesis of A1-1 are shown below.
  • the three-necked flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes, and then reacted at 60 ° C. for 5 hours. During the reaction, methanol as a by-product was distilled off. The obtained polysiloxane DAA solution was poured into a large amount of water to precipitate a polymer, filtered and dried to obtain an A1-2 precursor.
  • the weight average molecular weight in terms of polystyrene by GPC was 5000.
  • Analysis by 1 H-NMR confirmed that 70 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxyethylated in A1-2.
  • the types and molar ratios of the silane compounds used for the synthesis of A1-2 are shown below.
  • A2-4 synthesis Synthesis of polysiloxane having carboxy group protected with acid-decomposable group Using silane compound in the following compounds and molar ratio, changing the protecting group to ethoxyethyl group to adjust the amount Except that, A2-4 was synthesized in the same manner as A1-1 by mixing and reacting the following silane compounds and introducing a protecting group by polymer reaction. In analysis by 1 H-NMR, it was confirmed that A2-4 was ethoxyethylated in 85 mol% of the carboxy group.
  • the resulting polysiloxane solution (80.4 g) was solvent-substituted from an ethyl acetate solution to a tetrahydrofuran solution (solid content concentration: 20% by mass), and then charged into a three-necked flask equipped with a thermometer, a stirrer, and a cooler. 1.0 g (0.01 mol) of acid was added. Next, 19.4 g (0.23 mol) of ethyl-1-propenyl ether was added dropwise while keeping the internal temperature at 10 ° C. or less with a dropping funnel while cooling with ice at 10 ° C. or lower and stirring.
  • the organic layer was separated and concentrated by a rotary evaporator to obtain 49.0 g of polysiloxane A′-1 having a colorless and transparent silanol group protected by acetal.
  • the acetal substitution rate of A′-1 was calculated to be 32.5 mol% from the NMR results.
  • B-2 PAI101 (trade name, structure shown below, manufactured by Midori Chemical Co., Ltd.)
  • B-2 is a photoacid generator that generates an acid having a pKa of 3 or less.
  • B-3 DTS-105 (trade name, triarylsulfonium salt, manufactured by Midori Chemical Co., Ltd.)
  • B-3 is a photoacid generator that generates an acid having a pKa of 3 or less.
  • B-4 Structure shown below (synthesized according to the method described in paragraph 249 of WO2011 / 087011 pamphlet)
  • B-4 is a photoacid generator that generates an acid having a pKa of 3 or less.
  • B-5 GSID-26-1 (trade name, triarylsulfonium salt, structure shown below, manufactured by BASF)
  • B-5 is a photoacid generator that generates an acid having a pKa of 3 or less.
  • B-6 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate
  • B-6 is a photoacid generator that generates an acid having a pKa of 3 or less.
  • B-7 Structure shown below
  • B-7 is a photoacid generator that generates an acid having a pKa of 3 or less.
  • B′-1 (Structure shown below.
  • B′-1 is a compound that generates an acid having a pKa of more than 3.
  • C Solvent>
  • C-1 Propylene glycol 1-monomethyl ether 2-acetate
  • C-2 Methyl ethyl diglycol
  • C-3 Diethyl diglycol
  • C-4 Butylene glycol diacetate
  • C-5 Cyclohexanol acetate
  • C-6 Ethylene glycol monomethyl Ether acetate
  • S-2 The following compound (manufactured by Daicel Corporation, Celoxide 2021P, molecular weight 252)
  • S-2 The following compound (molecular weight 268, synthetic product) It was synthesized according to the method described in Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213-.
  • S-4 The following compound (manufactured by Daicel Corporation, Celoxide 2000, molecular weight 378)
  • S-5 The following compound (molecular weight 520)
  • S′-1 the following compound (polysiloxane having an epoxy group, molecular weight 362)
  • 200 g of toluene, 134 g (1 mol) of 1,1,3,3-tetramethyldisiloxane, 228 g (2 mol) of allyl glycidyl ether, and platinum-divinyltetra 9 mg of methyldisiloxane complex (Karstedt catalyst) was added and reacted at 50-60 ° C. for 15 hours with stirring.
  • S′-2 The following compound (polysiloxane having an alicyclic epoxy group) 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 172.2 g (0.7 mol), dimethyldimethoxysilane 18 g (0.15 mol), methyltrimethoxysilane 20.4 g (0.15 mol), DAA (Diacetone alcohol) 500 g was charged into a three-necked flask, and an aqueous phosphoric acid solution in which 0.176 g of phosphoric acid was dissolved in 54 g of water was added over 30 minutes while stirring at room temperature.
  • the three-necked flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes, and then reacted at 60 ° C. for 8 hours. During the reaction, methanol as a by-product was distilled off. The obtained polysiloxane DAA solution was poured into a large amount of water to precipitate a polymer, filtered and dried to obtain S′-2.
  • the weight average molecular weight in terms of polystyrene by GPC was 2500.
  • S′-3 The following compound (manufactured by Daicel Corporation, EHPE-3150)
  • S′-4 the following compound 3 (manufactured by Daicel Corporation, Celoxide 2000, molecular weight 124)
  • TBA Tributylamine
  • TPI Triphenylimidazole
  • DBA 9,10-dibutoxyanthracene
  • FA-630 Silicone surfactant (FA-630, trade name, manufactured by Shin-Etsu Chemical)
  • F-554 Perfluoroalkyl group-containing nonionic surfactant (Megafac F-554, trade name, manufactured by DIC)
  • a glass substrate having a size of 680 mm ⁇ 880 mm (EAGLE XG, 0.7 mm thickness (manufactured by Corning)) was exposed to hexamethyldisilazane vapor for 30 seconds, and each photosensitive resin composition was slit-coated, followed by 90 ° C./120 Pre-baked on a second hot plate to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 2.5 ⁇ m.
  • the obtained photosensitive resin composition layer was exposed with a mask pattern having a hole shape of 7 ⁇ m in diameter using MPA 7800CF manufactured by Canon Inc.
  • the exposed photosensitive resin composition layer was developed with an alkali developer (0.6% tetramethylammonium hydroxide aqueous solution) at 24 ° C./55 seconds, and then rinsed with ultrapure water for 15 seconds.
  • an alkali developer (0.6% tetramethylammonium hydroxide aqueous solution) at 24 ° C./55 seconds, and then rinsed with ultrapure water for 15 seconds.
  • the optimum i-line exposure amount (Eopt) when resolving a hole having a diameter of 7 ⁇ m was determined and used as the sensitivity. Evaluation was made according to the following criteria. 1, 2 and 3 are practical levels.
  • the obtained photosensitive resin composition layer was used with a mask of an isolated dot pattern in which a circular dot pattern having a diameter of 15 ⁇ m was formed on a lattice point having a side of 200 ⁇ m by using MPA 7800CF manufactured by Canon Inc. Only the optimum exposure amount was exposed.
  • the exposed photosensitive resin composition layer was developed with an alkali developer (0.6% tetramethylammonium hydroxide aqueous solution) at 24 ° C./55 seconds, and then rinsed with ultrapure water for 20 seconds. In this way, an isolated dot pattern was formed on the entire surface of the substrate. Arbitrary 100 dots selected from the entire surface of the substrate were observed with an optical microscope, and the number of defective dots was counted.
  • the state in which a part of the pattern is chipped or the state in which the pattern is peeled is defined as a defect. Evaluation was made according to the following criteria. 1, 2 and 3 are practical levels. 1: Less than 3 2: 3 or more, less than 6 3: 6 or more, less than 10 4: 10 or more, less than 20 5: 20 or more
  • the photosensitive resin compositions of the examples were excellent in sensitivity and developability. Moreover, the cured film formed with the photosensitive resin composition of an Example was excellent in transparency even if it heated to 300 degreeC, and was excellent in heat resistance. Moreover, the photosensitive resin composition of an Example was excellent also in storage stability. On the other hand, the photosensitive resin composition of the comparative example was inferior in either sensitivity or developability.
  • Example 100 ⁇ Production of liquid crystal display device> (Example 100)
  • a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 100 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film.
  • the substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the photosensitive resin of Example 1 is used.
  • HMDS hexamethyldisilazane
  • the obtained photosensitive resin composition layer is 40 mJ / cm 2 (energy intensity: 20 mW / cm 2 ) through a hole pattern mask of 10 ⁇ m ⁇ using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. , I-line).
  • MPA 5500CF high pressure mercury lamp
  • Example 101 In the liquid crystal display device described in FIG. 1 of JP-A-2007-328210, the organic insulating film PAS was formed by the following method to obtain a liquid crystal display device. First, according to Japanese Patent Application Laid-Open No. 2007-328210, an array substrate formed up to just before the organic insulating film PAS was produced. Next, this substrate was exposed to hexamethyldisilazane vapor for 30 seconds, and then the photosensitive resin composition of Example 1 was slit-coated and then pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent. A photosensitive resin composition layer was formed.
  • the obtained photosensitive resin composition layer was subjected to an optimum exposure dose mJ / cm 2 (energy intensity: 20 mW / cm 2) through a hole pattern mask of 8 ⁇ m ⁇ using MPA 7800CF manufactured by Canon Inc. i-line) exposure.
  • the exposed photosensitive resin composition layer was developed with an alkali developer (0.6% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
  • the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , measured by i-line), and then the substrate was heated at 280 ° C. in an oven at 30 ° C.
  • the organic insulating film PAS was obtained by heating for a few minutes.
  • a liquid crystal display device was obtained in accordance with Japanese Unexamined Patent Publication No. 2007-328210.
  • the interlayer insulating film IN3 is formed at the same temperature as the interlayer insulating film IN2. Thereby, IN3 could be made into a dense film.
  • a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed very good display characteristics and had high reliability.
  • Example 201 An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 3).
  • a bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3. .
  • the wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.
  • the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
  • the planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiation with i-line (365 nm) at 45 mJ / cm 2 (energy intensity 20 mW / cm 2 ) using a mercury lamp, development is performed with an alkaline aqueous solution (0.4% TMAH aqueous solution) to form a pattern.
  • the integrated dose was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and a heat treatment was performed at 230 ° C./30 minutes.
  • the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking.
  • the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
  • a bottom emission type organic EL element was formed on the obtained flattening film 4.
  • a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed.
  • pattern processing was performed by wet etching using an ITO etchant.
  • the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials).
  • the first electrode 5 thus obtained corresponds to the anode of the organic EL element.
  • an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed.
  • the photosensitive resin composition of Example 16 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus.
  • a second electrode made of Al was formed on the entire surface above the substrate.
  • substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
  • a touch panel was produced by the method described below.
  • etching resist was applied onto ITO and dried to form an etching resist layer.
  • the distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the etching resist layer is set to 100 ⁇ m, pattern exposure is performed at an exposure amount of 50 mJ / cm 2 (i-line), and development is performed with a developer.
  • a post-baking treatment at 130 ° C. for 30 minutes was performed to obtain a front plate on which a transparent electrode layer and a photosensitive resin layer pattern for etching were formed.
  • the front plate on which the transparent electrode layer and the photo-sensitive resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched resist.
  • ITO etchant hydroochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.
  • the exposed transparent electrode layer not covered with the layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern with an etching resist layer pattern.
  • the transparent electrode layer-patterned front plate with the etching resist layer pattern is immersed in a dedicated resist stripping solution, the etching photosensitive resin layer is removed, and the frame layer and the first transparent electrode pattern A front plate formed was obtained.
  • the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 ⁇ m, 90 ° C., 120 seconds) to form a photosensitive resin composition layer.
  • the distance between the surface of the exposure mask (quartz exposure mask having a pattern for insulating layer) and the photosensitive resin composition layer was set to 30 ⁇ m, and pattern exposure was performed with the optimum exposure amount obtained by sensitivity evaluation.
  • the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds and rinsed with ultrapure water for 10 seconds.
  • a post-baking process at 220 ° C. for 45 minutes was performed to obtain a front plate on which a frame layer, a first transparent electrode pattern, and an insulating layer pattern were formed.
  • the front plate formed up to the insulating layer pattern was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa).
  • An ITO thin film having a thickness of 80 nm was formed to obtain a front plate on which a transparent electrode layer was formed.
  • the surface resistance of the ITO thin film was 110 ⁇ / ⁇ .
  • etching was performed and the etching resist layer was removed to form the frame layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1.
  • a front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was obtained.
  • the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 ⁇ m) on the front plate formed up to the conductive element different from the first and second transparent electrode patterns. , 90 ° C. for 120 seconds) to obtain a photosensitive resin composition film. Further, exposure, heat treatment, development, post-exposure (1,000 mJ / cm 2 ), and post-bake treatment are performed to form the frame layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. Insulating layer pattern, second transparent electrode pattern, insulating layer formed using the photosensitive resin composition of Example 1 so as to cover all the conductive elements different from the first and second transparent electrode patterns A front plate laminated with a (transparent protective layer) was obtained.
  • a liquid crystal display device manufactured by the method described in Japanese Patent Application Laid-Open No. 2009-47936 was bonded to the previously manufactured front plate, and a touch panel including a capacitive touch panel as a constituent element was manufactured by a known method.

Abstract

Provided is a photosensitive resin composition exhibiting excellent developability and having favorable sensitivity. Further provided are a method for producing a cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel. This photosensitive resin composition contains a polysiloxane component, a photoacid generator for generating an acid having a pKa of 3 or less, a solvent, and an alicyclic epoxy compound represented by formula (EP) and having a molecular weight of 150-1,000. REP1 represents an alkyl group, p represents an integer between 0 and 7, inclusive, A represents a hydrocarbon group which has a valence of q and may contain an oxygen atom, and q represents an integer between 1 and 4, inclusive.

Description

感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置、有機エレクトロルミネッセンス表示装置およびタッチパネルPhotosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic electroluminescence display device, and touch panel
　本発明は、感光性樹脂組成物に関する。さらに詳しくは、液晶表示装置、有機エレクトロルミネッセンス表示装置、タッチパネル、集積回路素子、固体撮像素子などの電子部品の平坦化膜、保護膜および層間絶縁膜等の形成に好適な、感光性樹脂組成物に関する。また、硬化膜の製造方法、感光性樹脂組成物を硬化してなる硬化膜、硬化膜を用いた液晶表示装置、有機エレクトロルミネッセンス表示装置などの画像表示装置、およびタッチパネルなどの入力装置に関する。 The present invention relates to a photosensitive resin composition. More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film, an interlayer insulating film, and the like of electronic components such as a liquid crystal display device, an organic electroluminescence display device, a touch panel, an integrated circuit element, and a solid-state imaging element About. The present invention also relates to a method for producing a cured film, a cured film obtained by curing a photosensitive resin composition, a liquid crystal display device using the cured film, an image display device such as an organic electroluminescence display device, and an input device such as a touch panel.
　有機エレクトロルミネッセンス表示装置、液晶表示装置などの画像表示装置、タッチパネルなどの入力装置などには、パターン形成された層間絶縁膜が設けられている。層間絶縁膜の形成には、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が得られるといったことから、感光性樹脂組成物が広く使用されている。感光性樹脂組成物の特性としては、感度が良いことが求められている。 An image display device such as an organic electroluminescence display device and a liquid crystal display device, and an input device such as a touch panel are provided with a patterned interlayer insulating film. In forming an interlayer insulating film, a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained. As a characteristic of the photosensitive resin composition, good sensitivity is required.
　最近、製造の効率化や表示装置の高性能化のために、層間絶縁膜製造後の装置作製工程において、従来よりも高い温度（例えば３００℃程度）での熱処理や製膜がなされており、層間絶縁膜にも従来よりも高い温度に対する耐性が求められている。このような高耐熱性の層間絶縁膜として、ポリシロキサンを用いることが検討されている。 Recently, heat treatment and film formation at higher temperatures (for example, about 300 ° C.) have been performed in the device manufacturing process after manufacturing the interlayer insulating film in order to improve manufacturing efficiency and display device performance. The interlayer insulating film is also required to have higher temperature resistance than before. The use of polysiloxane as such a high heat resistant interlayer insulating film has been studied.
　特許文献１には、アルカリ可溶性シロキサン重合体と、１，２－ナフトキノンジアド基を有する感光性化合物とを含有する感光性樹脂組成物が開示されている。
　特許文献２には、（Ａ）成分として、酸分解性基で保護されたカルボン酸を有する構成単位を含むポリシロキサン、（Ｂ）成分として、光酸発生剤、（Ｃ）成分として有機溶剤、（Ｄ）成分としてエポキシ基含有シロキサン化合物を含有する感光性樹脂組成物が開示されている。
　特許文献３には、保護されたシラノール基を有する構成単位と、エポキシ基を有する構成単位とを含むポリシロキサンを含有する感光性樹脂組成物が開示されている。 Patent Document 1 discloses a photosensitive resin composition containing an alkali-soluble siloxane polymer and a photosensitive compound having a 1,2-naphthoquinone diad group.
In Patent Document 2, polysiloxane containing a structural unit having a carboxylic acid protected with an acid-decomposable group as component (A), a photoacid generator as component (B), an organic solvent as component (C), A photosensitive resin composition containing an epoxy group-containing siloxane compound as component (D) is disclosed.
Patent Document 3 discloses a photosensitive resin composition containing polysiloxane containing a structural unit having a protected silanol group and a structural unit having an epoxy group.
　一方、特許文献４には、アクリル樹脂と、光酸発生剤と、脂環式エポキシ化合物とを含む感光性樹脂組成物が開示されている。 On the other hand, Patent Document 4 discloses a photosensitive resin composition containing an acrylic resin, a photoacid generator, and an alicyclic epoxy compound.
特開２００３－２５５５４６号公報JP 2003-255546 A 特開２０１３－９２６３３号公報JP 2013-92633 A 特開２００９－２６３５２２号公報JP 2009-263522 A 国際公開２０１４／００２８６１号パンフレットInternational Publication No. 2014/002861 Pamphlet
　しかしながら、本発明者らが、特許文献１に開示された感光性樹脂組成物について検討したところ、感度が充分ではないことが分かった。
　また、ポリシロキサンは、アクリル樹脂などに比べて基材との密着性が低い傾向にあり、現像密着性が劣る傾向にあった。特許文献２、３に開示された感光性樹脂組成物について検討したところ、現像密着性が劣り、更には、パターン欠けや、現像残渣が生じやすいことが分かった。パターンを微細化するに伴い、これらの問題は顕著に生じる傾向にあり、微細パターンを安定して形成することが困難であった。 However, when the present inventors examined the photosensitive resin composition disclosed in Patent Document 1, it was found that the sensitivity was not sufficient.
In addition, polysiloxane tends to have lower adhesion to the substrate than acrylic resin and the like, and development adhesion tends to be inferior. When the photosensitive resin compositions disclosed in Patent Documents 2 and 3 were examined, it was found that the development adhesiveness was inferior, and further, pattern chipping and development residues were likely to occur. As the pattern is miniaturized, these problems tend to occur remarkably, and it is difficult to stably form the fine pattern.
　一方、特許文献４には、アクリル樹脂を用いた感光性樹脂組成物において、脂環式エポキシ化合物を含有させることで、感度および加熱後の透明性を維持しつつ、均一なコンタクトコールを形成することができると記載されているが、パターン欠陥や、現像残渣の抑制に関する記載はない。 On the other hand, in Patent Document 4, in a photosensitive resin composition using an acrylic resin, a uniform contact call is formed while maintaining sensitivity and transparency after heating by including an alicyclic epoxy compound. However, there is no description regarding suppression of pattern defects and development residues.
　よって、本発明の目的は、感度が良好で、パターン欠陥および現像残渣の抑制された感光性樹脂組成物を提供することにある。また、感光性樹脂組成物を用いた硬化膜の製造方法、硬化膜、液晶表示装置、有機エレクトロルミネッセンス表示装置およびタッチパネルを提供することにある。 Therefore, an object of the present invention is to provide a photosensitive resin composition having good sensitivity and having suppressed pattern defects and development residues. Moreover, it is providing the manufacturing method of a cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel.
　かかる状況のもと、本発明者らが検討を行った結果、ポリシロキサン成分と、ｐＫａが３以下の酸を発生する光酸発生剤と、溶剤と、後述する脂環式エポキシ化合物とを含む感光性樹脂組成物により、感度が良好で、パターン欠陥および現像残渣の抑制された感光性樹脂組成物が得られることを見出し、本発明を完成するに至った。本発明は以下を提供する。 Under such circumstances, as a result of investigations by the present inventors, a polysiloxane component, a photoacid generator that generates an acid having a pKa of 3 or less, a solvent, and an alicyclic epoxy compound described later are included. It has been found that a photosensitive resin composition having a good sensitivity and having suppressed pattern defects and development residues can be obtained by the photosensitive resin composition, and the present invention has been completed. The present invention provides the following.
　＜１＞　成分Ａとして下記１および２の少なくとも一方を満たすポリシロキサン成分、
　１：構成単位ａ１としてカルボキシ基が酸分解性基で保護された基、および、フェノール性水酸基が酸分解性基で保護された基から選ばれる少なくとも１種の基を有する構成単位と、構成単位ａ２として架橋性基を有する構成単位とを有するポリシロキサンを含むポリシロキサン成分、
　２：構成単位ａ１としてカルボキシ基が酸分解性基で保護された基、および、フェノール性水酸基が酸分解性基で保護された基から選ばれる少なくとも１種の基を有する構成単位を有するポリシロキサンと、構成単位ａ２として架橋性基を有する構成単位を有するポリシロキサンとを含むポリシロキサン成分、
　成分ＢとしてｐＫａが３以下の酸を発生する光酸発生剤、
　成分Ｃとして溶剤、ならびに、
　成分Ｓとして下式ＥＰで表される分子量１５０～１０００の脂環式エポキシ化合物を含む感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000004
 　式中、ＲＥＰ１はアルキル基を表し、
　ｐは０～７の整数を表し、ｐが２以上の場合、複数のＲＥＰ１は同一であってもよく、異なってもよく、
　Ａは、酸素原子を有していてもよい、ｑ価の炭化水素基を表し、
　ｑは１～４の整数を表す。
＜２＞　感光性樹脂組成物の全固形分に対して、脂環式エポキシ化合物を、０．１～１０質量％含有する、＜１＞に記載の感光性樹脂組成物。
＜３＞　脂環式エポキシ化合物の分子量が２００～４００である、＜１＞又は＜２＞に記載の感光性樹脂組成物。
＜４＞　脂環式エポキシ化合物が、下式ＥＰ１で表される化合物である、＜１＞～＜３＞のいずれかに記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000005
 　式中、ＲＥＰ２およびＲＥＰ３は、それぞれ独立にアルキル基を表し、
　ｐは０～７の整数を表し、ｐが２以上の場合、複数のＲＥＰ２およびＲＥＰ３は、同一であってもよく、異なってもよく、
　Ａ１は、－Ｏ－、－ＣＯＯ－および－ＯＣＯ－から選ばれる少なくとも１種を含む２価の炭化水素基を表す。
＜５＞　ポリシロキサン成分が有する酸分解性基は、アセタール基である＜１＞～＜４＞のいずれかに記載の感光性樹脂組成物。
＜６＞　構成単位ａ１が、下記一般式ａ１－１で表される構成単位、および、下記一般式ａ１－２で表される構成単位から選ばれる少なくとも１種である、＜１＞～＜５＞のいずれかに記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000006
 　一般式ａ１－１、および、一般式ａ１－２中、ａは０または１を表し、
　Ｒ１およびＲ２は、それぞれ独立に、水素原子、アルキル基またはアリール基を表し、Ｒ１およびＲ２の少なくとも一方は、アルキル基またはアリール基を表し、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、アルキル基、アリール基、または、アラルキル基を表し、
　Ｌ１は、単結合または２価の連結基を表し、
　Ｌ２は、単結合または２価の連結基を表し、
　Ｒｘは、アルキル基またはハロゲン原子を表し、
　ｍ１は、０～４の整数を表す。
＜７＞　ポリシロキサン成分が有する架橋性基が、環状エーテル、および、エチレン性不飽和結合を有する基から選ばれる少なくとも１種である、＜１＞～＜６＞のいずれかに記載の感光性樹脂組成物。
＜８＞　ポリシロキサンは、カルボキシ基およびフェノール性水酸基から選ばれる少なくとも１種の基を有する構成単位をさらに含む、＜１＞～＜７＞のいずれかに記載の感光性樹脂組成物。
＜９＞　光酸発生剤が、オニウム塩化合物、オキシムスルホネート化合物、および、イミドスルホネート化合物から選ばれる少なくとも１種である、＜１＞～＜８＞のいずれかに記載の感光性樹脂組成物。
＜１０＞　＜１＞～＜９＞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工程、基板に塗布された感光性樹脂組成物から溶剤を除去する工程、溶剤が除去された感光性樹脂組成物を露光する工程、露光された感光性樹脂組成物を現像する工程、および、現像された感光性樹脂組成物を熱硬化する工程、を含む硬化膜の製造方法。
＜１１＞　＜１＞～＜９＞のいずれかに記載の感光性樹脂組成物を硬化した硬化膜。
＜１２＞　層間絶縁膜である、＜１１＞に記載の硬化膜。
＜１３＞　＜１１＞または＜１２＞に記載の硬化膜を有する、液晶表示装置。
＜１４＞　＜１１＞または＜１２＞に記載の硬化膜を有する、有機エレクトロルミネッセンス表示装置。
＜１５＞　＜１１＞または＜１２＞に記載の硬化膜を有する、タッチパネル。 <1> Polysiloxane component satisfying at least one of the following 1 and 2 as component A,
1: a structural unit having at least one group selected from a group in which a carboxy group is protected by an acid-decomposable group and a group in which a phenolic hydroxyl group is protected by an acid-decomposable group as the structural unit a1, and a structural unit a polysiloxane component including a polysiloxane having a structural unit having a crosslinkable group as a2.
2: Polysiloxane having a structural unit having at least one group selected from a group in which a carboxy group is protected by an acid-decomposable group and a group in which a phenolic hydroxyl group is protected by an acid-decomposable group as the structural unit a1 And a polysiloxane component comprising a polysiloxane having a structural unit having a crosslinkable group as the structural unit a2.
A photoacid generator that generates an acid having a pKa of 3 or less as component B;
A solvent as component C, and
A photosensitive resin composition comprising, as component S, an alicyclic epoxy compound having a molecular weight of 150 to 1000 represented by the following formula EP;
Figure JPOXMLDOC01-appb-C000004
 In the formula, R EP1 represents an alkyl group,
p represents an integer of 0 to 7, and when p is 2 or more, a plurality of R EP1 may be the same or different,
A represents a q-valent hydrocarbon group which may have an oxygen atom,
q represents an integer of 1 to 4.
<2> The photosensitive resin composition according to <1>, containing 0.1 to 10% by mass of an alicyclic epoxy compound with respect to the total solid content of the photosensitive resin composition.
<3> The photosensitive resin composition according to <1> or <2>, wherein the alicyclic epoxy compound has a molecular weight of 200 to 400.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the alicyclic epoxy compound is a compound represented by the following formula EP1:
Figure JPOXMLDOC01-appb-C000005
 In the formula, R EP2 and R EP3 each independently represent an alkyl group,
p represents an integer of 0 to 7, and when p is 2 or more, the plurality of R EP2 and R EP3 may be the same or different,
A 1 represents a divalent hydrocarbon group containing at least one selected from —O—, —COO—, and —OCO—.
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the acid-decomposable group contained in the polysiloxane component is an acetal group.
<6> The structural unit a1 is at least one selected from a structural unit represented by the following general formula a1-1 and a structural unit represented by the following general formula a1-2. <1> to <5 > The photosensitive resin composition in any one of>
Figure JPOXMLDOC01-appb-C000006
 In general formula a1-1 and general formula a1-2, a represents 0 or 1,
R 1 and R 2 each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 represents an alkyl group or an aryl group, and R 3 represents an alkyl group or an aryl group. R 1 or R 2 and R 3 may be linked to form a cyclic ether,
R 4 represents an alkyl group, an aryl group, or an aralkyl group,
L 1 represents a single bond or a divalent linking group,
L 2 represents a single bond or a divalent linking group,
R x represents an alkyl group or a halogen atom,
m1 represents an integer of 0 to 4.
<7> The photosensitivity according to any one of <1> to <6>, wherein the crosslinkable group of the polysiloxane component is at least one selected from cyclic ether and a group having an ethylenically unsaturated bond. Resin composition.
<8> The photosensitive resin composition according to any one of <1> to <7>, wherein the polysiloxane further includes a structural unit having at least one group selected from a carboxy group and a phenolic hydroxyl group.
<9> The photosensitive resin composition according to any one of <1> to <8>, wherein the photoacid generator is at least one selected from an onium salt compound, an oxime sulfonate compound, and an imide sulfonate compound.
<10> A step of applying the photosensitive resin composition according to any one of <1> to <9> on the substrate, a step of removing the solvent from the photosensitive resin composition applied to the substrate, and the solvent being removed. A method for producing a cured film, comprising: exposing the exposed photosensitive resin composition; developing the exposed photosensitive resin composition; and thermally curing the developed photosensitive resin composition.
<11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <9>.
<12> The cured film according to <11>, which is an interlayer insulating film.
<13> A liquid crystal display device having the cured film according to <11> or <12>.
<14> An organic electroluminescence display device having the cured film according to <11> or <12>.
<15> A touch panel having the cured film according to <11> or <12>.
　感度が良好で、パターン欠陥および現像残渣の抑制された感光性樹脂組成物を提供可能になった。また、感光性樹脂組成物を用いた硬化膜の製造方法、硬化膜、液晶表示装置、有機エレクトロルミネッセンス表示装置およびタッチパネルを提供可能になった。 It is now possible to provide a photosensitive resin composition with good sensitivity and suppressed pattern defects and development residues. Moreover, the manufacturing method of the cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel can be provided now.
液晶表示装置の一例の構成概念図である。It is a composition conceptual diagram of an example of a liquid crystal display. 液晶表示装置の他の例の構成概念図である。It is a composition conceptual diagram of other examples of a liquid crystal display. 有機ＥＬ表示装置の一例の構成概念図を示す。1 shows a conceptual diagram of a configuration of an example of an organic EL display device. 静電容量方式のタッチパネルの構成例を示す断面図である。It is sectional drawing which shows the structural example of a capacitive touch panel. 前面板の一例を示す説明図である。It is explanatory drawing which shows an example of a front plate. 第一の透明電極パターンおよび第二の透明電極パターンの一例を示す説明図である。It is explanatory drawing which shows an example of a 1st transparent electrode pattern and a 2nd transparent electrode pattern.
　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。
　なお、本明細書において「～」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。
　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。
　本明細書における固形分濃度とは、２５℃における固形分の濃度をいう。
　本明細書における粘度とは、２５℃における粘度をいう。
　本明細書において、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）測定によるポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８１２０（東ソー（株）製）を用い、カラムとしてＴＳＫ　ｇｅｌ　Ｍｕｌｔｉｐｏｒｅ　ＨＸＬ－Ｍ（東ソー（株）製、７．８ｍｍＩＤ×３０．０ｃｍを、溶離液としてＴＨＦ（テトラヒドロフラン）を用いることによって求めることができる。 Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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).
The solid content concentration in this specification refers to the solid content concentration at 25 ° C.
The viscosity in this specification refers to a viscosity at 25 ° C.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by a gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, using HLC-8120 (manufactured by Tosoh Corp.) and using TSK gel Multipore HXL-M (manufactured by Tosoh Corp.) as a column. 7.8 mm ID × 30.0 cm can be determined by using THF (tetrahydrofuran) as the eluent.
＜感光性樹脂組成物＞
　本発明の感光性樹脂組成物は、（Ａ）後述するポリシロキサン成分と、（Ｂ）ｐＫａが３以下の酸を発生する光酸発生剤と、（Ｃ）溶剤と、（Ｄ）分子量１５０～１０００の後述する式（ＥＰ）で表される脂環式エポキシ化合物とを含有する。
　本発明の感光性樹脂組成物は、後述するポリシロキサン成分と、光酸発生剤を含むので、感度が良好である。また、ポリシロキサン成分を含ことにより、耐熱性に優れた硬化膜を形成することもできる。そして、脂環式エポキシ化合物を配合することで、パターンの端部がテーパー形状になり、基材に対する接地面積が大きくなるため現像密着性に優れる。従って、現像時の残渣や欠けの無い微細パターンを安定して形成することができる。
　本発明の感光性樹脂組成物は、化学増幅型ポジ型感光性樹脂組成物として好ましく用いることができる。
　以下、本発明の感光性樹脂組成物の各成分についてさらに詳しく説明する。 <Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises (A) a polysiloxane component described later, (B) a photoacid generator that generates an acid having a pKa of 3 or less, (C) a solvent, (D) a molecular weight of 150 to 1000 cycloaliphatic epoxy compounds represented by the formula (EP) described later.
Since the photosensitive resin composition of this invention contains the polysiloxane component mentioned later and a photo-acid generator, a sensitivity is favorable. Moreover, the cured film excellent in heat resistance can also be formed by including a polysiloxane component. And by mix | blending an alicyclic epoxy compound, the edge part of a pattern becomes a taper shape, and since the ground contact area with respect to a base material becomes large, it is excellent in image development adhesiveness. Therefore, it is possible to stably form a fine pattern free from residues and chips during development.
The photosensitive resin composition of the present invention can be preferably used as a chemically amplified positive photosensitive resin composition.
Hereinafter, each component of the photosensitive resin composition of the present invention will be described in more detail.
＜＜（Ａ）ポリシロキサン成分（Ａ成分）＞＞
　本発明の感光性樹脂組成物において、ポリシロキサン成分は、下記（１）および（２）の少なくとも一方を満たす。
　（１）（ａ１）カルボキシ基が酸分解性基で保護された基、および、フェノール性水酸基が酸分解性基で保護された基から選ばれる少なくとも１種の基を有する構成単位と、（ａ２）架橋性基を有する構成単位とを有するポリシロキサン（Ａ１）を含むポリシロキサン成分。
　（２）（ａ１）カルボキシ基が酸分解性基で保護された基、および、フェノール性水酸基が酸分解性基で保護された基から選ばれる少なくとも１種の基を有する構成単位を有するポリシロキサン（Ａ２）と、（ａ２）架橋性基を有する構成単位を有するポリシロキサン（Ａ３）とを含むポリシロキサン成分。
　（Ａ）ポリシロキサン成分は、特に述べない限り、上記ポリシロキサンに加え、必要に応じて添加される他のポリシロキサンを含めたものを意味する。
　（Ａ）ポリシロキサン成分に含まれる構成単位（ａ１）と構成単位（ａ２）とのモル比は、構成単位（ａ１）：構成単位（ａ２）＝１０：９０～９０：１０が好ましく、８０：２０～２０：８０がより好ましく、６０：４０～３０：７０が更に好ましい。 << (A) Polysiloxane Component (Component A) >>
In the photosensitive resin composition of the present invention, the polysiloxane component satisfies at least one of the following (1) and (2).
(1) (a1) a structural unit having at least one group selected from a group in which a carboxy group is protected with an acid-decomposable group and a group in which a phenolic hydroxyl group is protected with an acid-decomposable group; And a polysiloxane component comprising a polysiloxane (A1) having a structural unit having a crosslinkable group.
(2) (a1) Polysiloxane having a structural unit having at least one group selected from a group in which a carboxy group is protected with an acid-decomposable group and a group in which a phenolic hydroxyl group is protected with an acid-decomposable group A polysiloxane component comprising (A2) and (a2) polysiloxane (A3) having a structural unit having a crosslinkable group.
(A) Unless otherwise stated, a polysiloxane component means what included other polysiloxane added as needed in addition to the said polysiloxane.
(A) The molar ratio between the structural unit (a1) and the structural unit (a2) contained in the polysiloxane component is preferably structural unit (a1): structural unit (a2) = 10: 90 to 90:10, 80: 20 to 20:80 is more preferable, and 60:40 to 30:70 is still more preferable.
　上記（１）の態様では、少なくとも１種類のポリシロキサン（Ａ１）を含み、ポリシロキサン（Ａ１）が構成単位（ａ１）、および構成単位（ａ２）を有する態様である。構成単位（ａ１）や、構成単位（ａ２）は、それぞれ、２種類以上含んでいてもよい。また、後述する酸基を有する構成単位（ａ３）や、構成単位（ａ４）を含んでいてもよい。
　ポリシロキサン（Ａ１）の構成単位（ａ１）の割合は、感度の観点から、ポリシロキサン（Ａ１）の全構成単位に対して、１０～９０モル％が好ましい。下限は、１５モル％以上が好ましく、２０モル％以上が更に好ましい。上限は、８０モル％以下が好ましく、６０モル％以下が更に好ましい。
　また、構成単位（ａ２）の割合は、硬化膜特性の観点から、ポリシロキサン（Ａ１）の全構成単位に対して、１０～９０モル％が好ましい。下限は、２０モル％以上が好ましく、３０モル％以上が更に好ましい。上限は、８０モル％以下が好ましく、７０モル％以下が更に好ましい。
　また、構成単位（ａ３）の割合は、感度の観点から、ポリシロキサン（Ａ１）の全構成単位に対して、０～５０モル％が好ましい。下限は、１モル％以上が好ましく、５モル％以上が更に好ましい。上限は、３０モル％以下が好ましく、２０モル％以下が更に好ましい。
　また、構成単位（ａ４）の割合は、現像性、および、硬化膜特性の観点から、ポリシロキサン（Ａ１）の全構成単位に対して、０～４０モル％が好ましい。下限は、１モル％以上が好ましく、５モル％以上が更に好ましい。上限は、３０モル％以下が好ましく、２０モル％以下が更に好ましい。 In the aspect (1), at least one polysiloxane (A1) is contained, and the polysiloxane (A1) has the structural unit (a1) and the structural unit (a2). Each of the structural unit (a1) and the structural unit (a2) may contain two or more types. Moreover, the structural unit (a3) which has an acid group mentioned later, and the structural unit (a4) may be included.
The proportion of the structural unit (a1) of the polysiloxane (A1) is preferably 10 to 90 mol% with respect to the total structural units of the polysiloxane (A1) from the viewpoint of sensitivity. The lower limit is preferably 15 mol% or more, and more preferably 20 mol% or more. The upper limit is preferably 80 mol% or less, and more preferably 60 mol% or less.
The proportion of the structural unit (a2) is preferably 10 to 90 mol% with respect to all the structural units of the polysiloxane (A1) from the viewpoint of cured film characteristics. The lower limit is preferably 20 mol% or more, and more preferably 30 mol% or more. The upper limit is preferably 80 mol% or less, and more preferably 70 mol% or less.
In addition, the proportion of the structural unit (a3) is preferably 0 to 50 mol% with respect to all the structural units of the polysiloxane (A1) from the viewpoint of sensitivity. The lower limit is preferably 1 mol% or more, more preferably 5 mol% or more. The upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
The proportion of the structural unit (a4) is preferably 0 to 40 mol% with respect to all the structural units of the polysiloxane (A1) from the viewpoints of developability and cured film characteristics. The lower limit is preferably 1 mol% or more, more preferably 5 mol% or more. The upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
　上記（２）の態様では、構成単位（ａ１）を有するポリシロキサン（Ａ２）と、構成単位（ａ２）を有するポリシロキサン（Ａ３）とを含む態様である。構成単位（ａ１）を含むポリシロキサン（Ａ２）は、さらに、構成単位（ａ２）を含んでいても良い。同様に、構成単位（ａ２）を含むポリシロキサン（Ａ３）は、構成単位（ａ１）を含んでいても良い。このような場合、（１）と（２）の両方を満たす態様となる。また、ポリシロキサン（Ａ２）、ポリシロキサン（Ａ３）は、後述する酸基を有する構成単位（ａ３）や、構成単位（ａ４）を含んでいてもよい。
　ポリシロキサン（Ａ２）の構成単位（ａ１）の割合は、ポリシロキサン（Ａ２）の全構成単位に対して、１０～９０モル％が好ましい。下限は、３０モル％以上が好ましく、４０モル％以上が更に好ましい。上限は、９０モル％以下が好ましく、８０モル％以下が更に好ましい。また、構成単位（ａ３）の割合は、ポリシロキサン（Ａ２）の全構成単位に対して、０～５０モル％が好ましい。下限は、１モル％以上が好ましく、５モル％以上が更に好ましい。上限は、３０モル％以下が好ましく、２０モル％以下が更に好ましい。また、構成単位（ａ４）の割合は、ポリシロキサン（Ａ２）の全構成単位に対して、０～４０モル％が好ましい。下限は、１モル％以上が好ましく、５モル％以上が更に好ましい。上限は、３０モル％以下が好ましく、２０モル％以下が更に好ましい。
　ポリシロキサン（Ａ３）の構成単位（ａ２）の割合は、ポリシロキサン（Ａ３）の全構成単位に対して、１０～９０モル％が好ましい。下限は、３０モル％以上が好ましく、５０モル％以上が更に好ましい。上限は、９０モル％以下が好ましく、８０モル％以下が更に好ましい。また、構成単位（ａ４）の割合は、ポリシロキサン（Ａ３）の全構成単位に対して、０～４０モル％が好ましい。下限は、１モル％以上が好ましく、５モル％以上が更に好ましい。上限は、３０モル％以下が好ましく、２０モル％以下が更に好ましい。
　上記（２）の態様の場合には、構成単位（ａ１）を有するポリシロキサン（Ａ２）と、構成単位（ａ２）を有するポリシロキサン（Ａ３）との質量割合は、９５：５～５：９５が好ましく、８０：２０～２０：８０がより好ましく、７０：３０～３０：７０がさらに好ましい。 In the aspect (2), the polysiloxane (A2) having the structural unit (a1) and the polysiloxane (A3) having the structural unit (a2) are included. The polysiloxane (A2) containing the structural unit (a1) may further contain the structural unit (a2). Similarly, the polysiloxane (A3) containing the structural unit (a2) may contain the structural unit (a1). In such a case, the aspect satisfies both (1) and (2). Moreover, polysiloxane (A2) and polysiloxane (A3) may contain the structural unit (a3) which has the acid group mentioned later, and a structural unit (a4).
The proportion of the structural unit (a1) of the polysiloxane (A2) is preferably 10 to 90 mol% with respect to all the structural units of the polysiloxane (A2). The lower limit is preferably 30 mol% or more, and more preferably 40 mol% or more. The upper limit is preferably 90 mol% or less, and more preferably 80 mol% or less. The proportion of the structural unit (a3) is preferably 0 to 50 mol% with respect to all the structural units of the polysiloxane (A2). The lower limit is preferably 1 mol% or more, more preferably 5 mol% or more. The upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less. The proportion of the structural unit (a4) is preferably 0 to 40 mol% with respect to all the structural units of the polysiloxane (A2). The lower limit is preferably 1 mol% or more, more preferably 5 mol% or more. The upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
The proportion of the structural unit (a2) of the polysiloxane (A3) is preferably 10 to 90 mol% with respect to all the structural units of the polysiloxane (A3). The lower limit is preferably 30 mol% or more, and more preferably 50 mol% or more. The upper limit is preferably 90 mol% or less, and more preferably 80 mol% or less. The proportion of the structural unit (a4) is preferably 0 to 40 mol% with respect to all the structural units of the polysiloxane (A3). The lower limit is preferably 1 mol% or more, more preferably 5 mol% or more. The upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
In the case of the above aspect (2), the mass ratio of the polysiloxane (A2) having the structural unit (a1) and the polysiloxane (A3) having the structural unit (a2) is 95: 5 to 5:95. Is preferable, 80:20 to 20:80 is more preferable, and 70:30 to 30:70 is more preferable.
　本発明に用いるポリシロキサンの構造は、特に限定はない。直鎖状、環状、梯子状、網目状いずれでもよく、これらが相互に連結された構造でも良い。梯子状または、網目状の構造を含むことが硬化膜硬度の点で好ましい。
　ポリシロキサン成分に含まれるポリシロキサンの重量平均分子量は、１，０００～２００，０００が好ましく、２，０００～５０，０００がより好ましい。上記範囲内であると、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。 The structure of the polysiloxane used in the present invention is not particularly limited. Any of a straight chain shape, a ring shape, a ladder shape, and a mesh shape may be used, and a structure in which these are connected to each other may be used. It is preferable in terms of hardness of the cured film that a ladder-like or network-like structure is included.
The weight average molecular weight of the polysiloxane contained in the polysiloxane component is preferably 1,000 to 200,000, and more preferably 2,000 to 50,000. Various characteristics are favorable in the said range. The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
＜＜＜（ａ１）カルボキシ基が酸分解性基で保護された基、および、フェノール性水酸基が酸分解性基で保護された基から選ばれる少なくとも１種の基を有する構成単位＞＞＞
　本発明で用いるポリシロキサンは、カルボキシ基が酸分解性基で保護された基、および、フェノール性水酸基が酸分解性基で保護された基から選ばれる少なくとも１種の基を有する構成単位（ａ１）を有する。以下、カルボキシ基、および、フェノール性水酸基をあわせて酸基ともいう。
　本発明において、「カルボキシ基が酸分解性基で保護された基」、「フェノール性水酸基が酸分解性基で保護された基」とは、酸を触媒（または開始剤）として脱保護反応を起こし、上述した酸基と、再生された酸と、分解された構造とを生じる基を意味する。
　酸基は、カルボキシ基が好ましい。
　酸分解性基は、酸により比較的分解し易い基（例えば、後述するエステル構造、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。これらの基の中でも、アセタール基が好ましい。
　すなわち、構成単位（ａ１）は、カルボキシ基がアセタール基で保護された保護カルボキシ基、または、フェノール性水酸基がアセタール基で保護された保護フェノール基を有することが好ましく、カルボキシ基がアセタール基で保護された保護カルボキシ基を有することがより好ましい。この態様によれば、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。 << (a1) a structural unit having at least one group selected from a group in which a carboxy group is protected with an acid-decomposable group and a group in which a phenolic hydroxyl group is protected with an acid-decomposable group >>
The polysiloxane used in the present invention is a structural unit (a1) having at least one group selected from a group in which a carboxy group is protected with an acid-decomposable group and a group in which a phenolic hydroxyl group is protected with an acid-decomposable group. ). Hereinafter, the carboxy group and the phenolic hydroxyl group are also referred to as an acid group.
In the present invention, “a group in which a carboxy group is protected with an acid-decomposable group” and “a group in which a phenolic hydroxyl group is protected with an acid-decomposable group” are used for deprotection reaction using an acid as a catalyst (or an initiator). It means a group which is raised and produces the above-described acid group, regenerated acid, and decomposed structure.
The acid group is preferably a carboxy group.
An acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group described later) or a group that is relatively difficult to decompose by an acid ( For example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group) can be used. Among these groups, an acetal group is preferable.
That is, the structural unit (a1) preferably has a protected carboxy group in which a carboxy group is protected with an acetal group, or a protected phenol group in which a phenolic hydroxyl group is protected with an acetal group, and the carboxy group is protected with an acetal group. It is more preferable to have a protected carboxy group. According to this aspect, it is preferable from the viewpoints of basic physical properties of the photosensitive resin composition, particularly sensitivity, pattern shape, contact hole formability, and storage stability of the photosensitive resin composition.
　構成単位（ａ１）は、下記一般式（ａ１－１）で表される構成単位、および／または、下記一般式（ａ１－２）で表される構成単位であることが好ましい。 The structural unit (a1) is preferably a structural unit represented by the following general formula (a1-1) and / or a structural unit represented by the following general formula (a1-2).
Figure JPOXMLDOC01-appb-C000007
 　一般式（ａ１－１）、（ａ１－２）中、ａは０または１を表し、
　Ｒ１およびＲ２は、それぞれ独立に、水素原子、アルキル基またはアリール基を表し、Ｒ１およびＲ２の少なくとも一方は、アルキル基またはアリール基を表し、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、アルキル基、アリール基、または、アラルキル基を表し、
　Ｌ１は、単結合または２価の連結基を表し、
　Ｌ２は、単結合または２価の連結基を表し、
　Ｒｘは、アルキル基またはハロゲン原子を表し、
　ｍ１は、０～４の整数を表す。
Figure JPOXMLDOC01-appb-C000007
 In general formulas (a1-1) and (a1-2), a represents 0 or 1;
R 1 and R 2 each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 represents an alkyl group or an aryl group, and R 3 represents an alkyl group or an aryl group. R 1 or R 2 and R 3 may be linked to form a cyclic ether,
R 4 represents an alkyl group, an aryl group, or an aralkyl group,
L 1 represents a single bond or a divalent linking group,
L 2 represents a single bond or a divalent linking group,
R x represents an alkyl group or a halogen atom,
m1 represents an integer of 0 to 4.
　Ｒ１およびＲ２は、それぞれ独立に、水素原子、アルキル基またはアリール基を表し、Ｒ１およびＲ２の少なくとも一方がアルキル基またはアリール基である。
　アルキル基としては、炭素数１～１０のアルキル基が好ましく、炭素数１～８のアルキル基がより好ましく、炭素数１～６のアルキル基がさらに好ましい。アルキル基は、無置換であってもよく、置換基を有していてもよい。また、アルキル基は、直鎖、分岐、環状のいずれであってもよいが、直鎖のアルキル基が好ましい。アルキル基の具体例としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基等が例示される。アルキル基が有していてもよい置換基としては、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、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。これらの置換基は、さらに置換基を有していてもよい。
　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、炭素数６～１４のアリール基がより好ましく、炭素数６～１０のアリール基がさらに好ましい。アリール基は、無置換であってもよく、置換基を有していてもよい。アリール基の具体例としては、例えば、フェニル基、ナフチル基、アントラセニル基等が例示される。置換基としては、上述したものが挙げられる。また、炭素数１～１０のアルキル基を置換基とすることもできる。
　Ｒ１およびＲ２は、それぞれ独立に、水素原子、または、アルキル基であることが好ましく、水素原子、または、メチル基であることがより好ましく、Ｒ１およびＲ２の一方がメチル基であり、他方が水素原子であることが特に好ましい。 R 1 and R 2 each independently represents a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1 and R 2 is an alkyl group or an aryl group.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. The alkyl group may be unsubstituted or may have a substituent. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Examples of the substituent that the alkyl group may have include an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, and a halogen atom (fluorine atom, chlorine atom, bromine atom). , Iodine atom) and the like. These substituents may further have a substituent.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. The aryl group may be unsubstituted or may have a substituent. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the substituent include those described above. In addition, an alkyl group having 1 to 10 carbon atoms can be used as a substituent.
R 1 and R 2 are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and one of R 1 and R 2 is a methyl group. The other is particularly preferably a hydrogen atom.
　Ｒ３はアルキル基またはアリール基を表す。Ｒ３が表すアルキル基、およびアリール基は、Ｒ１およびＲ２におけるアルキル基、アリール基と同義である。Ｒ３は、メチル基、エチル基、プロピル基であることが好ましく、エチル基、プロピル基がより好ましい。
　Ｒ３は、Ｒ１またはＲ２と連結して環状エーテルを形成してもよい。Ｒ１またはＲ２と連結して形成される環状エーテルとしては、３～６員環の環状エーテルが好ましく、５～６員環の環状エーテルがより好ましい。 R 3 represents an alkyl group or an aryl group. The alkyl group and aryl group represented by R 3 have the same meanings as the alkyl group and aryl group in R 1 and R 2 . R 3 is preferably a methyl group, an ethyl group, or a propyl group, and more preferably an ethyl group or a propyl group.
R 3 may be linked to R 1 or R 2 to form a cyclic ether. The cyclic ether formed by linking with R 1 or R 2 is preferably a 3- to 6-membered cyclic ether, and more preferably a 5- to 6-membered cyclic ether.
　Ｒ４は、アルキル基、アリール基、または、アラルキル基を表す。
　アルキル基としては、炭素数１～１０のアルキル基が好ましく、炭素数１～８のアルキル基がより好ましく、炭素数１～６のアルキル基がさらに好ましい。アルキル基は、置換基を有していてもよい。また、アルキル基は、直鎖、分岐、環状のいずれであってもよい。
　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、炭素数６～１４のアリール基がより好ましく、炭素数６～１０のアリール基がさらに好ましい。アリール基は、置換基を有していてもよい。アリール基としては、例えば、フェニル基、ナフチル基、アントラセニル基等が例示される。
　アラルキル基としては、炭素数１～１０のアルキル基の水素原子の一部が、炭素数６～２０のアリール基に置換されている基が好ましい。アラルキル基は、置換基を有していてもよい。アラルキル基を構成するアルキル基は、直鎖、分岐、環状のいずれであってもよい。
　アルキル基、アリール基、アラルキル基が有してもよい置換基としては、Ｒ１、Ｒ２で説明した置換基と同様である。
　Ｒ４は、溶剤耐性や耐熱性の観点からメチル基、フェニル基、プロピル基、ブチル基、ヘキシル基が好ましく、メチル基、フェニル基がより好ましい。 R 4 represents an alkyl group, an aryl group, or an aralkyl group.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. The alkyl group may have a substituent. The alkyl group may be linear, branched or cyclic.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. The aryl group may have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.
As the aralkyl group, a group in which a part of hydrogen atoms of an alkyl group having 1 to 10 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms is preferable. The aralkyl group may have a substituent. The alkyl group constituting the aralkyl group may be linear, branched or cyclic.
The substituents that the alkyl group, aryl group, and aralkyl group may have are the same as the substituents described for R 1 and R 2 .
R 4 is preferably a methyl group, a phenyl group, a propyl group, a butyl group, or a hexyl group from the viewpoint of solvent resistance or heat resistance, and more preferably a methyl group or a phenyl group.
　Ｒｘは、アルキル基またはハロゲン原子を表す。アルキル基としては、炭素数１～４のアルキル基が好ましい。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が好ましい。 R x represents an alkyl group or a halogen atom. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.
　Ｌ１およびＬ２は、単結合または２価の連結基を表す。２価の連結基としては、炭素数１～１２のアルキレン基、炭素数１～１２のアルキレンオキサイド基、炭素数６～１２のアリーレン基が挙げられる。アルキレンオキサイド基、および、アルキレンオキサイド基は、直鎖、分岐、環状のいずれであってもよい。また、アルキレン基、アルキレンオキサイド基、アリーレン基は、置換基を有していてもよい。置換基としては、Ｒ１、Ｒ２で説明した置換基と同様である。また、カルボキシ基、フェノール基、スルホンアミド基、ホスホニル基、スルホニル基、スルホンアミド基、スルホニルイミド基等の酸基を置換基として有していてもよい。
　ｍ１は、０～４の整数を表し、０～２が好ましく、０～１がより好ましく、０が最も好ましい。 L 1 and L 2 represent a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 12 carbon atoms, and an arylene group having 6 to 12 carbon atoms. The alkylene oxide group and the alkylene oxide group may be linear, branched or cyclic. In addition, the alkylene group, alkylene oxide group, and arylene group may have a substituent. Examples of the substituent are the same as those described for R 1 and R 2 . Moreover, you may have acid groups, such as a carboxy group, a phenol group, a sulfonamide group, a phosphonyl group, a sulfonyl group, a sulfonamide group, a sulfonylimide group, as a substituent.
m1 represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and most preferably 0.
　上記一般式（ａ１－２）で表される構成単位は、下記一般式（ａ１－２－１）で表される構成単位であることが好ましい。 The structural unit represented by the general formula (a1-2) is preferably a structural unit represented by the following general formula (a1-2-1).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　一般式（ａ１－２－１）中、ａは０または１を表し、Ｒ１およびＲ２は、それぞれ独立に、水素原子、アルキル基またはアリール基を表し、Ｒ１およびＲ２の少なくとも一方がアルキル基またはアリール基を表し、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、アルキル基、アリール基、または、アラルキル基を表し、Ｌ２は、単結合または２価の連結基を表し、Ｒｘは、アルキル基またはハロゲン原子を表し、ｍ１は、０～４の整数を表す。 In general formula (a1-2-1), a represents 0 or 1, R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and at least one of R 1 and R 2 is Represents an alkyl group or an aryl group, R 3 represents an alkyl group or an aryl group, and R 1 or R 2 and R 3 may be linked to form a cyclic ether, and R 4 represents an alkyl group, An aryl group or an aralkyl group is represented, L 2 represents a single bond or a divalent linking group, R x represents an alkyl group or a halogen atom, and m1 represents an integer of 0 to 4.
　構成単位（ａ１）を得るために使用できるシラン化合物の具体例としては、例えば、以下に示すシラン化合物が挙げられる。 Specific examples of the silane compound that can be used for obtaining the structural unit (a1) include the following silane compounds.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
＜＜＜架橋性基を有する構成単位（ａ２）＞＞＞
　構成単位（ａ２）は、架橋性基を有する。本発明において、架橋性基とは、熱によって架橋反応を生じうる基を意味する。
架橋性基は、１気圧における加熱処理の際の架橋反応の開始温度が１００℃以上の基であれば特に限定はされない。架橋反応の開始温度は公知の手法を使って分析することができ、例えばＤＳＣ測定（Ｄｉｆｆｅｒｅｎｔｉａｌ　ｓｃａｎｎｉｎｇ　ｃａｌｏｒｉｍｅｔｒｙ）を用いた手法によって分析することができる。
　架橋性基としては、環状エーテル、エチレン性不飽和結合を有する基、アルコキシメチル基、メチロール基、アミノ基などが挙げられる。また、架橋性基は、連結基等を介して結合していてもよい。
　環状エーテルとしては、エポキシ基、オキセタニル基が挙げられる。
　エチレン性不飽和結合を有する基としては、ビニル基、アリル基、メタリル基、メタクリロイル基、アクリロイル基、アリルオキシカルボニル基、メタリルオキシカルボニル基などが挙げられる。
　アルコキシメチル基としては、「－ＣＨ２ＯＲ」で表される基が挙げられる。Ｒは炭素原子数１～８のアルキル基を表し、炭素数１～４のアルキル基が好ましく、メチル基がより好ましい。アルキル基は、直鎖、分岐、および、環状のいずれでもよいが、直鎖が好ましい。
　アミノ基としては、置換基を有するアミノ基であってもよく、無置換のアミノ基であってもよい。
　架橋性基は、環状エーテル、エチレン性不飽和結合を有する基が好ましく、環状エーテルがより好ましく、エポキシ基またはオキセタニル基がさらに好ましく、エポキシ基が特に好ましい。環状エーテルは、未反応の酸基を消費して強固な硬化膜を形成できる。このため、硬化膜に未反応の酸基が残存し難くできるので、耐熱性、耐溶剤性、基材密着性などに優れた硬化膜を形成できる。
　架橋性基の具体例としては、以下のものが挙げられるが、これらに限定されるものではない。式中＊は、他の基との連結部分を表す。 <<< Structural Unit (a2) Having Crosslinkable Group >>>
The structural unit (a2) has a crosslinkable group. In the present invention, the crosslinkable group means a group capable of causing a crosslinking reaction by heat.
The crosslinkable group is not particularly limited as long as it is a group having a crosslinking reaction starting temperature of 100 ° C. or higher during heat treatment at 1 atm. The initiation temperature of the cross-linking reaction can be analyzed using a known method, for example, by a method using DSC measurement (Differential scanning calorimetry).
Examples of the crosslinkable group include a cyclic ether, a group having an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, and an amino group. The crosslinkable group may be bonded via a linking group or the like.
Examples of the cyclic ether include an epoxy group and an oxetanyl group.
Examples of the group having an ethylenically unsaturated bond include vinyl group, allyl group, methallyl group, methacryloyl group, acryloyl group, allyloxycarbonyl group, and methallyloxycarbonyl group.
Examples of the alkoxymethyl group include a group represented by “—CH 2 OR”. R represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. The alkyl group may be linear, branched or cyclic, but is preferably linear.
The amino group may be an amino group having a substituent or an unsubstituted amino group.
The crosslinkable group is preferably a cyclic ether or a group having an ethylenically unsaturated bond, more preferably a cyclic ether, still more preferably an epoxy group or an oxetanyl group, and particularly preferably an epoxy group. Cyclic ethers can consume unreacted acid groups to form a strong cured film. For this reason, since unreacted acid groups can hardly remain in the cured film, a cured film excellent in heat resistance, solvent resistance, substrate adhesion, and the like can be formed.
Specific examples of the crosslinkable group include the following, but are not limited thereto. In the formula, * represents a connecting portion with another group.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　構成単位（ａ２）は、１つの構成単位中に架橋性基を少なくとも１個有していればよく、１～３個有していることが好ましく、１個がより好ましい。構成単位（ａ２）が架橋性基を複数有する場合は、すべて同一種類であってもよく、異なる種類であってもよい。架橋性基を複数含む場合は、同一の種類であることが好ましい。 The structural unit (a2) may have at least one crosslinkable group in one structural unit, preferably 1 to 3 and more preferably 1. When the structural unit (a2) has a plurality of crosslinkable groups, they may all be of the same type or different types. When a plurality of crosslinkable groups are included, the same kind is preferable.
　構成単位（ａ２）としては、下記一般式（ａ２’）で表される構成単位が挙げられる。 Examples of the structural unit (a2) include structural units represented by the following general formula (a2 ′).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　一般式（ａ２’）中、ａは０または１を表し、Ｒ５は、アルキル基、アリール基またはアラルキル基を表し、Ｌ３は、単結合、または、２価の連結基を表し、Ｘは架橋性基を表す。 In general formula (a2 ′), a represents 0 or 1, R 5 represents an alkyl group, an aryl group or an aralkyl group, L 3 represents a single bond or a divalent linking group, and X represents Represents a crosslinkable group.
　構成単位（ａ２）は、硬化膜特性の観点から、下記一般式（ａ２－１）で表される構成単位、および／または、下記一般式（ａ２－２）で表される構成単位であることが好ましい。 The structural unit (a2) is a structural unit represented by the following general formula (a2-1) and / or a structural unit represented by the following general formula (a2-2) from the viewpoint of cured film properties. Is preferred.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　一般式（ａ２－１）、（ａ２－２）中、ａは０または１を表し、Ｒ５は、アルキル基、アリール基またはアラルキル基を表し、Ｒｙは、アルキル基またはハロゲン原子を表し、Ｌ３は、単結合、または、２価の連結基を表し、ｎは、０または１を表し、ｍ２は、ｎが０の場合は０～２の整数を表し、ｎが１の場合は０～３の整数を表し、ｍ３は、０～６の整数を表す。 In general formulas (a2-1) and (a2-2), a represents 0 or 1, R 5 represents an alkyl group, an aryl group or an aralkyl group, R y represents an alkyl group or a halogen atom, L 3 represents a single bond or a divalent linking group, n represents 0 or 1, m 2 represents an integer of 0 to 2 when n is 0, and 0 when n is 1. Represents an integer from 3 to 3, and m3 represents an integer from 0 to 6.
　Ｒ５は、アルキル基、アリール基またはアラルキル基を表す。アルキル基、アリール基、アラルキル基としては、上述した（ａ１－１）及び（ａ１－２）のＲ４で説明した範囲と同様であり、好ましい範囲も同様である。
　Ｌ３は、単結合、または、２価の連結基を表す。２価の連結基としては、（ａ１－１）のＬ１及び（ａ１－２）のＬ２で説明した範囲と同様であり、好ましい範囲も同様である。
　Ｒｙは、アルキル基またはハロゲン原子を表す。アルキル基、および、ハロゲン原子としては、上述した（ａ１－２）のＲｘで説明した範囲と同様であり、好ましい範囲も同様である。
　ｎは、０または１を表し、０が好ましい。
　ｍ２は、ｎが０の場合は０～２の整数を表し、ｎが１の場合は０～３の整数を表す。ｍ２は０が好ましい。
　ｍ３は、０～６の整数を表し、０が好ましい。 R 5 represents an alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group and aralkyl group are the same as the ranges described for R 4 in the above (a1-1) and (a1-2), and the preferred ranges are also the same.
L 3 represents a single bond or a divalent linking group. The divalent linking group is the same as the range described for L 1 of (a1-1) and L 2 of (a1-2), and the preferred range is also the same.
R y represents an alkyl group or a halogen atom. The alkyl group and the halogen atom are the same as the range described for R x in (a1-2) described above, and the preferred range is also the same.
n represents 0 or 1, and 0 is preferable.
m2 represents an integer of 0 to 2 when n is 0, and represents an integer of 0 to 3 when n is 1. m2 is preferably 0.
m3 represents an integer of 0 to 6, and 0 is preferable.
　構成単位（ａ２）を得るために使用できるシランの具体例としては、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシランなどを挙げることができる。また、以下に示すシラン化合物を用いることもできる。 Specific examples of silanes that can be used to obtain the structural unit (a2) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxy. Mention may be made of propyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. . Moreover, the silane compound shown below can also be used.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
＜＜＜酸基を有する構成単位（ａ３）＞＞＞
　（Ａ）ポリシロキサン成分は、酸基を有する構成単位（ａ３）を含んでいてもよい。構成単位（ａ３）は、構成単位（ａ１）および構成単位（ａ２）から選ばれる少なくとも一つの構成単位を有するポリシロキサンが含んでいてもよい。また、構成単位（ａ１）および構成単位（ａ２）を実質的に含まないポリシロキサンが含んでいてもよい。
　具体的な酸基としては、カルボキシ基、スルホンアミド基、ホスホニル基、スルホニル基、フェノール性水酸基、スルホンアミド基、スルホニルイミド基が例示され、好ましい酸基としては、カルボキシ基、およびフェノール性水酸基が挙げられる。
　酸基を有する構成単位（ａ３）としては、例えば、以下の一般式（ａ３－１）で表される構造、および／または、一般式（ａ３－２）で表される構造が好ましい具体例として挙げられる。 <<< Structural Unit (a3) Having Acid Group >>>
(A) The polysiloxane component may contain the structural unit (a3) having an acid group. The structural unit (a3) may contain a polysiloxane having at least one structural unit selected from the structural unit (a1) and the structural unit (a2). Moreover, the polysiloxane which does not contain a structural unit (a1) and a structural unit (a2) substantially may be contained.
Specific examples of the acid group include a carboxy group, a sulfonamide group, a phosphonyl group, a sulfonyl group, a phenolic hydroxyl group, a sulfonamide group, and a sulfonylimide group. Preferred acid groups include a carboxy group and a phenolic hydroxyl group. Can be mentioned.
As the structural unit (a3) having an acid group, for example, a structure represented by the following general formula (a3-1) and / or a structure represented by the general formula (a3-2) are preferable specific examples. Can be mentioned.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　（一般式（ａ３－１）、（ａ３－２）中、ａは０または１を表し、Ｒ６は、アルキル基、アリール基、または、アラルキル基を表し、Ｌ４は、単結合または２価の連結基を表し、Ｌ５は、単結合または２価の連結基を表し、Ｒｚは、アルキル基またはハロゲン原子を表し、ｍ４は、０～４の整数を表す。） (In the general formulas (a3-1) and (a3-2), a represents 0 or 1, R 6 represents an alkyl group, an aryl group, or an aralkyl group, and L 4 represents a single bond or a divalent group. L 5 represents a single bond or a divalent linking group, R z represents an alkyl group or a halogen atom, and m4 represents an integer of 0 to 4.)
　Ｒ６は、アルキル基、アリール基、または、アラルキル基を表す。アルキル基、アリール基、アラルキル基としては、上述した（ａ１－１）及び（ａ１－２）のＲ４で説明した範囲と同様であり、好ましい範囲も同様である。
　Ｌ４は、単結合、または、２価の連結基を表す。２価の連結基としては、（ａ１－１）のＬ１で説明した範囲と同様であり、好ましい範囲も同様である。
　Ｌ５は、単結合、または、２価の連結基を表す。２価の連結基としては、（ａ１－２）のＬ２で説明した範囲と同様であり、好ましい範囲も同様である。
　Ｒｚは、アルキル基またはハロゲン原子を表す。アルキル基、および、ハロゲン原子としては、上述した（ａ１－２）のＲｘで説明した範囲と同様であり、好ましい範囲も同様である。
　ｍ４は、０～４の整数を表し、０～２が好ましく、０～１がより好ましく、０が最も好ましい。 R 6 represents an alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group and aralkyl group are the same as the ranges described for R 4 in the above (a1-1) and (a1-2), and the preferred ranges are also the same.
L 4 represents a single bond or a divalent linking group. The divalent linking group is the same as the range described for L 1 in (a1-1), and the preferred range is also the same.
L 5 represents a single bond or a divalent linking group. The divalent linking group is the same as the range described for L 2 in (a1-2), and the preferred range is also the same.
R z represents an alkyl group or a halogen atom. The alkyl group and the halogen atom are the same as the range described for R x in (a1-2) described above, and the preferred range is also the same.
m4 represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and most preferably 0.
　上記一般式（ａ３－２）で表される構成単位は、下記一般式（ａ３－２－１）で表される構成単位であることが好ましい。 The structural unit represented by the general formula (a3-2) is preferably a structural unit represented by the following general formula (a3-2-1).
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　一般式（ａ３－２－１）中、ａは０または１を表し、Ｒ６は、アルキル基、アリール基、または、アラルキル基を表し、Ｌ５は、単結合または２価の連結基を表し、Ｒｚは、アルキル基またはハロゲン原子を表し、ｍ４は、０～４の整数を表す。 In general formula (a3-2-1), a represents 0 or 1, R 6 represents an alkyl group, an aryl group, or an aralkyl group, and L 5 represents a single bond or a divalent linking group. , R z represents an alkyl group or a halogen atom, and m4 represents an integer of 0-4.
　構成単位（ａ３）を得るために使用できるシラン化合物としては、構成単位（ａ１）を得るために使用できるシラン化合物と同様のものを使用できる。 As the silane compound that can be used to obtain the structural unit (a3), the same silane compound that can be used to obtain the structural unit (a1) can be used.
＜＜＜（ａ１）～（ａ３）以外の構成単位（ａ４）＞＞＞
　ポリシロキサン成分は、上述した構成単位（ａ１）～（ａ３）以外の構成単位（ａ４）を含むことができる。
　構成単位（ａ４）としては、例えば、以下の一般式（ａ４－１）で表される構造が好ましい具体例として挙げられる。 <<< Structural Unit (a4) Other than (a1) to (a3) >>>
The polysiloxane component can contain a structural unit (a4) other than the structural units (a1) to (a3) described above.
As the structural unit (a4), for example, a structure represented by general formula (a4-1) shown below is preferred.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　一般式（ａ４－１）中、ａは０～３の整数を表し、ｂは０～３の整数を表す。ただし０≦ａ＋ｂ≦３である。Ｒ７およびＲ８は、それぞれ独立に、アルキル基、アリール基、または、アラルキル基を表す。
　Ｒ７、Ｒ８が示すアルキル基、アリール基、アラルキル基としては、上述した（ａ１－１）及び（ａ１－２）のＲ４で説明した範囲と同様であり、好ましい範囲も同様である。 In general formula (a4-1), a represents an integer of 0 to 3, and b represents an integer of 0 to 3. However, 0 ≦ a + b ≦ 3. R 7 and R 8 each independently represents an alkyl group, an aryl group, or an aralkyl group.
The alkyl group, aryl group and aralkyl group represented by R 7 and R 8 are the same as the ranges described for R 4 in (a1-1) and (a1-2) described above, and the preferred ranges are also the same.
　構成単位（ａ４）を得るために使用できるシラン化合物としては、アルコキシシラン化合物、クロロシラン化合物などが挙られる。具体的には、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、フェニルトリメトキシシラン、ヘキシルトリエトキシシラン、デシルトリメトキシシラン、トリフルオロプロピルトリメトキシシランなどを挙げることができる。また、以下に示すシラン化合物を用いることもできる。 Examples of silane compounds that can be used to obtain the structural unit (a4) include alkoxysilane compounds and chlorosilane compounds. Specific examples include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, and trifluoropropyltrimethoxysilane. Moreover, the silane compound shown below can also be used.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　（Ａ）ポリシロキサン成分は、感光性樹脂組成物に含まれるポリシロキサン全量中、構成単位（ａ１）のモル数および構成単位（ａ３）のモル数の合計と、構成単位（ａ２）のモル数の比が、１０：９０～９０：１０であることが好ましく３０：７０～７０：３０であることがより好ましく、４０：６０～６０：４０であることが更に好ましい。構成単位（ａ１）のモル数および構成単位（ａ３）のモル数の合計と、構成単位（ａ２）のモル数との比が上記範囲であれば、溶剤耐性に優れた硬化膜を形成できる。 (A) The polysiloxane component is the total number of moles of the structural unit (a1) and the moles of the structural unit (a3) and the number of moles of the structural unit (a2) in the total amount of polysiloxane contained in the photosensitive resin composition. The ratio is preferably 10:90 to 90:10, more preferably 30:70 to 70:30, and still more preferably 40:60 to 60:40. If the ratio between the total number of moles of the structural unit (a1) and the moles of the structural unit (a3) and the mole number of the structural unit (a2) is in the above range, a cured film having excellent solvent resistance can be formed.
　（Ａ）ポリシロキサン成分に含まれるポリシロキサンは、ポリシロキサンの重合時に残ったシラノール基を含んでいてもよい。ポリシロキサン全量中のシラノール基の数は、ポリシロキサン中のＳｉ原子数に対して０～０．５倍が好ましく、０～０．２倍が好ましく、０～０．０５倍が最も好ましい。シラノール基の数が上記範囲であれば、感光性樹脂組成物の保存安定性が良好である。なお、ここでいうポリシロキサン全量中のシラノール基の数とは、ポリシロキサン成分に含まるポリシロキサンが有するシラノール基の数の合計値を意味する。Ｓｉ原子数についても同様である。 (A) The polysiloxane contained in the polysiloxane component may contain silanol groups remaining during polymerization of the polysiloxane. The number of silanol groups in the total amount of polysiloxane is preferably 0 to 0.5 times, more preferably 0 to 0.2 times, and most preferably 0 to 0.05 times the number of Si atoms in the polysiloxane. When the number of silanol groups is in the above range, the storage stability of the photosensitive resin composition is good. The number of silanol groups in the total amount of polysiloxane here means the total number of silanol groups of the polysiloxane contained in the polysiloxane component. The same applies to the number of Si atoms.
　ポリシロキサンは、各構成単位に対応するシラン化合物や、オリゴシロキサンを混合および反応させることによって得られる。例えば対応するトリメトキシシランやジメトキシシランを加水分解、縮合させることによって得られる。加水分解、縮合は公知の方法、条件で適宜行うことができる。例えば、特開平１０－３２４７４８号公報（特に００８５段落～００８７段落）、特開２００５－２８３９９１号公報（特に００５２段落～０５４段落）、特開２００６ー２７６５９８号公報（特に０００９段落～００３０段落）等に記載された手順や条件を参考にすることができる。
　上述した構成単位（ａ１）の酸分解性基は、保護されたシラン化合物を用いて導入してもよいし、高分子反応で導入してもよい。
　なお、特開平１０－３２４７４８号公報（特に００８５段落～００８７段落）に記載のように、（Ａ）ポリシロキサンに、カルボキシ基を含む構成単位を導入する場合には、対応するカルボン酸のアルキルエステルを有するシランを用いてポリシロキサンを合成し、アルキルエステルを一般的な方法で加水分解してカルボキシ基を有する構成単位を得ることが好ましい。
　また、ポリシロキサンに、カルボキシ基が酸分解性基で保護された基を有する構成単位を導入するには、カルボキシ基を有する構成を有するポリシロキサンを合成後、所謂高分子反応で酸分解性基を導入してカルボキシ基を保護することが好ましい。
　また、ポリシロキサンに、フェノール性水酸基が酸分解性基で保護された基を有する構成単位を導入するには、フェノール性水酸基を有するポリシロキサンを合成後、所謂高分子反応で、酸分解性基を導入してフェノール性水酸基を保護することが好ましい。 The polysiloxane can be obtained by mixing and reacting a silane compound corresponding to each structural unit or oligosiloxane. For example, it can be obtained by hydrolysis and condensation of the corresponding trimethoxysilane or dimethoxysilane. Hydrolysis and condensation can be appropriately performed by known methods and conditions. For example, Japanese Patent Application Laid-Open No. 10-324748 (especially 0085 paragraph to 0087 paragraph), Japanese Patent Application Laid-Open No. 2005-283939 (particularly 0052 paragraph to 054 paragraph), Japanese Patent Application Laid-Open No. 2006-276598 (particularly 0009 paragraph to 0030 paragraph), etc. The procedures and conditions described in can be referred to.
The acid-decomposable group of the structural unit (a1) described above may be introduced using a protected silane compound or may be introduced by a polymer reaction.
As described in JP-A-10-324748 (particularly paragraphs 0085 to 0087), when a structural unit containing a carboxy group is introduced into (A) polysiloxane, the corresponding alkyl ester of carboxylic acid is used. It is preferable to synthesize a polysiloxane using a silane having an alkyl group and hydrolyze the alkyl ester by a general method to obtain a structural unit having a carboxy group.
In order to introduce a structural unit having a carboxy group protected with an acid-decomposable group into polysiloxane, after synthesizing a polysiloxane having a structure having a carboxy group, an acid-decomposable group is formed by a so-called polymer reaction. It is preferable to introduce carboxy to protect the carboxy group.
In order to introduce a structural unit having a group in which a phenolic hydroxyl group is protected with an acid-decomposable group into polysiloxane, after synthesizing a polysiloxane having a phenolic hydroxyl group, a so-called polymer reaction is performed to produce an acid-decomposable group. It is preferable to protect the phenolic hydroxyl group by introducing.
　以下に、（Ａ）ポリシロキサン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。
（第１の実施形態）
　上述した（１）の態様において、構成単位（ａ１）および構成単位（ａ２）を有するポリシロキサン（Ａ１）が、さらに、構成単位（ａ３）および／または構成単位（ａ４）を有する態様。
（第２の実施形態）
　上述した（２）の態様において、構成単位（ａ１）を有するポリシロキサン（Ａ２）が、さらに、構成単位（ａ３）および／または構成単位（ａ４）を有する態様。
（第３の実施形態）
　上述した（２）の態様において、構成単位（ａ２）を有するポリシロキサン（Ａ３）が、さらに、構成単位（ａ３）および／または構成単位（ａ４）を有する態様。
（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、少なくとも構成単位（ａ３）を含む態様。
（第５の実施形態）
　上述した（１）および／または（２）の態様において、実質的に構成単位（ａ１）および構成単位（ａ２）を含まずに、構成単位（ａ３）および／または構成単位（ａ４）を有するポリシロキサンを有する態様。
（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。 Hereinafter, preferred embodiments of the (A) polysiloxane component will be described, but the present invention is not limited thereto.
(First embodiment)
In the aspect (1) described above, the polysiloxane (A1) having the structural unit (a1) and the structural unit (a2) further has the structural unit (a3) and / or the structural unit (a4).
(Second Embodiment)
In the aspect (2) described above, the polysiloxane (A2) having the structural unit (a1) further has the structural unit (a3) and / or the structural unit (a4).
(Third embodiment)
In the aspect (2) described above, the polysiloxane (A3) having the structural unit (a2) further has the structural unit (a3) and / or the structural unit (a4).
(Fourth embodiment)
The aspect including at least the structural unit (a3) in any one of the first to third embodiments.
(Fifth embodiment)
In the aspect of (1) and / or (2) described above, a poly having a structural unit (a3) and / or a structural unit (a4) substantially not including the structural unit (a1) and the structural unit (a2). Embodiment with siloxane.
(Sixth embodiment)
A form comprising a combination of two or more of the first to fifth embodiments.
　実質的に構成単位（ａ１）および構成単位（ａ２）を含まずに、構成単位（ａ３）および／または構成単位（ａ４）を有するポリシロキサンを有する態様においては、構成単位（ａ１）および／または構成単位（ａ２）を有するポリシロキサンの合計量と、実質的に構成単位（ａ１）および構成単位（ａ２）を含まずに、構成単位（ａ３）および／または構成単位（ａ４）を有するポリシロキサンの合計量との質量割合は、９９：１～５：９５が好ましく、９７：３～３０：７０がより好ましく、９５：５～５０：５０がさらに好ましい。
　また、構成単位（ａ１）および／または構成単位（ａ２）を有するポリシロキサンの合計含有量は、ポリシロキサンの全含有量に対して６０質量％以上が好ましく、７０質量％以上が好ましく、９０質量％以上がもっとも好ましい。
　本発明の感光性樹脂組成物における（Ａ）ポリシロキサン成分の含有量は、感光性樹脂組成物の全固形分に対し、６０～９９質量％が好ましい。上限は、例えば、９８質量％以下がより好ましい。下限は、６５質量％以上がより好ましく、７０質量％以上が更に好ましい。 In the embodiment having the polysiloxane having the structural unit (a3) and / or the structural unit (a4) substantially free of the structural unit (a1) and the structural unit (a2), the structural unit (a1) and / or The total amount of the polysiloxane having the structural unit (a2) and the polysiloxane having the structural unit (a3) and / or the structural unit (a4) substantially not including the structural unit (a1) and the structural unit (a2) The mass ratio with respect to the total amount is preferably 99: 1 to 5:95, more preferably 97: 3 to 30:70, and still more preferably 95: 5 to 50:50.
The total content of the polysiloxane having the structural unit (a1) and / or the structural unit (a2) is preferably 60% by mass or more, preferably 70% by mass or more, and 90% by mass with respect to the total content of the polysiloxane. % Or more is most preferable.
The content of the (A) polysiloxane component in the photosensitive resin composition of the present invention is preferably 60 to 99% by mass with respect to the total solid content of the photosensitive resin composition. The upper limit is more preferably 98% by mass or less, for example. The lower limit is more preferably 65% by mass or more, and still more preferably 70% by mass or more.
＜＜（Ｂ）光酸発生剤（Ｂ成分）＞＞
　本発明の感光性樹脂組成物は、ｐＫａが３以下の酸を発生する光酸発生剤を含有する。光酸発生剤は、ｐＫａが２以下の酸を発生するものが好ましい。なお本発明において、ｐＫａは、基本的に２５℃の水中におけるｐＫａを指す。水中で測定できないものは、測定に適する溶剤に変更し測定したものを指す。具体的には、化学便覧等に記載のｐＫａが参考にできる。ｐＫａが３以下の酸としては、スルホン酸またはホスホン酸であることが好ましく、スルホン酸であることがより好ましい。 << (B) Photoacid Generator (B Component) >>
The photosensitive resin composition of the present invention contains a photoacid generator that generates an acid having a pKa of 3 or less. The photoacid generator is preferably one that generates an acid having a pKa of 2 or less. In the present invention, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to. The acid having a pKa of 3 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.
　光酸発生剤は、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。 The photoacid generator is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
　光酸発生剤の例として、オニウム塩化合物、トリクロロメチル－ｓ－トリアジン類、ジアゾメタン化合物、イミドスルホネート化合物、オキシムスルホネート化合物、および、イミド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、感度、現像性の観点から、オニウム塩化合物、オキシムスルホネート化合物、およびイミドスルホネート化合物から選ばれる１種以上が好ましく、オキシムスルホネート化合物、および、イミドスルホネート化合物から選ばれる１種以上がより好ましい。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。 Examples of the photoacid generator include onium salt compounds, trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and imide sulfonate compounds. Among these, from a sensitivity and developability viewpoint, 1 or more types chosen from an onium salt compound, an oxime sulfonate compound, and an imide sulfonate compound are preferable, and 1 or more types chosen from an oxime sulfonate compound and an imide sulfonate compound are more. preferable. A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
　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。 Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-212494A. It can be illustrated.
　オニウム塩化合物としては、ジフェニルヨードニウム塩、トリアリールスルホニウム塩、スルホニウム塩、ベンゾチアゾニウム塩、テトラヒドロチオフェニウム塩等が挙げられる。下記一般式（１）および／または一般式（２）で表される化合物が好ましい。 Examples of the onium salt compounds include diphenyliodonium salts, triarylsulfonium salts, sulfonium salts, benzothiazonium salts, tetrahydrothiophenium salts, and the like. Compounds represented by the following general formula (1) and / or general formula (2) are preferred.
Figure JPOXMLDOC01-appb-C000018
 （式中、Ｒ５、Ｒ６およびＲ７はそれぞれ独立にアルキル基またはアリール基を表し、アルキル基を表す場合、互いに連結し環を形成してもよく、ヘテロ原子を介して環を形成していてもよい。Ｒ８およびＲ９はそれぞれ独立にアリール基を表し、Ｘ－は共役塩基を表す。）
Figure JPOXMLDOC01-appb-C000018
 (In the formula, R 5 , R 6 and R 7 each independently represents an alkyl group or an aryl group, and in the case of representing an alkyl group, they may be linked together to form a ring, R 8 and R 9 each independently represents an aryl group, and X − represents a conjugate base.)
　Ｒ５、Ｒ６およびＲ７はそれぞれ独立にアルキル基またはアリール基を表し、アルキル基またはアリール基は置換基を有していてもよい。置換基としては、炭素数１～１０のアリール基、炭素数１～１０のチオアリール基、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、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。
　一般式（１）中、Ｒ５、Ｒ６およびＲ７がそれぞれ表すアルキル基としては、炭素数１～１０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、炭素数１～４のアルキル基がさらに好ましい。アルキル基としては、例えば、メチル基、エチル基、ｔ－ブチル基などが挙げられる。また、一般式（１）中、Ｒ５、Ｒ６およびＲ７のうち、２つ以上がアルキル基の場合、その２つ以上のアルキル基が互いに連結し環を形成してもよく、ヘテロ原子（例えば酸素原子、硫黄原子など）を介して環を形成していてもよい。そのような環形態としては硫黄原子を含んだ形で５員環（チアシクロペンタン）、または６員環（チアシクロヘキサン）が好ましい。アルキル基は、置換基を有していてもよい。
　一般式（１）中、Ｒ５、Ｒ６およびＲ７がそれぞれ表すアリール基としては、炭素数６～１５のアリール基が好ましく、炭素数６～１０のアリール基がより好ましい。アリール基は、置換基を有していてもよい。アリール基としては、フェニル基、ナフチル基、４－メトキシフェニル基、４－クロロフェニル基、４－メチルフェニル基、４－ターシャリーブチルフェニル基、４－フェニルチオフェニル基、２，４，６－トリメチルフェニル基、４－メトキシ－１－ナフチル基が挙げられる。中でも、フェニル基、４－メトキシフェニル基、４－クロロフェニル基が好ましい。
　Ｒ５、Ｒ６およびＲ７はアリール基であることが好ましく、同一の基を表すことが好ましい。 R 5 , R 6 and R 7 each independently represents an alkyl group or an aryl group, and the alkyl group or aryl group may have a substituent. Examples of the substituent include an aryl group having 1 to 10 carbon atoms, a thioaryl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a thioalkoxy group having 1 to 10 carbon atoms. , Hydroxyl group, cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. These substituents may further have a substituent.
In general formula (1), the alkyl groups represented by R 5 , R 6 and R 7 are each preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and 1 to More preferred is an alkyl group of 4. Examples of the alkyl group include a methyl group, an ethyl group, and a t-butyl group. In the general formula (1), when two or more of R 5 , R 6 and R 7 are alkyl groups, the two or more alkyl groups may be linked to each other to form a ring, and a hetero atom A ring may be formed via (for example, an oxygen atom, a sulfur atom, etc.). Such a ring form is preferably a 5-membered ring (thiacyclopentane) or a 6-membered ring (thiacyclohexane) containing a sulfur atom. The alkyl group may have a substituent.
In the general formula (1), the aryl group represented by R 5 , R 6 and R 7 is preferably an aryl group having 6 to 15 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may have a substituent. Aryl groups include phenyl, naphthyl, 4-methoxyphenyl, 4-chlorophenyl, 4-methylphenyl, 4-tertiarybutylphenyl, 4-phenylthiophenyl, 2,4,6-trimethyl. Examples thereof include a phenyl group and a 4-methoxy-1-naphthyl group. Of these, a phenyl group, a 4-methoxyphenyl group, and a 4-chlorophenyl group are preferable.
R 5 , R 6 and R 7 are preferably aryl groups, and preferably represent the same group.
　一般式（１）中、Ｘ－は共役塩基を表す。共役塩基は、アルキルスルホン酸の共役塩基、アリールスルホン酸の共役塩基、ビスパーフルオロスルホニルアミドの共役塩基を表し、特にアルキルスルホン酸およびアリールスルホン酸の共役塩基が好ましい。そのような共役塩基としては、炭素数１～７のアルキルスルホン酸の共役塩基が好ましく、更に炭素数１～４の共役塩基がより好ましく、酸の形で表記すると例えば、メタンスルホン酸、トリフルオロメタンスルホン酸、ｎ－プロパンスルホン酸、ヘプタンスルホン酸が特に好ましい。アリールスルホン酸の共役塩基としては、酸の形で表記すると例えば、ベンゼンスルホン酸、クロロベンゼンスルホン酸、パラトルエンスルホン酸が特に好ましい。 In the general formula (1), X − represents a conjugate base. The conjugate base represents a conjugate base of an alkyl sulfonic acid, a conjugate base of an aryl sulfonic acid, or a conjugate base of a bisperfluorosulfonylamide, and a conjugate base of an alkyl sulfonic acid or an aryl sulfonic acid is particularly preferable. As such a conjugate base, a conjugate base of an alkyl sulfonic acid having 1 to 7 carbon atoms is preferable, and a conjugate base having 1 to 4 carbon atoms is more preferable. When expressed in the form of an acid, for example, methanesulfonic acid, trifluoromethane Particularly preferred are sulfonic acid, n-propanesulfonic acid and heptanesulfonic acid. As the conjugate base of the aryl sulfonic acid, for example, benzene sulfonic acid, chlorobenzene sulfonic acid, and paratoluene sulfonic acid are particularly preferable when expressed in an acid form.
　一般式（２）中、Ｒ８およびＲ９がそれぞれ独立に表わすアリール基は、一般式（１）中のＲ５、Ｒ６およびＲ７が表わすアリール基と同義であり、好ましい範囲も同様である。
　Ｒ８およびＲ９は、具体的にはフェニル基、４－メトキシフェニル基、４－クロロフェニル基が特に好ましい。また、Ｒ８およびＲ９は、同一の基を表すことが好ましい。
　一般式（１）中、Ｘ－が表わす共役塩基は、一般式（１）中のＸ－と同義であり、好ましい範囲も同様である。 In general formula (2), the aryl groups independently represented by R 8 and R 9 are the same as the aryl groups represented by R 5 , R 6 and R 7 in general formula (1), and the preferred ranges are also the same. is there.
Specifically, R 8 and R 9 are particularly preferably a phenyl group, a 4-methoxyphenyl group, and a 4-chlorophenyl group. R 8 and R 9 preferably represent the same group.
In general formula (1), the conjugate base represented by X − has the same meaning as X − in general formula (1), and the preferred range is also the same.
　オニウム塩化合物の具体例としては、４，７－ジ－ｎ－ブトキシ－１－ナフチルテトラヒドロチオフェニウムトリフルオロメタンスルホネートなどが挙げられる。また、下記の化合物や、特開２０１１－２３２６４８号公報の段落００８３～００８５記載の化合物を挙げることができる。 Specific examples of the onium salt compound include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate. Moreover, the following compounds and the compounds described in JP-A-2011-232648, paragraphs 0083 to 0085 can be exemplified.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　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, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1).
Figure JPOXMLDOC01-appb-C000020
 （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。）
Figure JPOXMLDOC01-appb-C000020
 (In the general formula (B1), R 21 represents an alkyl group or an aryl group. A wavy line represents a bond with another group.)
　Ｒ２１におけるアルキル基、アリール基は、いずれの基も置換されてもよい。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。
　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、ハロゲン原子、炭素数６～１１のアリール基、炭素数１～１０のアルコキシ基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、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 of the alkyl group and aryl group in R 21 may be substituted. The alkyl group in R 21 may be linear, branched or cyclic.
The alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R 21 may be substituted with a halogen atom, an aryl group having 6 to 11 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
The aryl group for 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 with an alkyl group, an alkoxy group, or a halogen atom.
　オキシムスルホネート化合物の好ましい形態の一例としては、特開２０１３－１９０５０７号公報の段落番号０１０８～０１４１の記載が例示され、これらの内容は本明細書に組み込まれる。 As an example of a preferred form of the oxime sulfonate compound, description of paragraph numbers 0108 to 0141 of JP2013-190507A is exemplified, and the contents thereof are incorporated in the present specification.
　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の好ましい態様としては、下記一般式（Ｂ１－１）で表されるオキシムスルホネート化合物である。 A preferred embodiment of the compound containing the oxime sulfonate structure represented by the general formula (B1) is an oxime sulfonate compound represented by the following general formula (B1-1).
一般式（Ｂ１－１）
Figure JPOXMLDOC01-appb-C000021
 （式（Ｂ１－１）中、Ｒ４２は、置換されていても良い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。） General formula (B1-1)
Figure JPOXMLDOC01-appb-C000021
 (In the formula (B1-1), R 42 represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents 0-3. Represents an integer, and when m4 is 2 or 3, a plurality of Xs may be the same or different.
　Ｒ４２の好ましい範囲としては、上記Ｒ２１の好ましい範囲と同一である。
　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（Ｂ１－１）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。 Preferred ranges of R 42, the same as the preferable range of the R 21.
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 (B1-1), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound which is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
　一般式（Ｂ１－１）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、例えば、以下の化合物が例示できる。 Specific examples of the oxime sulfonate compound represented by the general formula (B1-1) include the following compounds.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　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の他の好ましい態様としては、下記一般式（Ｂ１－２）で表されるオキシムスルホネート化合物である。 Another preferred embodiment of the compound containing an oxime sulfonate structure represented by the above general formula (B1) is an oxime sulfonate compound represented by the following general formula (B1-2).
一般式（Ｂ１－２）
Figure JPOXMLDOC01-appb-C000023
 （式（Ｂ１－２）中、Ｒ４３は式（Ｂ１－１）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。） General formula (B1-2)
Figure JPOXMLDOC01-appb-C000023
 (In the formula (B1-2), R 43 has the same meaning as R 42 in the formula (B1-1), and X 1 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)
　上記一般式（Ｂ１－２）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。 R 43 in the above general formula (B1-2) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n- A propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
　上記一般式（Ｂ１－２）で表される化合物の具体例および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、例えば、以下の化合物が例示できる。また、以下に例示する化合物の他にも、特開２０１２－１６３９３７号公報の段落番号００８０～００８２の記載を参酌でき、この内容は本明細書に組み込まれる。 Specific examples of the compound represented by the general formula (B1-2) and specific examples of preferred oxime sulfonate compounds include the following compounds. In addition to the compounds exemplified below, paragraphs 0080 to 0082 of JP2012-163937A can be referred to, and the contents thereof are incorporated in the present specification.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　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の他の好ましい態様としては、下記一般式（ＯＳ－１）で表される化合物である。 Another preferred embodiment of the compound containing an oxime sulfonate structure represented by the above general formula (B1) is a compound represented by the following general formula (OS-1).
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　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。
　上述した官能基は、いずれも、さらに置換基を有していてもよい。 In the 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 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups. Or an aryl group.
R 121 to R 124 each independently represents 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 amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R 121 to R 124 may be bonded to each other to form a ring.
R 121 to R 124 are preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which 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 general formula (OS-1) include compounds described in paragraph numbers 0128 to 0132 of JP2011-212494A (exemplary compounds b-1 to b-34). However, the present invention is not limited to this.
　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の他の好ましい態様としては、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。 As another preferred embodiment of the compound containing the oxime sulfonate structure represented by the general formula (B1), the following general formula (OS-3), the following general formula (OS-4) or the following general formula (OS-5) It is an oxime sulfonate compound represented by these.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　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。） In the general formulas (OS-3) to (OS-5), R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group, and R 23 , R 26 and R 29 are Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X 1 to X 3 each independently represents an oxygen atom or a sulfur atom, n 1 to n 3 each independently represents 1 or 2, and m 1 to m 3 each independently represents an integer of 0 to 6 To express. )
　一般式（ＯＳ－３）～（ＯＳ－５）については、例えば、特開２０１２－１６３９３７号公報の段落番号００９８～０１１５の記載を参酌でき、この内容は本明細書に組み込まれる。一般式（ＯＳ－３）で表される化合物としては、例えば、以下が例示できる。 Regarding the general formulas (OS-3) to (OS-5), for example, the description of paragraph numbers 0098 to 0115 of JP2012-163937A can be referred to, and the contents thereof are incorporated in the present specification. Examples of the compound represented by the general formula (OS-3) include the following.
　また、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、例えば、特開２０１２－１６３９３７号公報の段落番号０１１７に記載されている、一般式（ＯＳ－６）～（ＯＳ－１１）のいずれかで表される化合物であることが特に好ましく、この内容は本明細書に組み込まれる。
　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。 In addition, the compound having an oxime sulfonate structure represented by the general formula (B1) is, for example, the general formulas (OS-6) to (OS-) described in paragraph No. 0117 of JP2012-163937A. It is particularly preferable that the compound is represented by any one of 11), the contents of which are incorporated herein.
Preferred ranges in the general formulas (OS-6) to (OS-11) are the preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. It is the same.
　一般式（ＯＳ－３）～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。 Specific examples of the oxime sulfonate compounds represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. The present invention is not limited to these.
　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の他の好ましい態様としては、下記一般式（Ｂ１－３）で表されるオキシムスルホネート化合物である。 Another preferred embodiment of the compound containing an oxime sulfonate structure represented by the general formula (B1) is an oxime sulfonate compound represented by the following general formula (B1-3).
一般式（Ｂ１－３）
Figure JPOXMLDOC01-appb-C000027
 General formula (B1-3)
Figure JPOXMLDOC01-appb-C000027
　一般式（Ｂ１－３）中、Ｒ１は、アルキル基またはアリール基を表し、Ｒ２は、アルキル基、アリール基、またはヘテロアリール基を表す。Ｒ３～Ｒ６は、それぞれ、水素原子、アルキル基、アリール基、ハロゲン原子を表す。但し、Ｒ３とＲ４、Ｒ４とＲ５、またはＲ５とＲ６が結合して脂環または芳香環を形成してもよい。Ｘは、－Ｏ－または－Ｓ－を表す。 In General Formula (B1-3), R 1 represents an alkyl group or an aryl group, and R 2 represents an alkyl group, an aryl group, or a heteroaryl group. R 3 to R 6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. However, R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may be bonded to form an alicyclic ring or an aromatic ring. X represents —O— or —S—.
　Ｒ１は、アルキル基またはアリール基を表す。アルキル基は、直鎖状、分岐状、環状が挙げられ、分岐状または環状が好ましい。
　アルキル基の炭素数は、好ましくは３～１０である。分岐状のアルキル基の場合、炭素数は３～６が好ましい。環状のアルキル基の場合、炭素数は５～７が好ましい。
　アルキル基の具体例としては、例えば、プロピル基、イソプロピル基、ｎ－ブチル基、ｓ－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、１，１－ジメチルプロピル基、ヘキシル基、２－エチルヘキシル基、シクロヘキシル基、オクチル基などが挙げられ、好ましくは、イソプロピル基、ｔｅｒｔ－ブチル基、ネオペンチル基、シクロヘキシル基である。
　アリール基の炭素数は、好ましくは６～１２であり、より好ましくは６～８であり、さらに好ましくは６～７である。アリール基の具体例としては、フェニル基、ナフチル基などが挙げられ、好ましくは、フェニル基である。
　Ｒ１が表すアルキル基およびアリール基は、置換基を有していてもよい。置換基としては、例えばハロゲン原子（フッ素原子、クロロ原子、臭素原子、ヨウ素原子）、直鎖、分岐状または環状のアルキル基（例えばメチル基、エチル基、プロピル基など）、アルケニル基、アルキニル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、シアノ基、カルボキシ基、水酸基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、ヘテロ環オキシ基、アシルオキシ基、アミノ基、ニトロ基、ヒドラジノ基、ヘテロ環基などが挙げられる。また、これらの基によってさらに置換されていてもよい。好ましくは、ハロゲン原子、メチル基である。 R 1 represents an alkyl group or an aryl group. Examples of the alkyl group include linear, branched, and cyclic groups, and branched or cyclic groups are preferable.
The alkyl group preferably has 3 to 10 carbon atoms. In the case of a branched alkyl group, the number of carbon atoms is preferably 3-6. In the case of a cyclic alkyl group, the number of carbon atoms is preferably 5 to 7.
Specific examples of the alkyl group include, for example, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group. Hexyl group, 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms. Specific examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R 1 may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chloro atom, bromine atom, iodine atom), linear, branched or cyclic alkyl group (eg, methyl group, ethyl group, propyl group), alkenyl group, alkynyl group. , Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxy group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group , A nitro group, a hydrazino group, a heterocyclic group, and the like. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.
　本発明の感光性樹脂組成物は、透明性の観点から、Ｒ１はアルキル基が好ましく、保存安定性と感度とを両立させる観点から、Ｒ１は、炭素数３～６の分岐状のアルキル基、炭素数５～７の環状のアルキル基、または、フェニル基が好ましく、炭素数３～６の分岐状のアルキル基、または炭素数５～７の環状のアルキル基がより好ましい。このようなかさ高い基（特に、かさ高いアルキル基）をＲ１として採用することにより、透明性をより向上させることが可能になる。
　かさ高い置換基の中でも、イソプロピル基、ｔｅｒｔ－ブチル基、ネオペンチル基、シクロヘキシル基が好ましく、ｔｅｒｔ－ブチル基、シクロヘキシル基がより好ましい。 In the photosensitive resin composition of the present invention, R 1 is preferably an alkyl group from the viewpoint of transparency, and R 1 is a branched alkyl group having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity. Group, a cyclic alkyl group having 5 to 7 carbon atoms, or a phenyl group is preferable, and a branched alkyl group having 3 to 6 carbon atoms or a cyclic alkyl group having 5 to 7 carbon atoms is more preferable. By adopting such a bulky group (particularly a bulky alkyl group) as R 1 , the transparency can be further improved.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.
　Ｒ２は、アルキル基、アリール基、またはヘテロアリール基を表す。Ｒ２が表すアルキル基としては、炭素数１～１０の、直鎖状、分岐状または環状のアルキル基が好ましい。アルキル基としては、例えば、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、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基などが挙げられ、好ましくは、メチル基である。
　アリール基としては、炭素数６～１０のアリール基が好ましい。アリール基としては、フェニル基、ナフチル基、ｐ－トルイル基（ｐ－メチルフェニル基）などが挙げられ、好ましくは、フェニル基、ｐ－トルイル基である。
　ヘテロアリール基としては、例えば、ピロール基、インドール基、カルバゾール基、フラン基、チオフェン基などが挙げられる。
　Ｒ２が表すアルキル基、アリール基、およびヘテロアリール基は、置換基を有していてもよい。置換基としては、Ｒ１が表すアルキル基およびアリール基が有していてもよい置換基と同義である。
　Ｒ２は、アルキル基またはアリール基が好ましく、アリール基がより好ましく、フェニル基がより好ましい。フェニル基の置換基としてはメチル基が好ましい。 R 2 represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R 2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group, preferably a methyl group. It is.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, and a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R 2 may have a substituent. Examples of the substituent include an alkyl group and an aryl group R 1 represents is same as the substituents which may be possessed.
R 2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.
　Ｒ３～Ｒ６は、それぞれ、水素原子、アルキル基、アリール基、またはハロゲン原子（フッ素原子、クロロ原子、臭素原子、ヨウ素原子）を表す。Ｒ３～Ｒ６が表すアルキル基としては、Ｒ２が表すアルキル基と同義であり、好ましい範囲も同様である。また、Ｒ３～Ｒ６が表すアリール基としては、Ｒ１が表すアリール基と同義であり、好ましい範囲も同様である。
　Ｒ３～Ｒ６のうち、Ｒ３とＲ４、Ｒ４とＲ５、またはＲ５とＲ６が結合して環を形成してもよく、環としては、脂環または芳香環を形成していることが好ましく、ベンゼン環がより好ましい。
　Ｒ３～Ｒ６は、水素原子、アルキル基、ハロゲン原子（フッ素原子、クロロ原子、臭素原子）、または、Ｒ３とＲ４、Ｒ４とＲ５、またはＲ５とＲ６が結合してベンゼン環を構成していることが好ましく、水素原子、メチル基、フッ素原子、クロロ原子、臭素原子またはＲ３とＲ４、Ｒ４とＲ５、またはＲ５とＲ６が結合してベンゼン環を構成していることがより好ましい。
　Ｒ３～Ｒ６の好ましい態様は以下の通りである。
（態様１）少なくとも２つは水素原子である。
（態様２）アルキル基、アリール基、またはハロゲン原子の数は、１つ以下である。
（態様３）Ｒ３とＲ４、Ｒ４とＲ５、またはＲ５とＲ６が結合してベンゼン環を構成している。
（態様４）上記態様１と２を満たす態様、および／または、上記態様１と３を満たす態様。 R 3 to R 6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom). The alkyl group represented by R 3 to R 6 has the same meaning as the alkyl group represented by R 2 , and the preferred range is also the same. The aryl group represented by R 3 to R 6 has the same meaning as the aryl group represented by R 1 , and the preferred range is also the same.
Among R 3 to R 6 , R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form a ring, and the ring forms an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
R 3 to R 6 are a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 It preferably constitutes a benzene ring, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are bonded to form a benzene ring Is more preferable.
Preferred embodiments of R 3 to R 6 are as follows.
(Aspect 1) At least two are hydrogen atoms.
(Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is one or less.
(Aspect 3) R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are combined to form a benzene ring.
(Aspect 4) An aspect satisfying the above aspects 1 and 2 and / or an aspect satisfying the above aspects 1 and 3.
　上記一般式（Ｂ１－３）の具体例としては、以下のような化合物が挙げられるが、本発明では特にこれに限定されない。なお、例示化合物中、Ｔｓはトシル基（ｐ－トルエンスルホニル基）を表し、Ｍｅはメチル基を表し、Ｂｕはｎ－ブチル基を表し、Ｐｈはフェニル基を表す。 Specific examples of the general formula (B1-3) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　イミドスルホネート化合物としては、下記一般式（Ｂ２）で表される構造を有するイミドスルホネート化合物を好ましく用いることができる。 As the imide sulfonate compound, an imide sulfonate compound having a structure represented by the following general formula (B2) can be preferably used.
Figure JPOXMLDOC01-appb-C000029
 　（一般式（Ｂ２）中、Ｒ２００は、炭素原子数１６以下の１価有機基を表す。波線は他の基との結合を表す。）
Figure JPOXMLDOC01-appb-C000029
 (In the general formula (B2), R 200 represents a monovalent organic group having 16 or less carbon atoms. The wavy line represents a bond with another group.)
　Ｒ２００は、炭素原子数１６以下の１価有機基を表す。Ｒ２００は、Ｃ、Ｈ、Ｏ、Ｆ以外を含まないことが好ましい。Ｒ２００としては、例えば、メチル基、トリフルオロメチル基、プロピル基、フェニル基、トシル基などが挙げられる。
　一般式（Ｂ２）で表される構造を含有する化合物の好ましい態様としては、下記一般式（Ｉ）で表されるイミドスルホネート化合物である。 R 200 represents a monovalent organic group having 16 or less carbon atoms. R 200 preferably does not contain other than C, H, O, and F. Examples of R 200 include a methyl group, a trifluoromethyl group, a propyl group, a phenyl group, and a tosyl group.
A preferred embodiment of the compound containing the structure represented by the general formula (B2) is an imide sulfonate compound represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000030
 　式中、Ｒ１およびＲ２は、それぞれ、下記一般式（Ａ）で表される基または水素原子を表す。Ｒ３は、ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１～１８の脂肪族炭化水素基、ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６～２０のアリール基、ハロゲン原子および／またはアルキルチオ基で置換されてもよい炭素数７～２０のアリールアルキル基、１０－カンファーイル基または、下記一般式（Ｂ）で表される基を表す。
Figure JPOXMLDOC01-appb-C000030
 In the formula, R 1 and R 2 each represent a group represented by the following general formula (A) or a hydrogen atom. R 3 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group, a halogen atom, an alkylthio group, an alkyl group and an acyl An aryl group having 6 to 20 carbon atoms which may be substituted with any one or more of the groups, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, 10-camphoryl group Or represents the group represented by the following general formula (B).
Figure JPOXMLDOC01-appb-C000031
 　一般式（Ａ）中、Ｘ１は、酸素原子または硫黄原子を表し、Ｙ１は、単結合または炭素数１～４のアルキレン基を表し、Ｒ４は、炭素数１～１２の炭化水素基を表し、Ｒ５は、炭素数１～４のアルキレン基を表し、Ｒ６は、水素原子、分岐していてもよい炭素数１～４のアルキル基、炭素数３～１０の脂環式炭化水素基、複素環基、または水酸基を表す。ｎは、０～５の整数を表し、ｎが２～５の場合、複数存在するＲ５は同一でも異なってもよい。
Figure JPOXMLDOC01-appb-C000031
 In general formula (A), X 1 represents an oxygen atom or a sulfur atom, Y 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R 4 represents a hydrocarbon group having 1 to 12 carbon atoms. R 5 represents an alkylene group having 1 to 4 carbon atoms, R 6 represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic carbon atom having 3 to 10 carbon atoms. Represents a hydrogen group, a heterocyclic group, or a hydroxyl group. n represents an integer of 0 to 5. When n is 2 to 5, a plurality of R 5 may be the same or different.
　式中、Ｘ１は、酸素原子又は硫黄原子を表し、Ｙ１は、単結合又は炭素数１～４のアルカンジイル基を表し、Ｒ１１は、炭素数１～１２の炭化水素基を表し、Ｒ１２は、炭素数１～４のアルカンジイル基を表し、Ｒ１３は、水素原子又は分岐を有してもよい炭素数１～４のアルキル基又は炭素数３～１０の脂環式炭化水素基若しくは複素環基を表し、ｍは、０～５を表し、ｍが２～５の場合、複数存在するＲ１２は同一でも異なってもよい。 In the formula, X 1 represents an oxygen atom or a sulfur atom, Y 1 represents a single bond or an alkanediyl group having 1 to 4 carbon atoms, R 11 represents a hydrocarbon group having 1 to 12 carbon atoms, R 12 represents an alkanediyl group having 1 to 4 carbon atoms, R 13 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a branch or an alicyclic hydrocarbon having 3 to 10 carbon atoms. Represents a group or a heterocyclic group, m represents 0 to 5, and when m is 2 to 5, a plurality of R 12 may be the same or different.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　一般式（Ｂ）中、Ｙ２は、単結合または炭素数１～４のアルキレン基を表し、Ｒ７は、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基、または炭素数６～２０のハロゲン化アリーレン基を表し、Ｒ８は、単結合、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基または炭素数６～２０のハロゲン化アリーレン基を表し、Ｒ９は、分岐していてもよい炭素数１～１８のアルキル基、分岐していてもよい炭素数１～１８のハロゲン化アルキル基、炭素数６～２０のアリール基、炭素数６～２０のハロゲン化アリール基、炭素数７～２０のアリールアルキル基、または炭素数７～２０のハロゲン化アリールアルキル基を表す。ａおよびｂはそれぞれ独立に０または１を表し、ａおよびｂの少なくとも一方は１である。 In general formula (B), Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms, R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms, and R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R 9 represents an alkyl group having 1 to 18 carbon atoms which may be branched, or 1 to 1 carbon atoms which may be branched. 18 halogenated alkyl groups, aryl groups having 6 to 20 carbon atoms, halogenated aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, or halogenated arylalkyl groups having 7 to 20 carbon atoms. To express. a and b each independently represents 0 or 1, and at least one of a and b is 1.
　一般式（Ｉ）については、例えば、国際公開ＷＯ１１／０８７０１１号公報の段落番号００１９～００６３の記載を参酌でき、この内容は本明細書に組み込まれる。一般式（Ｉ）で表される化合物としては、例えば、以下が例示できる。また、以下に例示する化合物の他にも、国際公開ＷＯ１１／０８７０１１号公報の段落番号００６５～００７５の記載や特許５５１０３４７号公報の段落００８４の記載を参酌でき、この内容は本明細書に組み込まれる。 Regarding the general formula (I), for example, the description of paragraph numbers 0019 to 0063 of International Publication No. WO11 / 087011 can be referred to, and the contents thereof are incorporated in the present specification. Examples of the compound represented by the general formula (I) include the following. In addition to the compounds exemplified below, the description of paragraphs 0065 to 0075 of International Publication No. WO11 / 087011 and the description of paragraph 0084 of Japanese Patent No. 5510347 can be taken into account, the contents of which are incorporated herein. .
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　本発明の感光性樹脂組成物における（Ｂ）光酸発生剤の含有量は、感光性樹脂組成物の全固形分に対し、０．１～１０質量％が好ましく、０．５～１０質量％がより好ましく、１～５質量％がさらに好ましい。
　また、（Ｂ）光酸発生剤は、（Ａ）ポリシロキサン成分１００質量部に対し、０．１～１０質量部含有することが好ましく、０．５～１０質量部がより好ましく、１～５質量部がさらに好ましい。
　（Ｂ）光酸発生剤は、１種のみであってもよいし、２種以上を併用することもできる。２種以上併用する場合は、その合計量が上記範囲となることが好ましい。 The content of the (B) photoacid generator in the photosensitive resin composition of the present invention is preferably 0.1 to 10% by mass, and preferably 0.5 to 10% by mass with respect to the total solid content of the photosensitive resin composition. Is more preferable, and 1 to 5% by mass is even more preferable.
The (B) photoacid generator is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the (A) polysiloxane component. Part by mass is more preferable.
(B) Only 1 type may be sufficient as a photo-acid generator, and it can also use 2 or more types together. When using 2 or more types together, it is preferable that the total amount becomes the said range.
＜＜（Ｃ）溶剤（Ｃ成分）＞＞
　本発明の感光性樹脂組成物は、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溶剤に溶解した溶液として調製されることが好ましい。溶剤としては、必須成分及び任意成分を均一に溶解し、各成分と反応しないものが用いられる。
　本発明において溶剤としては、公知の溶剤を用いることができる。例えば、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、特開２０１１－２２１４９４号公報の段落番号０１７４～０１７８に記載の溶剤、特開２０１２－１９４２９０公報の段落番号０１６７～０１６８に記載の溶剤も挙げられ、これらの内容は本明細書に組み込まれる。例えば、溶剤の具体例の一例としては、プロピレングリコール１－モノメチルエーテル２－アセタート、メチルエチルジグリコールなどが挙げられる。 << (C) Solvent (Component C) >>
The photosensitive resin composition of the present invention contains a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent. As the solvent, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
In the present invention, a known solvent can be used as the solvent. For example, 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 Examples thereof include monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Further, the solvent described in paragraph Nos. 0174 to 0178 of JP2011-221494A and the solvent described in paragraph numbers 0167 to 0168 of JP2012-194290A are also included, and the contents thereof are incorporated in the present specification. . For example, specific examples of the solvent include propylene glycol 1-monomethyl ether 2-acetate, methyl ethyl diglycol and the like.
　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, 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 as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.
　また、溶剤は、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。 The solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (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溶剤の含有量は、感光性樹脂組成物中の全成分１００質量部に対し、５０～９５質量部であることが好ましい。５５質量％以上がより好ましく、６０質量部以上がさらに好ましい。上限は、９０質量部以下がより好ましい。溶剤は、１種類のみ用いてもよいし、２種類以上用いてもよい。２種類以上用いる場合は、その合計量が上記範囲となることが好ましい。 The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition. 55 mass% or more is more preferable, and 60 mass parts or more is further more preferable. The upper limit is more preferably 90 parts by mass or less. Only one type of solvent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.
＜（Ｓ）脂環式エポキシ化合物（Ｓ成分）＞
　本発明の感光性樹脂組成物は、式（ＥＰ）で表される分子量１５０～１０００の脂環式エポキシ化合物（以下、単に「脂環式エポキシ化合物」ということがある。）を含有する。なお、本発明において、「（Ｓ）脂環式エポキシ化合物」は、上述した（Ａ）ポリシロキサン成分で説明したポリシロキサンとは異なる化合物である。
Figure JPOXMLDOC01-appb-C000034
 　式中、ＲＥＰ１はアルキル基を表し、
　ｐは０～７の整数を表し、ｐが２以上の場合、複数のＲＥＰ１は同一であってもよく、異なってもよく、
　Ａは、酸素原子を含んでもよいｑ価の炭化水素基を表し、
　ｑは１～４の整数を表す。 <(S) Alicyclic epoxy compound (S component)>
The photosensitive resin composition of the present invention contains an alicyclic epoxy compound having a molecular weight of 150 to 1000 represented by the formula (EP) (hereinafter sometimes simply referred to as “alicyclic epoxy compound”). In the present invention, “(S) alicyclic epoxy compound” is a compound different from the polysiloxane described in the above (A) polysiloxane component.
Figure JPOXMLDOC01-appb-C000034
 In the formula, R EP1 represents an alkyl group,
p represents an integer of 0 to 7, and when p is 2 or more, a plurality of R EP1 may be the same or different,
A represents a q-valent hydrocarbon group that may contain an oxygen atom,
q represents an integer of 1 to 4.
　ｑは１～４の整数を表し、１～３が好ましく、２～３がより好ましく、２が特に好ましい。
　ＲＥＰ１はアルキル基を表す。
　アルキル基は、直鎖、分岐、環状が挙げられる。アルキル基の炭素数は、１～１５が好ましく、１～１０が更に好ましく、１～５がより好ましく、１～３が特に好ましい。
　ｐは０～７の整数を表し、０～３が好ましく、０または１がより好ましい。 q represents an integer of 1 to 4, preferably 1 to 3, more preferably 2 to 3, and particularly preferably 2.
R EP1 represents an alkyl group.
Examples of the alkyl group include linear, branched and cyclic. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
p represents an integer of 0 to 7, preferably 0 to 3, more preferably 0 or 1.
　Ａは、酸素原子を含んでもよいｑ価の炭化水素基を表す。
　１価の炭化水素基としては、アルキル基、アリール基などが挙げられ、アルキル基が好ましい。
　アルキル基の炭素数は、１～１５が好ましく、１～１０がより好ましい。アルキル基は直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましく、直鎖がより好ましい。アルキル基は、無置換であってもよく、置換基を有していてもよい。置換基としては、ハロゲン原子、アルコキシ基、アリール基、アリールオキシ基などが挙げられる。
　アリール基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が更に好ましい。アリール基は、無置換であってもよく、置換基を有していてもよい。置換基としては、上述したものが挙げられる。
　２価の炭化水素基としては、アルキレン基、アリーレン基などが挙げられ、アルキレン基がより好ましい。
　アルキレン基の炭素数は、１～１５が好ましく、１～１０がより好ましい。アルキレン基は直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましく、直鎖がより好ましい。アルキレン基は、無置換であってもよく、置換基を有していてもよい。置換基としては、ハロゲン原子、アルコキシ基、アリール基、アリールオキシ基などが挙げられる。
　アリーレン基の炭素数は、６～３０が好ましく、６～２０がより好ましく、６～１２が更に好ましい。アリーレン基は、無置換であってもよく、置換基を有していてもよい。置換基としては、上述したものが挙げられる。
　３価の炭化水素基、４価の炭化水素基は、上述した２価の炭化水素基から水素原子を１つまたは２つ除いた基が挙げられる。
　酸素原子を含む炭化水素基としては、上述した炭化水素基と、－Ｏ－、－ＣＯ－、－ＣＯＯ－および－ＯＣＯ－から選ばれる少なくとも１種の基とを組み合わせてなる基が挙げられ、上述した炭化水素基と、－Ｏ－、－ＣＯＯ－および－ＯＣＯ－から選ばれる少なくとも一種とを組み合わせてなる基がより好ましく、上述した炭化水素基と、－ＣＯＯ－または－ＯＣＯ－とを組み合わせてなる基がさらに好ましい。 A represents a q-valent hydrocarbon group that may contain an oxygen atom.
Examples of the monovalent hydrocarbon group include an alkyl group and an aryl group, and an alkyl group is preferable.
The alkyl group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear. The alkyl group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, an aryl group, and an aryloxy group.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. The aryl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
Examples of the divalent hydrocarbon group include an alkylene group and an arylene group, and an alkylene group is more preferable.
The alkylene group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkylene group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear. The alkylene group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, an aryl group, and an aryloxy group.
The carbon number of the arylene group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The arylene group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
Examples of the trivalent hydrocarbon group and the tetravalent hydrocarbon group include groups obtained by removing one or two hydrogen atoms from the above-described divalent hydrocarbon group.
Examples of the hydrocarbon group containing an oxygen atom include a group formed by combining the above-described hydrocarbon group and at least one group selected from —O—, —CO—, —COO—, and —OCO—, A group formed by combining the above-described hydrocarbon group and at least one selected from —O—, —COO—, and —OCO— is more preferable, and the above-described hydrocarbon group and —COO— or —OCO— are combined. The group consisting of
　脂環式エポキシ化合物は、下式（ＥＰ１）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000035
 　式中、ＲＥＰ２およびＲＥＰ３は、それぞれ独立にアルキル基を表し、
　ｐは０～７の整数を表し、ｐが２以上の場合、複数のＲＥＰ２およびＲＥＰ３は、同一であってもよく、異なってもよく、
　Ａ１は、－Ｏ－、－ＣＯＯ－および－ＯＣＯ－から選ばれる少なくとも一種を含む２価の炭化水素基を表す。 The alicyclic epoxy compound is preferably a compound represented by the following formula (EP1).
Figure JPOXMLDOC01-appb-C000035
 In the formula, R EP2 and R EP3 each independently represent an alkyl group,
p represents an integer of 0 to 7, and when p is 2 or more, the plurality of R EP2 and R EP3 may be the same or different,
A 1 represents a divalent hydrocarbon group containing at least one selected from —O—, —COO—, and —OCO—.
　ＲＥＰ２、ＲＥＰ３、ｐは、一般式（ＥＰ）におけるＲＥＰ、ｐと同義であり、好ましい範囲も同様である。
　Ａ１は、－Ｏ－、－ＣＯＯ－および－ＯＣＯ－から選ばれる少なくとも一種を含む２価の炭化水素基を表す。２価の炭化水素基としては、一般式（ＥＰ）で説明したものが挙げられ、アルキレン基が好ましい。
　アルキレン基の炭素数は、１～１５が好ましく、１～１０がより好ましい。アルキレン基は直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましく、直鎖がより好ましい。アルキレン基は、無置換であってもよく、置換基を有していてもよい。置換基としては、上述したものが挙げられる。 R EP2, R EP3, p has the same meaning as R EP, p in the general formula (EP), and preferred ranges are also the same.
A 1 represents a divalent hydrocarbon group containing at least one selected from —O—, —COO—, and —OCO—. As a bivalent hydrocarbon group, what was demonstrated by general formula (EP) is mentioned, An alkylene group is preferable.
The alkylene group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkylene group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear. The alkylene group may be unsubstituted or may have a substituent. Examples of the substituent include those described above.
　脂環式エポキシ化合物は、下式（ＥＰ２）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000036
 　式中、ＲＥＰ２およびＲＥＰ３は、それぞれ独立にアルキル基を表し、
　ｐは０～７の整数を表し、ｐが２以上の場合、複数のＲＥＰ２およびＲＥＰ３は、同一であってもよく、異なってもよく、
　Ａ２は、アルキレン基を表す。 The alicyclic epoxy compound is preferably a compound represented by the following formula (EP2).
Figure JPOXMLDOC01-appb-C000036
 In the formula, R EP2 and R EP3 each independently represent an alkyl group,
p represents an integer of 0 to 7, and when p is 2 or more, the plurality of R EP2 and R EP3 may be the same or different,
A 2 represents an alkylene group.
　ＲＥＰ２、ＲＥＰ３、ｐは、一般式（ＥＰ）におけるＲＥＰ、ｐと同義であり、好ましい範囲も同様である。
　Ａ２は、アルキレン基を表す。アルキレン基の炭素数は、１～１５が好ましく、１～１０がより好ましい。アルキレン基は直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましく、直鎖がより好ましい。アルキレン基は、置換基を有していてもよいが、無置換が好ましい。 R EP2, R EP3, p has the same meaning as R EP, p in the general formula (EP), and preferred ranges are also the same.
A 2 represents an alkylene group. The alkylene group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkylene group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear. The alkylene group may have a substituent, but is preferably unsubstituted.
　上記式（１）～（３）の具体例としては、以下のような化合物が挙げられるが、本発明では特にこれに限定されるものではない。
Figure JPOXMLDOC01-appb-C000037
 Specific examples of the above formulas (1) to (3) include the following compounds, but the present invention is not particularly limited thereto.
Figure JPOXMLDOC01-appb-C000037
　本発明で用いる脂環式エポキシ化合物は、その製法は問わないが、例えば、丸善ＫＫ出版、第四版実験化学講座２０有機合成ＩＩ、２１３～、平成４年、Ｅｄ．ｂｙ　Ａｌｆｒｅｄ　Ｈａｓｆｎｅｒ，　Ｔｈｅ　ｃｈｅｍｉｓｔｒｙ　ｏｆ　ｈｅｔｅｒｏｃｙｃｌｉｃ　ｃｏｍｐｏｕｎｄｓ－Ｓｍａｌｌ　Ｒｉｎｇ　Ｈｅｔｅｒｏｃｙｃｌｅｓ　ｐａｒｔ３　ｏｘｉｒａｎｅｓ，　Ｊｏｈｎ＆Ｗｉｌｅｙ　ａｎｄ　Ｓｏｎｓ，　Ａｎ　Ｉｎｔｅｒｓｃｉｅｎｃｅ　Ｐｕｂｌｉｃａｔｉｏｎ，　Ｎｅｗ　Ｙｏｒｋ，　１９８５、吉村、接着、２９巻１２号、３２、１９８５、吉村、接着、３０巻５号、４２、１９８６、吉村、接着、３０巻７号、４２、１９８６、特開平１－１００３７８号、特許第２９０６２４５号、特許第２９２６２６２号の各公報等の文献を参考にして合成できる。 The production method of the alicyclic epoxy compound used in the present invention is not limited. For example, Maruzen KK Publishing, 4th Edition Experimental Chemistry Course 20 Organic Synthesis II, 213-, 1992, Ed. by Alfred Hasfner, The chemistry of heterocyclic compounds-Small Ring Heterocycles part3 oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, adhesive, Vol. 29 No. 12, 32,1985, Yoshimura, adhesive, Vol. 30, No. 5 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, JP-A-1-100388, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.
　本発明で用いる脂環式エポキシ化合物の分子量は、１５０～１０００であり、２００～４００が好ましく、２００～３００が最も好ましい。このような範囲とすることにより、本発明の効果がより効果的に発揮される。なお、脂環式エポキシ化合物の分子量は、構造式から算出した理論値であり、構造式から算出できない場合は、ＧＰＣ測定によるポリスチレン換算値による重量平均分子量である。 The molecular weight of the alicyclic epoxy compound used in the present invention is 150 to 1000, preferably 200 to 400, and most preferably 200 to 300. By setting it as such a range, the effect of this invention is exhibited more effectively. In addition, the molecular weight of an alicyclic epoxy compound is a theoretical value calculated from the structural formula, and when the molecular weight cannot be calculated from the structural formula, it is a weight average molecular weight based on a polystyrene conversion value by GPC measurement.
　本発明の感光性樹脂組成物中における脂環式エポキシ化合物の含有量は、感光性樹脂組成物の全固形分に対し、０．１～１０質量％が好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上が更に好ましい。上限は、８質量％以下がより好ましく、５質量％以下更に好ましい。脂環式エポキシ化合物は、１種類のみ用いてもよいし、２種類以上用いてもよい。２種類以上用いる場合は、その合計量が上記範囲となることが好ましい。 The content of the alicyclic epoxy compound in the photosensitive resin composition of the present invention is preferably 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. As for an upper limit, 8 mass% or less is more preferable, and 5 mass% or less is still more preferable. Only one type of alicyclic epoxy compound may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.
＜＜増感剤＞＞
　本発明の感光性樹脂組成物は、光酸発生剤との組み合わせにおいて、光酸発生剤の分解を促進させるために、増感剤を含有することができる。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３５０～４５０ｎｍの波長域のいずれかに吸収波長を有する化合物が挙げられる。 << Sensitizer >>
The photosensitive resin composition of the present invention can contain a sensitizer in order to promote the decomposition of the photoacid generator in combination with the photoacid generator. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferable sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges of 350 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）、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 ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 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. Of the polynuclear aromatics, anthracene derivatives are most preferred.
　増感剤の含有量は、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。増感剤は、１種のみであってもよいし、２種以上を併用することもできる。２種以上を併用する場合は、合計量が上記範囲であることが好ましい。 The content of the sensitizer is preferably 0 to 1000 parts by weight, more preferably 10 to 500 parts by weight, and more preferably 50 to 200 parts by weight with respect to 100 parts by weight of the photoacid generator. Further preferred. Only one type of sensitizer may be used, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount is the said range.
＜＜架橋剤＞＞
　本発明の感光性樹脂組成物は、必要に応じて、架橋剤を含有することができる。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。
　架橋剤は、架橋基を分子内に少なくとも２つ以上含有する化合物である。架橋基とは、熱により、ポリシロキサンの、架橋性基、ベンゼン環、ヒドロキシ基、および、カルボキシ基から選ばれる１種以上と反応する基を意味する。架橋基としては、メチロール基、エポキシ基、オキセタニル基、アルコキシメチル基、メタクリロイル基およびアクリロイル基が好ましく、メチロール基、エポキシ基、アルコキシメチル基、メタクリロイル基およびアクリロイル基がより好ましい。
　架橋剤一分子中の架橋基の数は、３以上であることが好ましく、４以上であることがより好ましい。
　架橋基は、同じ種類の架橋基を分子内に２つ以上有していてもよいし、異なる種類の架橋基を分子内に２つ以上有していてもよい。
　架橋剤の分子量は、１５０～３００００が好ましく、２００～１００００がより好ましい。このような範囲とすることにより、本発明の効果がより効果的に発揮される。 << Crosslinking agent >>
The photosensitive resin composition of this invention can contain a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is a compound containing at least two crosslinking groups in the molecule. The cross-linking group means a group that reacts with one or more kinds selected from a cross-linkable group, a benzene ring, a hydroxy group, and a carboxy group of polysiloxane by heat. As the crosslinking group, a methylol group, an epoxy group, an oxetanyl group, an alkoxymethyl group, a methacryloyl group and an acryloyl group are preferable, and a methylol group, an epoxy group, an alkoxymethyl group, a methacryloyl group and an acryloyl group are more preferable.
The number of crosslinking groups in one molecule of the crosslinking agent is preferably 3 or more, and more preferably 4 or more.
The cross-linking group may have two or more of the same type of cross-linking group in the molecule, or may have two or more different types of cross-linking groups in the molecule.
The molecular weight of the crosslinking agent is preferably from 150 to 30,000, more preferably from 200 to 10,000. By setting it as such a range, the effect of this invention is exhibited more effectively.
　本発明の感光性樹脂組成物が、架橋剤を含有する場合、架橋剤の含有量は、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。上記範囲であれば、機械的強度および溶剤耐性に優れた硬化膜が得られる。架橋剤は１種のみであってもよいし、２種以上を併用することもできる。２種以上を併用する場合は、合計量が上記範囲であることが好ましい。
　また、本発明の感光性樹脂組成物は、架橋剤を実質的に含まない構成とすることもできる。実施的に含まない構成とは、架橋剤が感光性樹脂組成物の固形分の、例えば、１質量％以下であることをいう。 When the photosensitive resin composition of the present invention contains a crosslinking agent, the content of the crosslinking agent is 0.01 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. Preferably, the amount is 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass. If it is the said range, the cured film excellent in mechanical strength and solvent tolerance will be obtained. Only one type of crosslinking agent may be used, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount is the said range.
Moreover, the photosensitive resin composition of this invention can also be set as the structure which does not contain a crosslinking agent substantially. The configuration that is not practically used means that the crosslinking agent is, for example, 1% by mass or less of the solid content of the photosensitive resin composition.
＜＜＜分子内に２個以上のエポキシ基を有する化合物＞＞＞
　本発明では、架橋剤として、上述した（Ｓ）脂環式エポキシ化合物とは異なる化合物であって、分子内に２個以上のエポキシ基を有する化合物を用いることができる。
　架橋剤として用いる分子内に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、エポキシ基含有構成単位有するアクリル樹脂等を挙げることができる。
　これらは市販品として入手できる。例えば、ＪＥＲ１５２、ＪＥＲ１５７Ｓ７０、ＪＥＲ１５７Ｓ６５、ＪＥＲ８０６、ＪＥＲ８２８、ＪＥＲ１００７（（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、その他にも、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－３２１Ｌ、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、セロキサイド ２０８１、ＥＨＰＥ３１５０、ＥＨＰＥ３１５０ＣＥ（以上（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。
　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。 <<< Compound having two or more epoxy groups in the molecule >>>
In the present invention, as the crosslinking agent, a compound that is different from the above-described (S) alicyclic epoxy compound and has two or more epoxy groups in the molecule can be used.
Specific examples of compounds having two or more epoxy groups in the molecule used as a crosslinking agent include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins, and aliphatic epoxy resins. And an acrylic resin having an epoxy group-containing structural unit.
These are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) and the like are commercially available products described in paragraph No. 0189 of JP2011-212494, etc. 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- 321L, 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, X-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase Chemtech), YH-300 YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.), Celoxide 2021P, Celoxide 2081, EHPE3150, EHPE3150CE (above, Daicel Corporation), and the like. These can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.
＜＜＜分子内に２個以上のアルコキシメチル基またはメチロール基を含有する架橋剤＞＞＞
　本発明では、架橋剤として、アルコキシメチル基またはメチロール基を含有する架橋剤を用いることができる。分子内に２個以上のアルコキシメチル基またはメチロール基を含有する架橋剤としては、下記一般式（１）または一般式（２）で表される構造を分子内に２個以上有する架橋剤であり、アルコキシメチル基とメチロール基のいずれか一方または両方を合計で２個以上分子内に含有する。
　－ＣＨ２ＯＲ１　（１）
（式中、Ｒ１は炭素原子数１～８のアルキル基を表し、炭素数１～４のアルキル基が好ましく、メチル基がより好ましい。）
　－ＣＨ２ＯＨ　（２） <<< Crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule >>>
In the present invention, a crosslinking agent containing an alkoxymethyl group or a methylol group can be used as the crosslinking agent. The crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule is a crosslinking agent having two or more structures represented by the following general formula (1) or general formula (2) in the molecule. , One or both of an alkoxymethyl group and a methylol group are contained in the molecule in a total of two or more.
—CH 2 OR 1 (1)
(Wherein R 1 represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.)
—CH 2 OH (2)
　アルコキシメチル基またはメチロール基は、窒素原子または芳香族環を形成する炭素原子に結合していることが好ましい。 The alkoxymethyl group or methylol group is preferably bonded to a nitrogen atom or a carbon atom forming an aromatic ring.
　アルコキシメチル基またはメチロール基が、窒素原子に結合している架橋剤としては、アルコキシメチル化メラミン、メチロール化メラミン、アルコキシメチル化ベンゾグアナミン、メチロール化ベンゾグアナミン、アルコキシメチル化グリコールウリル、メチロール化グリコールウリル、アルコキシメチル化尿素およびメチロール化尿素等が好ましい。アルコキシメチル化メラミン、アルコキシメチル化ベンゾグアナミン、アルコキシメチル化グリコールウリル、アルコキシメチル化尿素は、それぞれメチロール化メラミン、メチロール化ベンゾグアナミン、メチロール化グリコールウリル、または、メチロール化尿素のメチロール基をアルコキシメチル基に変換することにより得られる。このアルコキシメチル基の種類については、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基等を挙げることができるが、アウトガスの発生量の観点から、メトキシメチル基が特に好ましい。
　これらの化合物のうち、アルコキシメチル化メラミン、メチロール化メラミン、アルコキシメチル化ベンゾグアナミン、メチロール化ベンゾグアナミン、アルコキシメチル化グリコールウリル、メチロール化グリコールウリルが好ましく、透明性の観点から、アルコキシメチル化グリコールウリルおよびメチロール化グリコールウリルが特に好ましい。
　また、特開２０１２－８２２３号公報の段落番号０１０７に記載のアルコキシメチル基含有架橋剤を用いることができ、これらの内容は本明細書に組み込まれる。 Examples of the crosslinking agent in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxy Methylated urea and methylolated urea are preferred. Alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, and alkoxymethylated urea convert methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylol group of methylolated urea to alkoxymethyl group, respectively. Can be obtained. Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group, and the methoxymethyl group is particularly preferable from the viewpoint of outgas generation amount.
Of these compounds, alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril are preferred, and from the viewpoint of transparency, alkoxymethylated glycoluril and methylol Glycoluril is particularly preferred.
In addition, an alkoxymethyl group-containing crosslinking agent described in paragraph No. 0107 of JP2012-8223A can be used, and the contents thereof are incorporated herein.
　分子内に２個以上のアルコキシメチル基またはメチロール基を含有する架橋剤の好ましい構造として、下記式（８－１）～（８－４）で示される化合物及を挙げることができる。
Figure JPOXMLDOC01-appb-C000038
 　上記式（８－１）～（８－４）中、Ｒ７はそれぞれ独立して水素原子または炭素数１～８のアルキル基を表し、Ｒ８～Ｒ１１はそれぞれ独立して、水素原子、水酸基、アルキル基またはアルコキシル基を表し、Ｘ２は、単結合、メチレン基または酸素原子を表す。 Preferred structures of the crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule include compounds represented by the following formulas (8-1) to (8-4).
Figure JPOXMLDOC01-appb-C000038
 In the above formulas (8-1) to (8-4), R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R 8 to R 11 each independently represents a hydrogen atom, A hydroxyl group, an alkyl group or an alkoxyl group is represented, and X 2 represents a single bond, a methylene group or an oxygen atom.
　Ｒ７が表すアルキル基は、炭素数１～８であり、炭素数１～４がより好ましく、例えばメチル基、エチル基、プロピル基が挙げられる。
　Ｒ８～Ｒ１１が表すアルキル基は、炭素数１～８が好ましく、炭素数１～４がより好ましく、例えば、メチル基、エチル基、プロピル基が挙げられる。
　Ｒ８～Ｒ１１が表すアルコキシル基は、炭素数１～８が好ましく、炭素数１～４がより好ましく、例えばメトキシ基、エトキシ基、プロポキシ基が挙げられる。Ｘ２は単結合またはメチレン基であるのが好ましい。
　Ｒ７～Ｒ１１、Ｘ２は、メチル基、エチル基等のアルキル基、ハロゲン原子などで置換されていてもよい。複数個のＲ７、Ｒ８～Ｒ１１は、各々同一でも異なっていてもよい。 The alkyl group represented by R 7 has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
The alkyl group represented by R 8 to R 11 preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
The alkoxyl group represented by R 8 to R 11 preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. X 2 is preferably a single bond or a methylene group.
R 7 to R 11 and X 2 may be substituted with an alkyl group such as a methyl group or an ethyl group, or a halogen atom. The plurality of R 7 and R 8 to R 11 may be the same or different.
　分子内に２個以上のアルコキシメチル基またはメチロール基を含有する架橋剤は、市販品としても入手可能であり、例えば、サイメル３００、３０１、３０３、３７０、３２５、３２７、７０１、２６６、２６７、２３８、１１４１、２７２、２０２、１１５６、１１５８、１１２３、１１７０、１１７４、ＵＦＲ６５、３００（以上、三井サイアナミッド（株）製）、ニカラックＭＸ－７５０、－０３２、－７０６、－７０８、－４０、－３１、－２７０、－２８０、－２９０、－７５０ＬＭ、ニカラックＭＳ－１１、ニカラックＭＷ－３０ＨＭ、－１００ＬＭ、－３９０、（以上、（株）三和ケミカル製）などを好ましく使用することができる。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。 Crosslinkers containing two or more alkoxymethyl groups or methylol groups in the molecule are also available as commercial products, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalac MX-750, -032, -706, -708, -40,- 31, -270, -280, -290, -750LM, Nicarak MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used. These can be used alone or in combination of two or more.
＜＜＜分子内に２個以上のメタクリロイル基またはアクリロイル基を含む化合物＞＞＞
　本発明では、架橋剤として、メタクリロイル基またはアクリロイル基を含む化合物を使用してもよい。メタクリロイル基またはアクリロイル基を含む化合物とは、アクリル酸エステル、メタクリル酸エステルからなる群から選択される化合物である。アクリロイル基、メタクリロイル基は１分子中に２個以上、さらに好ましくは３官能以上ある化合物であることが好ましい。 <<< Compound containing two or more methacryloyl groups or acryloyl groups in the molecule >>>
In the present invention, a compound containing a methacryloyl group or an acryloyl group may be used as a crosslinking agent. The compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. It is preferable that the acryloyl group and the methacryloyl group are compounds having two or more, more preferably trifunctional or more in one molecule.
　２官能（メタ）アクリレートとしては、例えば、エチレングリコール（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ビスフェノキシエタノールフルオレンジアクリレート、ビスフェノキシエタノールフルオレンジアクリレートなどが挙げられる。
　３官能以上の（メタ）アクリレートとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリ（（メタ）アクリロイロキシエチル）フォスフェート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートなどが挙げられる。 
　好ましい市販品としては、日本化薬社製　ＫＡＹＡＲＡＤ　ＤＰＨＡ、新中村化学工業社製　ＮＫエステルシリーズで、二官能のＡ－２００、Ａ－４００、Ａ－６００、Ａ－１０００、ＡＢＥ－３００、Ａ－ＢＰＥ－４、Ａ－ＢＰＥ－１０、Ａ－ＢＰＥ－２０、Ａ－ＢＰＥ－３０、Ａ－ＢＰＰ－３、Ａ－ＤＯＤ、Ａ－ＤＣＰ、Ａ－ＩＢＤ－２Ｅ、Ａ－ＮＰＧ、７０１Ａ、Ａ－Ｂ１２０６ＰＥ、Ａ－ＨＤ－Ｎ、Ａ－ＮＯＤ－Ｎ、ＡＰＧ－１００、ＡＰＧ－２００、ＡＰＧ－４００、ＡＰＧ－７００、１Ｇ、２Ｇ、３Ｇ、４Ｇ、９Ｇ、１４Ｇ、２３Ｇ、ＢＧ、ＢＤ、ＨＤ－Ｎ、ＮＯＤ、ＩＮＤ、ＢＰＥ－１００、ＢＰＥ－２００、ＢＰＥ－３００、ＢＰＥ－５００、ＢＰＥ－９００、ＢＰＥ－１３００Ｎ、ＮＰＧ、ＤＣＰ、１２０６ＰＥ、７０１、３ＰＧ、９ＰＧ、３官能のＡ－９３００、ＡＴ－３０Ｅ、Ａ－ＴＭＰＴ－３ＥＯ、Ａ－ＴＭＰＴ－９ＥＯ、Ａ－ＴＭＰＴ－３ＰＯ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、ＴＭＰＴ、ＴＭＰＴ－９ＥＯ、４官能以上のＡＴＭ－３５Ｅ、ＡＴＭ－４Ｅ、ＡＤ－ＴＭＰ、ＡＤ－ＴＭＰ－Ｌ、ＡＴＭ－４Ｐ、Ａ－ＴＭＭＴ、Ａ－ＤＰＨ等を挙げることができる。 Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the tri- or more functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Preferable commercially available products are KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., NK ester series manufactured by Shin-Nakamura Chemical Co., Ltd., bifunctional A-200, A-400, A-600, A-1000, ABE-300, A- BPE-4, A-BPE-10, A-BPE-20, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A- B1206PE, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, BD, HD- N, NOD, IND, BPE-100, BPE-200, BPE-300, BPE-500, BPE-900, BPE-1300N, NPG, DCP, 1206PE, 701, 3 G, 9PG, trifunctional A-9300, AT-30E, A-TMPT-3EO, A-TMPT-9EO, A-TMPT-3PO, A-TMM-3, A-TMM-3L, A-TMM-3LM -N, TMPT, TMPT-9EO, tetra- or higher functional ATM-35E, ATM-4E, AD-TMP, AD-TMP-L, ATM-4P, A-TMMT, A-DPH and the like can be mentioned.
＜＜＜分子内に２個以上のオキセタニル基を含む化合物＞＞＞
　本発明では、架橋剤として、オキセタニル基を含む化合物を使用してもよい。オキセタニル基は分子内に２個以上あることが好ましい。分子内に２個以上のオキセタニル基を有する化合物としては、特開２００８－２２４９７０号公報の段落０１３４～０１４５記載の化合物が挙げられ、その内容は本明細書に組み込まれる。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。 <<< Compound containing two or more oxetanyl groups in the molecule >>>
In the present invention, a compound containing an oxetanyl group may be used as a crosslinking agent. It is preferable that there are two or more oxetanyl groups in the molecule. Examples of the compound having two or more oxetanyl groups in the molecule include the compounds described in paragraphs 0134 to 0145 of JP-A-2008-224970, the contents of which are incorporated herein. As specific examples, Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.
＜＜塩基性化合物＞＞
　本発明の感光性樹脂組成物は、塩基性化合物を含有することができる。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、これらの内容は本明細書に組み込まれる。
　具体的には、脂肪族アミンとしては、例えば、トリメチルアミン、ジエチルアミン、トリエチルアミン、ジ－ｎ－プロピルアミン、トリ－ｎ－プロピルアミン、トリブチルアミン、ジ－ｎ－ペンチルアミン、トリ－ｎ－ペンチルアミン、ジエタノールアミン、トリエタノールアミン、ジシクロヘキシルアミン、ジシクロヘキシルメチルアミンなどが挙げられる。
　芳香族アミンとしては、例えば、アニリン、ベンジルアミン、Ｎ，Ｎ－ジメチルアニリン、ジフェニルアミンなどが挙げられる。
　複素環式アミンとしては、例えば、ピリジン、２－メチルピリジン、４－メチルピリジン、２－エチルピリジン、４－エチルピリジン、２－フェニルピリジン、４－フェニルピリジン、Ｎ－メチル－４－フェニルピリジン、４－ジメチルアミノピリジン、イミダゾール、ベンズイミダゾール、４－メチルイミダゾール、２－フェニルベンズイミダゾール、２，４，５－トリフェニルイミダゾール、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、８－オキシキノリン、ピラジン、ピラゾール、ピリダジン、プリン、ピロリジン、ピペリジン、ピペラジン、モルホリン、４－メチルモルホリン、Ｎ－シクロヘキシル－Ｎ’－［２－（４－モルホリニル）エチル］チオ尿素、１，５－ジアザビシクロ［４．３．０］－５－ノネン、１，８－ジアザビシクロ［５．３．０］－７－ウンデセンなどが挙げられる。
　第四級アンモニウムヒドロキシドとしては、例えば、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、テトラ－ｎ－ブチルアンモニウムヒドロキシド、テトラ－ｎ－ヘキシルアンモニウムヒドロキシドなどが挙げられる。
　カルボン酸の第四級アンモニウム塩としては、例えば、テトラメチルアンモニウムアセテート、テトラメチルアンモニウムベンゾエート、テトラ－ｎ－ブチルアンモニウムアセテート、テトラ－ｎ－ブチルアンモニウムベンゾエートなどが挙げられる。 << basic compound >>
The photosensitive resin composition of the present invention can contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
Specifically, as the aliphatic amine, for example, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tributylamine, di-n-pentylamine, tri-n-pentylamine, Examples include diethanolamine, triethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
　塩基性化合物の含有量は、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。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。２種以上を併用する場合は、合計量が上記範囲であることが好ましい。 The content of the basic compound is preferably 0.001 to 3 parts by mass and more preferably 0.005 to 1 part by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. preferable. A basic compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.
＜＜界面活性剤＞＞
　本発明の感光性樹脂組成物は、界面活性剤を含有することができる。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。本発明の組成物に用いられる界面活性剤としては、例えば、特開２０１２－８８４５９号公報の段落番号０２０１～０２０５に記載のものや、特開２０１１－２１５５８０号公報の段落番号０１８５～０１８８に記載のものを用いることができ、これらの記載は本明細書に組み込まれる。
　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、ＦＡ－６３０、ＫＰ－３４１、Ｘ－２２－８２２（信越化学工業（株）製）、ポリフローＮｏ．９９Ｃ（共栄社化学（株）製）、エフトップ（三菱マテリアル化成社製）、メガファックＦ－４３０、Ｆ－４４４、Ｆ－４７７、Ｆ－５５３、Ｆ－５５４、Ｆ－５５６、Ｆ－５５７、Ｆ－５５９、Ｆ－５６２、Ｆ－５６５、Ｆ－５６７、Ｆ－５６９、Ｒ－４０（ＤＩＣ（株）製）、フロラードノベックＦＣ－４４３０（住友スリーエム（株）製）、サーフロンＳ－２４２（ＡＧＣセイミケミカル社製）、ＰｏｌｙＦｏｘＰＦ－６３２０（ＯＭＮＯＶＡ社製）、ＳＨ－８４００（東レ・ダウコーニングシリコーン）、フタージェントＦＴＸ－２１８Ｇ（ネオス社製）等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－１－１）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）を溶媒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。 << Surfactant >>
The photosensitive resin composition of the present invention can contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are FA-630, KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), Ftop (manufactured by Mitsubishi Materials Kasei), MegaFuck F-430, F-444, F-477, F-553, F-554, F-556, F-557, F-559, F-562, F-565, F-567, F-569, R-40 (manufactured by DIC Corporation), Florard Novec FC-4430 (manufactured by Sumitomo 3M Corporation), Surflon S- 242 (manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and Fategent FTX-218G (manufactured by Neos).
Further, the surfactant is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.
一般式（Ｉ－１－１）
Figure JPOXMLDOC01-appb-C000039
 （式（Ｉ－１－１）中、Ｒ４０１およびＲ４０３はそれぞれ独立に、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。） Formula (I-1-1)
Figure JPOXMLDOC01-appb-C000039
 (In formula (I-1-1), R 401 and R 403 each independently represent a hydrogen atom or a methyl group, R 402 represents a linear alkylene group having 1 to 4 carbon atoms, and R 404 represents hydrogen. Represents an atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. The following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.
　上記Ｌは、下記一般式（Ｉ－１－２）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－１－２）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。 L is preferably a branched alkylene group represented by the following general formula (I-1-2). R 405 in formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.
一般式（Ｉ－１－２）
Figure JPOXMLDOC01-appb-C000040
 Formula (I-1-2)
Figure JPOXMLDOC01-appb-C000040
　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 from 1,500 to 5,000.
　界面活性剤の含有量は、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。界面活性剤は、１種単独で使用しても、２種以上を併用してもよい。２種以上を併用する場合は、合計量が上記範囲であることが好ましい。 The content of the surfactant is preferably 10 parts by mass or less, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, the content is 0.01 to 3 parts by mass. Surfactant may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.
＜＜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。
　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フェノール系酸化防止剤、ヒンダードアミン系酸化防止剤、リン系酸化防止剤、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く、フェノール系酸化防止剤が最も好ましい。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。
　具体例としては、特開２００５－２９５１５号公報の段落番号００２６～００３１に記載の化合物、特開２０１１－２２７１０６号公報の段落番号０１０６～０１１６に記載の化合物を挙げる事ができ、これらの内容は本願明細書に組み込まれる。
　好ましい市販品として、アデカスタブＡＯ－２０、アデカスタブＡＯ－６０、アデカスタブＡＯ－８０、アデカスタブＬＡ－５２、アデカスタブＬＡ－８１、アデカスタブＡＯ－４１２Ｓ、アデカスタブＰＥＰ－３６、イルガノックス１０３５、イルガノックス１０９８、チヌビン１４４を挙げる事ができる。
　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、透明性に優れた膜を形成しやすい。更には、パターン形成時の感度も良好となる。 << 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, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur antioxidants from the viewpoint of coloring the cured film and reducing film thickness Agents are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515, and compounds described in paragraph numbers 0106 to 0116 of JP-A-2011-227106. It is incorporated herein.
Preferred commercially available products are ADK STAB AO-20, ADK STAB AO-60, ADK STAB AO-80, ADK STAB LA-52, ADK STAB LA-81, ADK STAB AO-412S, ADK STAB PEP-36, IRGANOX 1035, IRGANOX 1098, and Tinuvin 144. Can be mentioned.
The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, it is easy to form a film having excellent transparency. Furthermore, the sensitivity at the time of pattern formation is also good.
＜＜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。
　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。
　酸増殖剤の具体例としては、特開２０１１－２２１４９４の段落番号０２２６～０２２８に記載の酸増殖剤が挙げられ、この内容は本明細書に組み込まれる。 << Acid Proliferator >>
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid.
Specific examples of the acid proliferating agent include acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-212494A, the contents of which are incorporated herein.
＜＜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に記載されているものを参酌でき、この内容は本明細書に組み込まれる。
　本発明の感光性樹脂組成物における現像促進剤の含有量は、感度と残膜率の観点から、感光性樹脂組成物の全固形分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。現像促進剤は、１種単独で使用しても、２種以上を併用してもよい。２種以上を併用する場合は、合計量が上記範囲であることが好ましい。 << Development accelerator >>
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated herein.
The content 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 resin composition from the viewpoint of sensitivity and residual film ratio. More preferably, it is 1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass. A development accelerator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.
＜＜アルコキシシラン化合物＞＞
　本発明の感光性樹脂組成物は、アルコキシシラン化合物を含有することができる。
　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。
　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。 << alkoxysilane compound >>
The photosensitive resin composition of the present invention can contain an alkoxysilane compound.
As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. The alkoxy group contained in the alkoxysilane compound preferably has 1 to 5 carbon atoms.
The alkoxysilane compound is a compound that improves the adhesion between an insulating material and an inorganic material serving as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. It is preferable. Specifically, a known silane coupling agent or the like is also effective.
＜＜その他の成分＞＞
　本発明の感光性樹脂組成物は、可塑剤、熱ラジカル発生剤、熱酸発生剤、熱ラジカル発生剤、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。また、これらの化合物としては、例えば特開２０１２－８８４５９号公報の段落番号０２０１～０２２４の記載も参酌でき、これらの内容は本明細書に組み込まれる。 << Other ingredients >>
The photosensitive resin composition of the present invention is a known additive such as a plasticizer, a thermal radical generator, a thermal acid generator, a thermal radical generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. An agent can be added. As these compounds, for example, the description of paragraph numbers 0201 to 0224 of JP2012-88459A can be referred to, and the contents thereof are incorporated in the present specification.
＜感光性樹脂組成物の調製方法＞
　本発明の感光性樹脂組成物は、各成分を所定の割合でかつ任意の方法で混合し、撹拌溶解して調製することができる。例えば、各成分を、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本発明の感光性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、例えば孔径０．２μｍのフィルター等を用いてろ過した後に、使用することもできる。 <Method for preparing photosensitive resin composition>
The photosensitive resin composition of the present invention can be prepared by mixing each component at a predetermined ratio and by any method, stirring and dissolving. For example, the photosensitive resin composition of the present invention can also be prepared by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 μm.
　本発明の感光性樹脂組成物の２５℃における固形分濃度は、１～６０質量％が好ましく、３～４０質量％がより好ましく、５～３０質量％がさらに好ましく、５～１７質量％が特に好ましい。粘度は、１～１００ｍＰａ・ｓが好ましく、２～６０ｍＰａ・ｓがより好ましく、３～４０ｍＰａ・ｓが最も好ましい。感光性樹脂組成物の固形分濃度や粘度を上記範囲とすることで、高品位な塗布が可能となる。粘度は、例えば、東機産業製　粘度計　ＲＥ８５Ｌ（ローター：１°３４’×Ｒ２４測定範囲０．６～１２００ｍＰａ・ｓ）を使用し、２５℃に温度調製を施した状態で測定することができる。 The solid content concentration of the photosensitive resin composition of the present invention at 25 ° C. is preferably 1 to 60% by mass, more preferably 3 to 40% by mass, further preferably 5 to 30% by mass, and particularly preferably 5 to 17% by mass. preferable. The viscosity is preferably 1 to 100 mPa · s, more preferably 2 to 60 mPa · s, and most preferably 3 to 40 mPa · s. By setting the solid content concentration and viscosity of the photosensitive resin composition within the above ranges, high-quality coating can be achieved. Viscosity can be measured, for example, using a viscometer RE85L (rotor: 1 ° 34 ′ × R24 measurement range 0.6 to 1200 mPa · s) manufactured by Toki Sangyo Co., Ltd., with the temperature adjusted to 25 ° C. .
　本発明の感光性樹脂組成物は、例えば１０℃以上３０℃以下の温度で保存することもできる。また、０℃以上１０℃℃未満、好ましくは０℃以上５℃未満の温度で保存することもできる。また、０℃未満、好ましくは－５℃以下、さらに好ましくは－２０℃以下、より好ましくは－２０～－４０℃の温度で保存することもできる。
　長期の保存安定性を確保したい場合には、所謂冷凍保管（好ましくは－５℃以下、さらに好ましくは－２０℃以下、より好ましくは－２０～－４０℃）が好ましい。 The photosensitive resin composition of this invention can also be preserve | saved at the temperature of 10 to 30 degreeC, for example. Further, it can be stored at a temperature of 0 ° C. or higher and lower than 10 ° C., preferably 0 ° C. or higher and lower than 5 ° C. Further, it can be stored at a temperature of less than 0 ° C., preferably −5 ° C. or less, more preferably −20 ° C. or less, more preferably −20 to −40 ° C.
In order to ensure long-term storage stability, so-called frozen storage (preferably −5 ° C. or lower, more preferably −20 ° C. or lower, more preferably −20 to −40 ° C.) is preferable.
＜硬化膜の製造方法＞
　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（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工程（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工程（露光工程）
　（４）露光された感光性樹脂組成物を現像液により現像する工程（露光工程）
　（５）現像された感光性樹脂組成物を熱硬化する工程（ポストベーク工程）
　以下に各工程を順に説明する。 <Method for producing cured film>
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the photosensitive resin composition of this invention on a board | substrate (application | coating process)
(2) Step of removing the solvent from the applied photosensitive resin composition (solvent removal step)
(3) Step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays (exposure step)
(4) Step of developing the exposed photosensitive resin composition with a developer (exposure step)
(5) Step of thermosetting the developed photosensitive resin composition (post-baking step)
Each step will be described below in order.
　（１）の工程では、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。
　（１）の工程では、基板に感光性樹脂組成物を塗布する前に、基板に対してアルカリ洗浄やプラズマ洗浄などの洗浄を行ってもよい。また、洗浄後の基板に対してヘキサメチルジシラザンなどで基板表面を処理してもよい。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中に基板を晒しておく方法等が挙げられる。
　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、最終製品の形態によって、例えば薄膜トランジスタ（ＴＦＴ）のような多層積層構造が形成されていてもよい。
　基板への感光性樹脂組成物の塗布方法は特に限定されず、例えば、インクジェット法、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。
　スリットコート法の場合には基板とスリットダイとの相対移動速度を５０～１２０ｍｍ／ｓｅｃとすることが好ましい。
　感光性樹脂組成物を塗布したときの湿潤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。例えば、０．５～１０μｍが好ましい。
　基板に本発明の感光性樹脂組成物を塗布する前に、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。 In the step (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.
In the step (1), before the photosensitive resin composition is applied to the substrate, the substrate may be subjected to cleaning such as alkali cleaning or plasma cleaning. Further, the substrate surface may be treated with hexamethyldisilazane or the like with respect to the cleaned substrate. The method of treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
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 such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound And the like.
These substrates are rarely used in the above-described form, and a multilayer laminated structure such as a thin film transistor (TFT) may be formed depending on the form of the final product.
The method for applying the photosensitive resin composition to the substrate is not particularly limited. For example, an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, etc. Can be used.
In the case of the slit coating method, the relative movement speed between the substrate and the slit die is preferably 50 to 120 mm / sec.
The wet film thickness when the photosensitive resin composition is applied is not particularly limited, and can be applied with a film thickness according to the application. For example, 0.5 to 10 μm is preferable.
Before applying the photosensitive resin composition of the present invention to the substrate, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
　（２）の工程では、感光性樹脂組成物を塗布して形成した上記の湿潤膜から、減圧（バキューム）および／または加熱等により、溶剤を除去して基板上に乾燥膜を形成させる。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 step (2), the solvent is removed from the wet film formed by applying the photosensitive resin composition by vacuum (vacuum) and / or heating to form a dry film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.
　（３）の工程では、乾燥膜を設けた基板に所定のパターンの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、カルボキシ基、フェノール性水酸基などが生成する。
　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、ｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）、ｇ線（４３６ｎｍ）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。露光量は好ましくは１～５００ｍＪ／ｃｍ２である。
　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、レンズスキャナ、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。また、所謂超解像技術を用いた露光をすることもできる。超解像技術としては、複数回露光する多重露光や、位相シフトマスクを用いる方法、輪帯照明法に代表される変形証明法などが挙げられる。これら超解像技術を用いることでより高精細なパターン形成が可能となり、好ましい。
　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基、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。 In the step (3), the substrate provided with the dry film is irradiated with actinic rays 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-decomposable group contained in the coating film component is hydrolyzed to generate a carboxy group, a phenolic hydroxyl group, and the like.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, i-line (365 nm), h-line (405 nm), g-line ( Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm 2 .
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 lens scanner, and a laser exposure can be used. Further, exposure using so-called super-resolution technology can also be performed. Examples of the super-resolution technique include multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, a deformation proof method represented by an annular illumination method, and the like. By using these super-resolution techniques, it is possible to form a higher definition pattern, which is preferable.
In order to accelerate the hydrolysis reaction 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. PEB can promote the formation of a carboxy group and a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
　（４）の工程では、遊離したカルボキシ基、フェノール性水酸基を有する共重合体を、現像液を用いて現像して、ポジ画像が形成する。
　現像工程で使用する現像液には、塩基性化合物の水溶液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、炭酸セシ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、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ジエチルジメチルアンモニウムヒドロキシド等のテトラアルキルアンモニウムヒドロキシド類：コリン等の（ヒドロキシアルキル）トリアルキル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ケイ酸塩類；エチルアミン、プロピルアミン、ジエチルアミン、トリエチルアミン等のアルキルアミン類；ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類；１，８－ジアザビシクロ－［５．４．０］－７－ウンデセン、１，５－ジアザビシクロ－［４．３．０］－５－ノネン等の脂環式アミン類を使用することができる。
　これらのうち、水酸化ナトリウム、水酸化カリウム、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、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、コリン（２－ヒドロキシエチルトリメチルアンモニウムヒドロキシド）が好ましい。
　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。
　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（パドル法）、シャワー法、ディップ法等の何れでもよい。
　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 step (4), a copolymer having a free carboxy group and a phenolic hydroxyl group is developed using a developer to form a positive image.
The developer used in the development step preferably contains an aqueous solution of 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, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; Alcoholamines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] Cycloaliphatic amines such as 5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
　（５）の工程では、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てカルボキシ基、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１８０～４００℃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。このように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、９０～１８０℃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。 In the step (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxy group and a phenolic hydroxyl group, and crosslinked with a crosslinking group, a crosslinking agent, etc. A cured film can be formed.
This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 400 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 180 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. The preferred exposure amount in the case of including a post-exposure step, preferably 100 ~ 3,000mJ / cm 2, particularly preferably 100 ~ 500mJ / cm 2.
　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。 The cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
＜硬化膜＞
　本発明の硬化膜は、上述した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。また、本発明の硬化膜は、上述した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。
　本発明の硬化膜は、層間絶縁膜として好適に用いることができる。硬化膜の少なくとも一部を金属部に接触させて用いることが好ましく、特に、金属配線の絶縁基板として好ましく用いることができる。
　本発明の感光性樹脂組成物は、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、液晶表示装置、有機エレクトロルミネッセンス表示装置、タッチパネル等の用途に有用である。 <Curing film>
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention. 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 mentioned above.
The cured film of the present invention can be suitably used as an interlayer insulating film. It is preferable to use at least a part of the cured film in contact with the metal part, and it can be particularly preferably used as an insulating substrate for metal wiring.
The photosensitive resin composition of the present invention can provide an interlayer insulating film having high transparency even when baked at a high temperature. The interlayer insulation film formed using the photosensitive resin composition of the present invention has high transparency and is useful for applications such as a liquid crystal display device, an organic electroluminescence display device, and a touch panel.
＜液晶表示装置＞
　本発明の液晶表示装置は、本発明の硬化膜を有する。
　本発明の液晶表示装置としては、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の有機絶縁膜（１１５）や、特開２００５－３４６０５４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。例えば白色発光ダイオード（ＬＥＤ）、青色・赤色・緑色などの多色ＬＥＤ、蛍光灯（冷陰極管）、有機エレクトロルミネッセンス（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号公報に記載の第２層間絶縁膜（４８）や、特開２００９－２５８７５８号公報に記載の層間絶縁膜（５２０）、特開２００７－３２８２１０号公報の図１に記載の有機絶縁膜（ＰＡＳ）として用いることができる。
　さらに、スタティック駆動方式の液晶表示装置でも、本発明を適用することで意匠性の高いパターンを表示させることも可能である。例として、特開２００１－１２５０８６号公報に記載されているようなポリマーネットワーク型液晶の絶縁膜として本発明を適用することができる。 <Liquid crystal display device>
The liquid crystal display device of the present invention has 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 planarizing film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures. Can be mentioned.
For example, specific examples of TFTs 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.
Further, the liquid crystal driving methods that can be adopted by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of Japanese Patent Application Laid-Open No. 2005-284291, or Japanese Patent Application Laid-Open No. 2005-346054. It can be used as an organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The 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 disposed on all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. Corresponding TFT 16 elements are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, white light emitting diodes (LEDs), multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), organic electroluminescence (organic EL), and the like can be given.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, a flexible type can also be used. The second interlayer insulating film (48) described in JP2011-145686A, the interlayer insulating film (520) described in JP2009-258758A, JP It can be used as an organic insulating film (PAS) described in FIG. 1 of 2007-328210.
Further, even in a static drive type liquid crystal display device, a pattern with high designability can be displayed by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A-2001-125086.
　特開２００７－３２８２１０号公報の図１に記載の液晶表示装置について、図２を用いて説明する。
　図２において、符号ＳＵＢ１は、ガラス基板であり、複数の走査信号線と、複数の走査信号線に交差する複数の映像信号線とを有している。各交点近傍には、ＴＦＴを有している。
　ガラス基板ＳＵＢ１の上には、下から順に下地膜ＵＣ、シリコン等の半導体膜ＰＳ、ゲート絶縁膜ＧＩ、ＴＦＴのゲート電極ＧＴ、第１の層間絶縁膜ＩＮ１が形成されている。第１の層間絶縁膜ＩＮ１の上には、ＴＦＴのドレイン電極ＳＤ１と、ＴＦＴのソース電極ＳＤ２とが形成されている。
　ドレイン電極ＳＤ１は、ゲート絶縁膜ＧＩ及び第１の層間絶縁膜ＩＮ１に形成されたコンタクトホールを介してＴＦＴのドレイン領域に接続されている。ソース電極ＳＤ２は、ゲート絶縁膜ＧＩ及び第１の層間絶縁膜ＩＮ１に形成されたコンタクトホールを介してＴＦＴのソース領域に接続されている。
　ドレイン電極ＳＤ１及びソース電極ＳＤ２の上には、第２の層間絶縁膜ＩＮ２が形成されている。第２の層間絶縁膜ＩＮ２の上には、有機絶縁膜ＰＡＳが形成されている。有機絶縁膜ＰＡＳは、本発明の感光性樹脂組成物を用いて形成できる。
　有機絶縁膜ＰＡＳの上には、対向電極ＣＴ及び反射膜ＲＡＬが形成されている。
　対向電極ＣＴ及び反射膜ＲＡＬの上には、第３の層間絶縁膜ＩＮ３が形成されている。第３の層間絶縁膜ＩＮ３の上には、画素電極ＰＸが形成されている。画素電極ＰＸは、第２の層間絶縁膜ＩＮ２及び第３の層間絶縁膜ＩＮ３に形成されたコンタクトホールを介してＴＦＴのソース電極ＳＤ２と接続されている。
　有機絶縁膜ＰＡＳを、本発明の感光性樹脂組成物を用いて形成した場合においては、有機絶縁膜ＰＡＳの耐熱性が優れているため、第３の層間絶縁膜ＩＮ３の製膜温度を高めることができ、より緻密な膜を製膜できる。
　なお、第１の層間絶縁膜ＩＮ１、第２の層間絶縁膜ＩＮ２、第３の層間絶縁膜ＩＮ３も本発明の感光性樹脂組成物を用いて形成することができる。
　図２に示す液晶表示装置の詳細については、特開２００７－３２８２１０号公報の記載を参酌でき、この内容は本明細書に組み込まれることとする。 The liquid crystal display device shown in FIG. 1 of Japanese Patent Application Laid-Open No. 2007-328210 will be described with reference to FIG.
In FIG. 2, reference numeral SUB1 denotes a glass substrate, which has a plurality of scanning signal lines and a plurality of video signal lines intersecting with the plurality of scanning signal lines. A TFT is provided in the vicinity of each intersection.
On the glass substrate SUB1, a base film UC, a semiconductor film PS such as silicon, a gate insulating film GI, a TFT gate electrode GT, and a first interlayer insulating film IN1 are formed in this order from the bottom. A drain electrode SD1 of the TFT and a source electrode SD2 of the TFT are formed on the first interlayer insulating film IN1.
The drain electrode SD1 is connected to the drain region of the TFT through a contact hole formed in the gate insulating film GI and the first interlayer insulating film IN1. The source electrode SD2 is connected to the source region of the TFT through a contact hole formed in the gate insulating film GI and the first interlayer insulating film IN1.
A second interlayer insulating film IN2 is formed on the drain electrode SD1 and the source electrode SD2. An organic insulating film PAS is formed on the second interlayer insulating film IN2. The organic insulating film PAS can be formed using the photosensitive resin composition of the present invention.
On the organic insulating film PAS, a counter electrode CT and a reflective film RAL are formed.
A third interlayer insulating film IN3 is formed on the counter electrode CT and the reflective film RAL. A pixel electrode PX is formed on the third interlayer insulating film IN3. The pixel electrode PX is connected to the source electrode SD2 of the TFT through a contact hole formed in the second interlayer insulating film IN2 and the third interlayer insulating film IN3.
In the case where the organic insulating film PAS is formed using the photosensitive resin composition of the present invention, since the heat resistance of the organic insulating film PAS is excellent, the film forming temperature of the third interlayer insulating film IN3 is increased. And a denser film can be formed.
Note that the first interlayer insulating film IN1, the second interlayer insulating film IN2, and the third interlayer insulating film IN3 can also be formed using the photosensitive resin composition of the present invention.
The details of the liquid crystal display device shown in FIG. 2 can be referred to the description in Japanese Patent Application Laid-Open No. 2007-328210, and the contents thereof are incorporated in this specification.
＜有機エレクトロルミネッセンス表示装置＞
　本発明の有機エレクトロルミネッセンス（有機ＥＬ）表示装置は、本発明の硬化膜を有する。
　本発明の有機ＥＬ表示装置としては、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３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、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上に平坦化膜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、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３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 electroluminescence display device>
The organic electroluminescence (organic EL) display device of the present invention has the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic materials having various structures. An EL display device and a liquid crystal display device can be given.
For example, specific examples of TFTs included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 3 is a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. be able to.
Further, although not shown in FIG. 3, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.
　本発明の感光性樹脂組成物は、感度が良好で、現像時のパターン密着性に優れるため、ＭＥＭＳ（Ｍｉｃｒｏ　Ｅｌｅｃｔｒｏ　Ｍｅｃｈａｎｉｃａｌ　Ｓｙｓｔｅｍｓ）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。ＭＥＭＳデバイスとしては、例えばＳＡＷ（Ｓｕｒｆａｃｅ　Ａｃｏｕｓｔｉｃ　Ｗａｖｅ）フィルター、ＢＡＷ（Ｂｕｌｋ　Ａｃｏｕｓｔｉｃ　Ｗａｖｅ）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、特開２００８－２５０２００、特開２００９－２６３５４４等に例示されている。 Since the photosensitive resin composition of the present invention has good sensitivity and excellent pattern adhesion during development, it is formed using the photosensitive resin composition of the present invention as a structural member of a MEMS (Micro Electro Mechanical Systems) device. The resist pattern thus formed is used as a partition wall or incorporated as a part of a mechanical drive component. Examples of MEMS devices include parts such as SAW (Surface Acoustic Wave) filters, BAW (Bulk Acoustic Wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, biochips, and sealants. It is done. More specific examples are exemplified in JP-T-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。この他、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、ファクシミリ、電子複写機、固体撮像素子等のオンチップカラーフィルターの結像光学系あるいは光ファイバコネクタのマイクロレンズにも好適に用いることができる。 Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) described in FIG. 4 (a) of Japanese Patent No. 9793, the bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of Japanese Patent Application Laid-Open No. 2010-27591. ), The second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and the flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12) and a pixel isolation insulating film (14). In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.
＜タッチパネル及びタッチパネル表示装置＞
　本発明のタッチパネルは、絶縁層及び／又は保護層の、全部又は一部が本発明の感光性樹脂組成物の硬化物からなるタッチパネルである。また、本発明のタッチパネルは、透明基板、電極及び絶縁層及び／又は保護層を少なくとも有することが好ましい。
　本発明のタッチパネル表示装置は、本発明のタッチパネルを有するタッチパネル表示装置であることが好ましい。本発明のタッチパネルとしては、抵抗膜方式、静電容量方式、超音波方式、電磁誘導方式など公知の方式いずれでもよい。中でも、静電容量方式が好ましい。
　静電容量方式のタッチパネルとしては、特開２０１０－２８１１５号公報に開示されるものや、国際公開第２０１２／０５７１６５号に開示されるものが挙げられる。
　タッチパネル表示装置としては、いわゆる、インセル型（例えば、特表２０１２－５１７０５１号公報の図５、図６、図７、図８）、いわゆる、オンセル型（例えば、特開２０１３－１６８１２５の図１９）、ＯＧＳ型、ＴＯＬ型、その他の構成（例えば、特開２０１３－１６４８７１号公報の図６）を挙げることができる
　静電容量方式のタッチパネルは、前面板と、前面板の非接触側に、少なくとも下記（１）～（５）の要素を有し、（４）の絶縁層が本発明の感光性樹脂組成物を用いた硬化膜であることが好ましい。
　（１）額縁層
　（２）複数のパッド部分が接続部分を介して第一の方向に延在して形成された複数の第一の透明電極パターン
　（３）第一の透明電極パターンと電気的に絶縁され、第一の方向に交差する方向に延在して形成された複数のパッド部分からなる複数の第二の透明電極パターン
　（４）第一の透明電極パターンと第二の透明電極パターンとを電気的に絶縁する絶縁層
　（５）第一の透明電極パターンおよび第二の透明電極パターンの少なくとも一方に電気的に接続され、第一の透明電極パターンおよび第二の透明電極パターンとは別の導電性要素
　本発明の静電容量型入力装置は、さらに上記（１）～（５）の要素の全てまたは一部を覆うように透明保護層を設置することが好ましく、透明保護層が本発明の硬化膜であることがより好ましい。 <Touch panel and touch panel display device>
The touch panel of the present invention is a touch panel in which all or part of the insulating layer and / or protective layer is made of a cured product of the photosensitive resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an electrode, an insulating layer, and / or a protective layer at least.
The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention. As the touch panel of the present invention, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, and an electromagnetic induction method may be used. Among these, the electrostatic capacity method is preferable.
Examples of the capacitive touch panel include those disclosed in JP 2010-28115 A and those disclosed in International Publication No. 2012/057165.
As a touch panel display device, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7 and FIG. 8 of JP-A-2012-517051), a so-called on-cell type (for example, FIG. 19 of JP2013-168125A). , OGS type, TOL type, and other configurations (for example, FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164877). The capacitive touch panel has at least a front plate and a non-contact side of the front plate. The following (1) to (5) elements are preferable, and the insulating layer (4) is preferably a cured film using the photosensitive resin composition of the present invention.
(1) Frame layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) First transparent electrode pattern and electrical And a plurality of second transparent electrode patterns comprising a plurality of pad portions formed extending in a direction crossing the first direction. (4) First transparent electrode pattern and second transparent electrode pattern (5) The first transparent electrode pattern and the second transparent electrode pattern are electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern. Another conductive element In the capacitive input device of the present invention, it is preferable that a transparent protective layer is further provided so as to cover all or a part of the elements (1) to (5). The cured film of the present invention is more preferable. There.
　まず、静電容量方式のタッチパネルの構成について説明する。図４は、静電容量方式のタッチパネルの構成例を示す断面図である。図４において静電容量方式のタッチパネル３０は、前面板３１と、額縁層３２と、第一の透明電極パターン３３と、第二の透明電極パターン３４と、絶縁層３５と、導電性要素３６と、透明保護層３７とから構成されている。 First, the configuration of the capacitive touch panel will be described. FIG. 4 is a cross-sectional view illustrating a configuration example of a capacitive touch panel. In FIG. 4, the capacitive touch panel 30 includes a front plate 31, a frame layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, and a conductive element 36. And a transparent protective layer 37.
　前面板３１は、ガラス基板等の透明基板で構成されており、コーニング社のゴリラガラスに代表される強化ガラスなどを用いることができる。なお、透明基板としては、ガラス基板、石英基板、透明樹脂基板等が好ましく挙げられる。また、図４において、前面板３１の各要素が設けられている側を非接触面と称する。静電容量方式のタッチパネル３０においては、前面板３１の接触面（非接触面の反対の面）に指などを接触などさせて入力が行われる。以下、前面板を、「基材」と称する場合がある。 The front plate 31 is made of a transparent substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. In addition, as a transparent substrate, a glass substrate, a quartz substrate, a transparent resin substrate, etc. are mentioned preferably. Moreover, in FIG. 4, the side in which each element of the front plate 31 is provided is called a non-contact surface. In the capacitive touch panel 30, input is performed by bringing a finger or the like into contact with the contact surface of the front plate 31 (the surface opposite to the non-contact surface). Hereinafter, the front plate may be referred to as a “base material”.
　また、前面板３１の非接触面上には額縁層３２が設けられている。額縁層３２は、タッチパネル前面板の非接触側に形成された表示領域周囲の額縁状のパターンであり、引回し配線等が見えないようにするために形成される。
　静電容量方式のタッチパネルには、図５に示すように、前面板３１の一部の領域（図５においては入力面以外の領域）を覆うように額縁層３２が設けることができる。さらに、前面板３１には、図５に示すように一部に開口部３８を設けることができる。開口部３８には、押圧によるメカニカルなスイッチを設置することができる。 A frame layer 32 is provided on the non-contact surface of the front plate 31. The frame layer 32 is a frame-like pattern around the display area formed on the non-contact side of the front panel of the touch panel, and is formed so as not to show the lead wiring and the like.
As shown in FIG. 5, the capacitive touch panel may be provided with a frame layer 32 so as to cover a part of the front plate 31 (a region other than the input surface in FIG. 5). Further, the front plate 31 can be provided with an opening 38 in part as shown in FIG. A mechanical switch by pressing can be installed in the opening 38.
　図６に示すように、前面板３１の非接触面には、複数のパッド部分が接続部分を介して第一の方向に延在して形成された複数の第一の透明電極パターン３３と、第一の透明電極パターン３３と電気的に絶縁され、第一の方向に交差する方向に延在して形成された複数のパッド部分からなる複数の第二の透明電極パターン３４と、第一の透明電極パターン３３と第二の透明電極パターン３４を電気的に絶縁する絶縁層３５とが形成されている。第一の透明電極パターン３３と、第二の透明電極パターン３４と、後述する導電性要素３６とは、例えば金属膜で作製することができる。このような金属膜としては、ＩＴＯ（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ）膜；ＩＺＯ（Ｉｎｄｉｕｍ　Ｚｉｎｃ　Ｏｘｉｄｅ）膜；Ａｌ、Ｃｕ、Ａｇ、Ｔｉ、Ｍｏ、これらの合金等の金属膜；ＳｉＯ２等の金属酸化膜などが挙げられる。この際、各要素の膜厚は１０～２００ｎｍとすることができる。また、焼成によりアモルファスのＩＴＯ膜を多結晶のＩＴＯ膜へと結晶化させ、電気的抵抗を低減することもできる。また、第一の透明電極パターン３３と、第二の透明電極パターン３４と、後述する導電性要素３６とは、導電性繊維を用いた感光性樹脂組成物を有する感光性転写材料を用いて製造することもできる。その他、ＩＴＯ等によって第一の導電性パターン等を形成する場合には、特許第４５０６７８５号公報の段落００１４～００１６等を参酌することができ、この内容は本明細書に組み込まれる。 As shown in FIG. 6, on the non-contact surface of the front plate 31, a plurality of first transparent electrode patterns 33 formed with a plurality of pad portions extending in the first direction via the connection portions, A plurality of second transparent electrode patterns consisting of a plurality of pad portions that are electrically insulated from the first transparent electrode pattern 33 and extend in a direction crossing the first direction; An insulating layer 35 that electrically insulates the transparent electrode pattern 33 and the second transparent electrode pattern 34 is formed. The 1st transparent electrode pattern 33, the 2nd transparent electrode pattern 34, and the electroconductive element 36 mentioned later can be produced with a metal film, for example. As such a metal film, an ITO (Indium Tin Oxide) film; an IZO (Indium Zinc Oxide) film; a metal film such as Al, Cu, Ag, Ti, Mo, and alloys thereof; a metal oxide film such as SiO 2 ; Is mentioned. At this time, the film thickness of each element can be 10 to 200 nm. Further, the amorphous ITO film can be crystallized into a polycrystalline ITO film by firing, and the electrical resistance can be reduced. Moreover, the 1st transparent electrode pattern 33, the 2nd transparent electrode pattern 34, and the electroconductive element 36 mentioned later are manufactured using the photosensitive transfer material which has the photosensitive resin composition using a conductive fiber. You can also In addition, when the first conductive pattern or the like is formed of ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to, and the contents thereof are incorporated in this specification.
　また、第一の透明電極パターン３３および第二の透明電極パターン３４の少なくとも一方は、前面板３１の非接触面および額縁層３２の前面板３１とは逆側の面の両方の領域にまたがって設置することができる。図４においては、第二の透明電極パターンが、前面板３１の非接触面および額縁層３２の前面板３１とは逆側の面の両方の領域にまたがって設置されている図が示されている。 Further, at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 extends over both the non-contact surface of the front plate 31 and the region of the frame layer 32 opposite to the front plate 31. Can be installed. In FIG. 4, a diagram is shown in which the second transparent electrode pattern is installed across both areas of the non-contact surface of the front plate 31 and the surface opposite to the front plate 31 of the frame layer 32. Yes.
　図６を用いて第一の透明電極パターン３３および第二の透明電極パターン３４について説明する。図６は、第一の透明電極パターンおよび第二の透明電極パターンの一例を示す説明図である。図６に示すように、第一の透明電極パターン３３は、パッド部分３３ａが接続部分３３ｂを介して第一の方向に延在して形成されている。また、第二の透明電極パターン３４は、第一の透明電極パターン３３と絶縁層３５によって電気的に絶縁されており、第一の方向に交差する方向（図６における第二の方向）に延在して形成された複数のパッド部分によって構成されている。ここで、第一の透明電極パターン３３を形成する場合、パッド部分３３ａと接続部分３３ｂとを一体として作製してもよいし、接続部分３３ｂのみを作製して、パッド部分３３ａと第二の透明電極パターン３４とを一体として作製（パターニング）してもよい。パッド部分３３ａと第二の透明電極パターン３４とを一体として作製（パターニング）する場合、図６に示すように接続部分３３ｂの一部とパッド部分３３ａの一部とが連結され、かつ、絶縁層３５によって第一の透明電極パターン３３と第二の透明電極パターン３４とが電気的に絶縁されるように各層が形成される。 The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. FIG. 6 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern. As shown in FIG. 6, the first transparent electrode pattern 33 is formed such that the pad portion 33a extends in the first direction via the connection portion 33b. The second transparent electrode pattern 34 is electrically insulated by the first transparent electrode pattern 33 and the insulating layer 35, and extends in a direction intersecting the first direction (second direction in FIG. 6). It is constituted by a plurality of pad portions that are formed. Here, when the first transparent electrode pattern 33 is formed, the pad portion 33a and the connection portion 33b may be manufactured integrally, or only the connection portion 33b is manufactured, and the pad portion 33a and the second transparent electrode pattern 33 are formed. The electrode pattern 34 may be integrally formed (patterned). When the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 6, a part of the connection part 33b and a part of the pad part 33a are connected and an insulating layer is formed. Each layer is formed so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by 35.
　図４において、額縁層３２の前面板３１とは逆側の面側には導電性要素３６が設置されている。導電性要素３６は、第一の透明電極パターン３３および第二の透明電極パターン３４の少なくとも一方に電気的に接続され、かつ、第一の透明電極パターン３３および第二の透明電極パターン３４とは別の要素である。図４においては、導電性要素３６が第二の透明電極パターン３４に接続されている図が示されている。 In FIG. 4, a conductive element 36 is installed on the surface side of the frame layer 32 opposite to the front plate 31. The conductive element 36 is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34, and is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34. Is another element. In FIG. 4, a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.
　また、図４においては、各構成要素の全てを覆うように透明保護層３７が設置されている。透明保護層３７は、各構成要素の一部のみを覆うように構成されていてもよい。絶縁層３５と透明保護層３７とは、同一材料であってもよいし、異なる材料であってもよい。 Moreover, in FIG. 4, the transparent protective layer 37 is installed so that all of each component may be covered. The transparent protective layer 37 may be configured to cover only a part of each component. The insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.
　静電容量方式のタッチパネルおよび静電容量方式のタッチパネルを構成要素として備えるタッチパネル表示装置は、「最新タッチパネル技術」（２００９年７月６日発行（株）テクノタイムズ）、三谷雄二監修、「タッチパネルの技術と開発」シーエムシー出版（２００４，１２）、「ＦＰＤ　Ｉｎｔｅｒｎａｔｉｏｎａｌ　２００９　Ｆｏｒｕｍ　Ｔ－１１講演テキストブック」、「Ｃｙｐｒｅｓｓ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ　Ｃｏｒｐｏｒａｔｉｏｎ　アプリケーションノートＡＮ２２９２」等に開示されている構成を適用することができる。 The touch panel display device including the capacitive touch panel and the capacitive touch panel as a constituent element is “Latest Touch Panel Technology” (Techno Times, issued July 6, 2009), supervised by Yuji Mitani, “Touch Panel The configurations disclosed in “Technology and Development” CMC Publishing (2004, 12), “FPD International 2009 Forum T-11 Lecture Textbook”, “Cypress Semiconductor Corporation Application Note AN2292” and the like can be applied.
　本発明のタッチパネルは、例えば、次のようにして製造できる。
　すなわち、ＩＴＯ電極に接するように、本発明の感光性樹脂組成物をインクジェット塗布方式など各種方法により塗布する工程１、上記ＩＴＯ電極に塗布した感光性樹脂組成物上に所定形状の開口パターンを有するマスクを載置し、活性エネルギー線照射を行い露光する工程２、露光後の感光性樹脂組成物を現像する工程３、および、現像後の感光性樹脂組成物を加熱する工程４を経て製造できる。 The touch panel of the present invention can be manufactured, for example, as follows.
That is, the photosensitive resin composition of the present invention is applied by various methods such as an inkjet coating method so as to be in contact with the ITO electrode, and an opening pattern having a predetermined shape is formed on the photosensitive resin composition applied to the ITO electrode. It can be manufactured through Step 2 in which a mask is placed and exposed by irradiation with active energy rays, Step 3 in which the exposed photosensitive resin composition is developed, and Step 4 in which the photosensitive resin composition after development is heated. .
　工程１において、ＩＴＯ電極に接するように、感光性樹脂組成物を塗布する際、塗布された本発明の感光性樹脂組成物の少なくとも一部が、ＩＴＯ電極に接していればよい。
　工程２は、上述した露光工程と同様に行うことができ、好ましい態様も同様である。
　工程３は、上述した現像工程と同様に行うことができ、好ましい態様も同様である。
　工程４は、上述したポストベーク工程と同様に行うことができ、好ましい態様も同様である。
　また、本発明のタッチパネルにおけるＩＴＯ電極パターンの一例としては、上述した図６に示すパターンが好ましく挙げられる。 In Step 1, when the photosensitive resin composition is applied so as to be in contact with the ITO electrode, it is sufficient that at least a part of the applied photosensitive resin composition of the present invention is in contact with the ITO electrode.
Step 2 can be performed in the same manner as the exposure step described above, and the preferred embodiment is also the same.
Step 3 can be performed in the same manner as the development step described above, and the preferred embodiment is also the same.
Step 4 can be performed in the same manner as the post-baking step described above, and the preferred embodiment is also the same.
Moreover, as an example of the ITO electrode pattern in the touch panel of this invention, the pattern shown in FIG. 6 mentioned above is mentioned preferably.
　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限定されるものではない。
　なお、ＮＭＲは、核磁気共鳴の略称である。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the following.
NMR is an abbreviation for nuclear magnetic resonance.
＜ポリシロキサンの合成例＞
（Ａ１－１の合成）　酸分解性基で保護されたカルボキシ基と、エポキシ基とを有するポリシロキサンの合成
　３－トリクロロシリル－１－シクロヘキシルカルボン酸メチルエステル１２．４ｇ（０．０４５ｍｏｌ）、グリシドキシプロピルトリクロロシラン１１．２ｇ（０．０４５ｍｏｌ）、メチルトリクロロシラン０．７４５ｇ（０．００５ｍｏｌ）、フェニルトリクロロシラン１．０６ｇ（０．００５ｍｏｌ）をトルエン１５０ｇに溶解し、水３００ｇ中へ室温で撹拌しながら滴下添加した。滴下終了後、反応混合物より酸性水層を分離し、次いで水１Ｌで有機層を水洗し、水層が中性になってからさらに２回水洗を行った。有機層をエバポレーターにより溶媒留去した。その濃縮液を６０℃で５時間加熱し、重合した。
　重合物にテトラヒドロフラン８００ｇを加えて溶解したものを、１０％水酸化ナトリウム溶液１，０００ｇへ滴下し、４０℃で３時間加熱し、メチルエステル基を加水分解した。塩酸で酸性にしてポリマーを晶出し、濾過、乾燥を行いＡ１－１前駆体（Ａ１－１のカルボキシ基がテトラヒドロフラニル保護されていないポリマー）を得た。
　得られたＡ１－１前駆体の１００ｇを、テトラヒドロフラン４００ｍＬに溶解させ、触媒量のｐ－トルエンスルホン酸を添加後、２０℃で撹拌しながらジヒドロフラン３０ｇをテトラヒドロフラン３０ｇに溶解させた溶液を滴下した。
　３０分反応させた後、濃アンモニア水により中和し、水５Ｌに中和した反応液を滴下したところ、白色固体が得られた。これを濾過後、アセトン３００ｍｌに溶解させ、水５Ｌに滴下し、濾過後、乾燥してＡ１－１を得た。Ａ１－１は、テトラヒドロフラニル基で保護されたカルボキシ基、カルボキシ基、エポキシ基、メチル基、および、フェニル基を側鎖に有するポリシロキサンであった。
　１Ｈ－ＮＭＲによる分析により、Ａ１－１においては、カルボキシ基の７８モル％がテトラヒドロフラニル化されたことが分かった。
　Ａ１－１の合成に使用したシラン化合物の種類及びモル比を以下に示す。
Figure JPOXMLDOC01-appb-T000041
 <Synthesis example of polysiloxane>
(Synthesis of A1-1) Synthesis of polysiloxane having a carboxyl group protected with an acid-decomposable group and an epoxy group 12.4 g (0.045 mol) of 3-trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester, 11.2 g (0.045 mol) of Sidoxypropyltrichlorosilane, 0.745 g (0.005 mol) of methyltrichlorosilane and 1.06 g (0.005 mol) of phenyltrichlorosilane were dissolved in 150 g of toluene and dissolved in 300 g of water at room temperature. Added dropwise with stirring. After completion of the dropwise addition, the acidic aqueous layer was separated from the reaction mixture, then the organic layer was washed with 1 L of water, and further washed twice with water after the aqueous layer became neutral. The organic layer was evaporated using an evaporator. The concentrate was heated at 60 ° C. for 5 hours to polymerize.
A polymer dissolved in 800 g of tetrahydrofuran was dropped into 1,000 g of a 10% sodium hydroxide solution and heated at 40 ° C. for 3 hours to hydrolyze the methyl ester group. The polymer was crystallized with hydrochloric acid, crystallized, filtered and dried to obtain A1-1 precursor (polymer in which the carboxyl group of A1-1 was not protected with tetrahydrofuranyl).
100 g of the resulting A1-1 precursor was dissolved in 400 mL of tetrahydrofuran, and after adding a catalytic amount of p-toluenesulfonic acid, a solution in which 30 g of dihydrofuran was dissolved in 30 g of tetrahydrofuran was added dropwise with stirring at 20 ° C. .
After reacting for 30 minutes, the reaction solution was neutralized with concentrated aqueous ammonia and neutralized with 5 L of water, and a white solid was obtained. This was filtered, dissolved in 300 ml of acetone, dropped into 5 L of water, filtered and dried to obtain A1-1. A1-1 was a polysiloxane having a carboxy group, a carboxy group, an epoxy group, a methyl group, and a phenyl group protected by a tetrahydrofuranyl group in the side chain.
Analysis by 1 H-NMR revealed that 78 mol% of the carboxy group was tetrahydrofuranylated in A1-1.
The types and molar ratios of the silane compounds used for the synthesis of A1-1 are shown below.
Figure JPOXMLDOC01-appb-T000041
　（Ａ１－２の合成）　酸分解性基で保護されたフェノール性水酸基と、エポキシ基とを有するポリシロキサンの合成
　４－ヒドロキシベンジルトリメトキシシラン１１４．２ｇ（０．５モル）、３－グリシドキシプロピルトリメトキシシラン９４．５ｇ（０．４モル）、メチルトリメトキシシラン６．８ｇ（０．０５モル）、フェニルトリメトキシシラン９．９ｇ（０．０５モル）、ＤＡＡ（ジアセトンアルコール）２５０ｇを、三口フラスコに仕込み、室温で攪拌しながら、水５４ｇにリン酸０．１７６ｇ（仕込みシラン化合物に対して０．１重量％）を溶かしたリン酸水溶液を、３０分かけて添加した。その後、三口フラスコを４０℃のオイルバスに浸けて３０分攪拌した後、６０℃で５時間反応させた。
　反応中に副生成物であるメタノールが留出した。得られたポリシロキサンのＤＡＡ溶液を多量の水に注いでポリマーを析出させ、ろ過、乾燥してＡ１－２前駆体を得た。
　得られたＡ１―２前駆体の１００ｇを、テトラヒドロフラン４００ｍＬに溶解させ、触媒量のｐ－トルエンスルホン酸を添加後、２０℃で撹拌しながらエチルビニルエーテル３０ｇをテトラヒドロフラン３０ｇに溶解させた溶液を滴下した。
　３０分反応させた後、濃アンモニア水により中和し、水５Ｌに中和した反応液を滴下したところ、白色固体が得られた。これを濾過後、アセトン３００ｍｌに溶解させ、水５Ｌに滴下し、濾過後、乾燥してＡ１－２を得た。
　ＧＰＣによるポリスチレン換算の重量平均分子量は５０００であった。
　1Ｈ－ＮＭＲによる分析において、Ａ１－２においては、フェノール性水酸基の水素原子の７０モル％がエトキシエチル化されたことが確認された。
　Ａ１－２の合成に使用したシラン化合物の種類及びモル比を以下に示す。
Figure JPOXMLDOC01-appb-T000042
 (Synthesis of A1-2) Synthesis of polysiloxane having phenolic hydroxyl group protected with acid-decomposable group and epoxy group 114.2 g (0.5 mol) of 4-hydroxybenzyltrimethoxysilane, 3-glycid 94.5 g (0.4 mol) of xylpropyltrimethoxysilane, 6.8 g (0.05 mol) of methyltrimethoxysilane, 9.9 g (0.05 mol) of phenyltrimethoxysilane, 250 g of DAA (diacetone alcohol) Was added to a three-necked flask, and an aqueous phosphoric acid solution in which 0.176 g of phosphoric acid (0.1 wt% with respect to the charged silane compound) was dissolved in 54 g of water was added over 30 minutes while stirring at room temperature. Thereafter, the three-necked flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes, and then reacted at 60 ° C. for 5 hours.
During the reaction, methanol as a by-product was distilled off. The obtained polysiloxane DAA solution was poured into a large amount of water to precipitate a polymer, filtered and dried to obtain an A1-2 precursor.
100 g of the resulting A1-2 precursor was dissolved in 400 mL of tetrahydrofuran, and after adding a catalytic amount of p-toluenesulfonic acid, a solution in which 30 g of ethyl vinyl ether was dissolved in 30 g of tetrahydrofuran was added dropwise with stirring at 20 ° C. .
After reacting for 30 minutes, the reaction solution was neutralized with concentrated aqueous ammonia and neutralized with 5 L of water, and a white solid was obtained. This was filtered, dissolved in 300 ml of acetone, dropped into 5 L of water, filtered and dried to obtain A1-2.
The weight average molecular weight in terms of polystyrene by GPC was 5000.
Analysis by 1 H-NMR confirmed that 70 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxyethylated in A1-2.
The types and molar ratios of the silane compounds used for the synthesis of A1-2 are shown below.
Figure JPOXMLDOC01-appb-T000042
（Ａ１－４の合成）　酸分解性基で保護されたカルボキシ基と、エポキシ基とを有するポリシロキサンの合成
　シラン化合物を、以下に示す化合物及びモル比で使用し、保護基の種類と量を調整した以外はＡ１－１と同様にして、下記シラン化合物を混合、反応させ、高分子反応で保護基を導入し、Ａ１ー４を合成した。
　１Ｈ－ＮＭＲによる分析において、Ａ１ー４においては、カルボキシ基の７８モル％がテトラヒドロフラニル化されたことが確認された。
Figure JPOXMLDOC01-appb-T000043
 (Synthesis of A1-4) Synthesis of polysiloxane having a carboxyl group protected with an acid-decomposable group and an epoxy group A silane compound was used in the following compounds and molar ratios, and the types and amounts of the protecting groups were changed. A1-4 was synthesized in the same manner as A1-1 except that the following silane compounds were mixed and reacted and a protecting group was introduced by a polymer reaction.
Analysis by 1 H-NMR confirmed that 78 mol% of the carboxy group was tetrahydrofuranylated in A1-4.
Figure JPOXMLDOC01-appb-T000043
（Ａ１－５合成）　酸分解性基で保護されたカルボキシ基と、エポキシ基とを有するポリシロキサンの合成
　シラン化合物を、以下に示す化合物及びモル比で使用し、保護基をエトキシエチル基に変更して量を調整した以外はＡ１－１と同様にして、下記シラン化合物を混合、反応させ、高分子反応で保護基を導入し、Ａ１－５を合成した。
　１Ｈ－ＮＭＲによる分析において、Ａ１－５においては、カルボキシ基の７０モル％がエトキシエチル化されたことが確認された。 (Synthesis of A1-5) Synthesis of polysiloxane having a carboxyl group protected with an acid-decomposable group and an epoxy group The silane compound is used in the following compounds and molar ratio, and the protective group is changed to an ethoxyethyl group The following silane compounds were mixed and reacted in the same manner as A1-1 except that the amount was adjusted, and a protective group was introduced by a polymer reaction to synthesize A1-5.
Analysis by 1 H-NMR confirmed that 70 mol% of the carboxy group was ethoxyethylated in A1-5.
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000044
（Ａ１－６合成）　酸分解性基で保護されたカルボキシ基と、エポキシ基とを有するポリシロキサンの合成
　シラン化合物を、以下に示す化合物及びモル比で使用し、保護基の種類と量を調整した以外は、Ａ１-１と同様にして、下記シラン化合物を混合、反応させ、高分子反応で保護基を導入し、Ａ１－５を合成した。
　１Ｈ－ＮＭＲによる分析において、Ａ１－５においては、カルボキシ基の８２モル％がテトラヒドロフラニル化されたことが確認された。
Figure JPOXMLDOC01-appb-T000045
 (Synthesis of A1-6) Synthesis of polysiloxane having a carboxyl group protected with an acid-decomposable group and an epoxy group The silane compound is used in the following compounds and molar ratios, and the kind and amount of the protecting group are adjusted. Except for the above, A1-5 was synthesized in the same manner as A1-1 by mixing and reacting the following silane compounds and introducing a protecting group by a polymer reaction.
The analysis by 1 H-NMR confirmed that 82 mol% of the carboxy group was tetrahydrofuranylated in A1-5.
Figure JPOXMLDOC01-appb-T000045
　（Ａ２－１の合成）　酸分解性基で保護されたカルボキシ基を有するポリシロキサンの合成
　シラン化合物を、以下に示す化合物及びモル比で使用し、保護基の種類と量を調整した以外はＡ１－１と同様にして下記シラン化合物を混合、反応させてＡ２－１前駆体を得た（カルボキシ基がテトラヒドロフランで保護される前のポリシロキサン）。
　Ａ２－１前駆体に対し、高分子反応で保護基を導入して、Ａ２－１を合成した。
　Ａ２－１においては、カルボキシ基の９０モル％がテトラヒドロフラニル化されたことがＮＭＲで確認された。ＧＰＣによるポリスチレン換算の重量平均分子量は５０００であった。
Figure JPOXMLDOC01-appb-T000046
 (Synthesis of A2-1) Synthesis of polysiloxane having a carboxy group protected with an acid-decomposable group A1 except that the silane compound was used in the following compounds and molar ratios and the type and amount of the protecting group were adjusted. In the same manner as -1, the following silane compounds were mixed and reacted to obtain an A2-1 precursor (polysiloxane before the carboxy group was protected with tetrahydrofuran).
A2-1 was synthesized by introducing a protecting group into the A2-1 precursor by a polymer reaction.
In A2-1, it was confirmed by NMR that 90 mol% of the carboxy group was tetrahydrofuranylated. The weight average molecular weight in terms of polystyrene by GPC was 5000.
Figure JPOXMLDOC01-appb-T000046
　（Ａ２－２の合成）　酸分解性基で保護されたフェノール性水酸基を有するポリシロキサンの合成
　シラン化合物を、以下に示す化合物及びモル比で使用し、保護基の種類と量を調整した以外はＡ１－２と同様にして、下記シラン化合物を混合、反応させ、高分子反応で保護基を導入し、Ａ２－２を合成した。
　１Ｈ－ＮＭＲによる分析において、Ａ２－２においては、フェノール性水酸基の水素原子の８５モル％がエトキシエチル化されたことが確認された。
　ＧＰＣによるポリスチレン換算の重量平均分子量は６０００であった。
Figure JPOXMLDOC01-appb-T000047
 (Synthesis of A2-2) Synthesis of polysiloxane having a phenolic hydroxyl group protected with an acid-decomposable group The silane compound was used in the following compounds and molar ratios, and the type and amount of the protecting group were adjusted. In the same manner as A1-2, the following silane compounds were mixed and reacted, and a protective group was introduced by a polymer reaction to synthesize A2-2.
Analysis by 1 H-NMR confirmed that 85 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxyethylated in A2-2.
The weight average molecular weight in terms of polystyrene by GPC was 6000.
Figure JPOXMLDOC01-appb-T000047
（Ａ２－４合成）酸分解性基で保護されたカルボキシ基を有するポリシロキサンの合成
　シラン化合物を、以下に示す化合物及びモル比で使用し、保護基をエトキシエチル基に変更して量を調整した以外はＡ１－１と同様にして、下記シラン化合物を混合、反応させ、高分子反応で保護基を導入し、Ａ２－４を合成した。
　１Ｈ－ＮＭＲによる分析において、Ａ２－４は、カルボキシ基の８５モル％がエトキシエチル化されたことが確認された。
Figure JPOXMLDOC01-appb-T000048
 (A2-4 synthesis) Synthesis of polysiloxane having carboxy group protected with acid-decomposable group Using silane compound in the following compounds and molar ratio, changing the protecting group to ethoxyethyl group to adjust the amount Except that, A2-4 was synthesized in the same manner as A1-1 by mixing and reacting the following silane compounds and introducing a protecting group by polymer reaction.
In analysis by 1 H-NMR, it was confirmed that A2-4 was ethoxyethylated in 85 mol% of the carboxy group.
Figure JPOXMLDOC01-appb-T000048
　（Ａ３－１の合成）　カルボキシ基とエポキシ基とを有するポリシロキサンの合成
　シラン化合物を、以下に示す化合物及びモル比で使用し、ジヒドロフランによる保護反応を行わない以外はＡ１－１と同様にして下記シラン化合物を混合、反応させ、カルボキシ基とエポキシ基とを有するポリシロキサンＡ３－１を合成した。
　ＧＰＣによるポリスチレン換算の重量平均分子量は５０００であった。
Figure JPOXMLDOC01-appb-T000049
 (Synthesis of A3-1) Synthesis of polysiloxane having a carboxy group and an epoxy group A silane compound was used in the following compounds and molar ratios, and the same reaction as in A1-1 was conducted except that a protective reaction with dihydrofuran was not performed. The following silane compounds were mixed and reacted to synthesize polysiloxane A3-1 having a carboxy group and an epoxy group.
The weight average molecular weight in terms of polystyrene by GPC was 5000.
Figure JPOXMLDOC01-appb-T000049
　（Ａ３－２の合成）　フェノール性水酸基とエポキシ基とを有するポリシロキサンの合成
　シラン化合物を、以下に示す化合物及びモル比で使用し、保護基導入を行わないこと以外はＡ１－２と同様にして、下記シラン化合物を混合、反応させ、Ａ３－２を合成した。
　ＧＰＣによるポリスチレン換算の重量平均分子量は６０００であった。
Figure JPOXMLDOC01-appb-T000050
 (Synthesis of A3-2) Synthesis of polysiloxane having phenolic hydroxyl group and epoxy group The same as A1-2 except that a silane compound is used in the following compounds and molar ratio and no protective group is introduced. Then, the following silane compounds were mixed and reacted to synthesize A3-2.
The weight average molecular weight in terms of polystyrene by GPC was 6000.
Figure JPOXMLDOC01-appb-T000050
　（Ａ３－３の合成）　カルボキシ基とオキセタニル基とを有するポリシロキサンの合成
　シラン化合物を、以下に示す化合物及びモル比で使用し、保護基導入を行わないこと以外はＡ１－１と同様にして、下記シラン化合物を混合、反応させ、Ａ３－３を合成した。
　ＧＰＣによるポリスチレン換算の重量平均分子量は６０００であった。 (Synthesis of A3-3) Synthesis of polysiloxane having a carboxy group and an oxetanyl group As in A1-1, except that a silane compound is used in the following compounds and molar ratio and no protective group is introduced. Then, the following silane compounds were mixed and reacted to synthesize A3-3.
The weight average molecular weight in terms of polystyrene by GPC was 6000.
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000051
　（Ａ’－１の合成）　酸分解性基で保護されたシラノール基と、エポキシ基とを有するポリシロキサン
　フェニルトリメトキシシラン８９．２ｇ（０．４５モル）、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン１１０．９ｇ（０．４５モル）、メタノール３６０ｇを三つ口フラスコに仕込み、撹拌しながら１０℃以下に氷冷した。滴下ロートに０．１Ｍの酢酸水溶液９０ｇを仕込み、氷冷しながら滴下したところ、発熱を伴い加水分解縮合反応が進行した。内温を室温まで上昇させ、２時間撹拌熟成した後、エステルアダプターを設置し、加熱常圧にてメタノール留去を行った。内温がメタノールの沸点を超えるまで留去を続けることによって、白濁粘ちょうなポリシロキサン溶液を得た。この時、捕捉したメタノール量は３８２ｇであった。このポリシロキサン溶液に酢酸エチル３００ｇを添加し、溶解した溶液を純水にて２回水洗を行った。このポリシロキサン溶液をロータリーエバポレーターにて濃縮することにより、無色透明のポリシロキサン溶液を２３３ｇ（固形分濃度６２．２質量％）得た。
　得られたポリシロキサン溶液８０．４ｇを酢酸エチル溶液からテトラヒドロフラン溶液（固形分濃度２０質量％）に溶媒置換した後、温度計、撹拌機、冷却器を備えた三つ口フラスコに仕込み、メタンスルホン酸１．０ｇ（０．０１モル）を添加した。
　次に、１０℃以下に氷冷し撹拌しながら、エチル－１－プロペニルエーテル１９．４ｇ（０．２３モル）を滴下ロートにて内温を１０℃以下に保ちながら滴下した。滴下後室温にて２時間反応させた後、トリエチルアミン１．０ｇ（０．０１モル）を添加し反応を終了した。反応液を１Ｌナスフラスコに移し、常温減圧下ロータリーエバポレーターにてテトラヒドロフランを留去し、メチルイソブチルケトン３００ｇ及び０．０１Ｎ酢酸水溶液２５０ｍｌを添加し反応液を水洗浄した。この洗浄操作を合計３回繰り返した後、有機層を分離、ロータリーエバポレーターにて濃縮して、無色透明のシラノール基がアセタール保護されたポリシロキサンＡ‘－１を４９．０ｇ得た。
　Ａ‘－１のアセタール置換率はＮＭＲの結果より３２．５モル％と算出された。 (Synthesis of A′-1) 89.2 g (0.45 mol) of polysiloxane phenyltrimethoxysilane having a silanol group protected with an acid-decomposable group and an epoxy group, 2- (3,4-epoxycyclohexyl) ) 110.9 g (0.45 mol) of ethyltrimethoxysilane and 360 g of methanol were charged into a three-necked flask and cooled on ice at 10 ° C. or lower with stirring. When 90 g of 0.1 M acetic acid aqueous solution was charged into the dropping funnel and dropped while cooling with ice, hydrolysis condensation reaction proceeded with heat generation. After raising the internal temperature to room temperature and aging for 2 hours, an ester adapter was installed, and methanol was distilled off under heating and normal pressure. Distillation was continued until the internal temperature exceeded the boiling point of methanol to obtain a cloudy viscous polysiloxane solution. At this time, the amount of captured methanol was 382 g. To this polysiloxane solution, 300 g of ethyl acetate was added, and the dissolved solution was washed twice with pure water. The polysiloxane solution was concentrated with a rotary evaporator to obtain 233 g of a colorless and transparent polysiloxane solution (solid content concentration: 62.2% by mass).
The resulting polysiloxane solution (80.4 g) was solvent-substituted from an ethyl acetate solution to a tetrahydrofuran solution (solid content concentration: 20% by mass), and then charged into a three-necked flask equipped with a thermometer, a stirrer, and a cooler. 1.0 g (0.01 mol) of acid was added.
Next, 19.4 g (0.23 mol) of ethyl-1-propenyl ether was added dropwise while keeping the internal temperature at 10 ° C. or less with a dropping funnel while cooling with ice at 10 ° C. or lower and stirring. After dropping, the mixture was reacted at room temperature for 2 hours, and then 1.0 g (0.01 mol) of triethylamine was added to complete the reaction. The reaction solution was transferred to a 1 L eggplant flask, tetrahydrofuran was distilled off with a rotary evaporator under reduced pressure at room temperature, 300 g of methyl isobutyl ketone and 250 ml of 0.01N acetic acid aqueous solution were added, and the reaction solution was washed with water. After repeating this washing operation three times in total, the organic layer was separated and concentrated by a rotary evaporator to obtain 49.0 g of polysiloxane A′-1 having a colorless and transparent silanol group protected by acetal.
The acetal substitution rate of A′-1 was calculated to be 32.5 mol% from the NMR results.
＜感光性樹脂組成物の調製＞
　下記表に記載のように各成分を配合・撹拌して溶剤溶液とし、孔径０．２μｍのポリテトラフルオロエチレン製フィルターで濾過して、各実施例および比較例の感光性樹脂組成物を得た。 <Preparation of photosensitive resin composition>
As shown in the following table, each component was blended and stirred to obtain a solvent solution, and filtered through a polytetrafluoroethylene filter having a pore size of 0.2 μm to obtain photosensitive resin compositions of Examples and Comparative Examples. .
　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。
＜（Ａ）ポリシロキサン成分＞
　Ａ１－１、Ａ１－２、Ａ１－４、Ａ１－５、Ａ１－６、Ａ２－１、Ａ２－２、Ａ２－４、Ａ３－１、Ａ３－２、Ａ３－３、Ａ１－１前駆体、Ａ’－１：上記合成例に従って合成したポリシロキサン
＜（Ｂ）光酸発生剤＞
　Ｂ－１：ＰＡＧ－１０３（商品名、下記に示す構造、ＢＡＳＦ社製）
　Ｂ－１は、ｐＫａが３以下の酸を発生する光酸発生剤である。
Figure JPOXMLDOC01-appb-C000052
 　Ｂ－２：ＰＡＩ１０１（商品名、下記に示す構造、みどり化学（株）製）
　Ｂ－２は、ｐＫａが３以下の酸を発生する光酸発生剤である。
Figure JPOXMLDOC01-appb-C000053
 　Ｂ－３：ＤＴＳ－１０５（商品名、トリアリールスルホニウム塩、みどり化学社製）
　Ｂ－３は、ｐＫａが３以下の酸を発生する光酸発生剤である。
　Ｂ－４：下記に示す構造（ＷＯ２０１１／０８７０１１号パンフレットの２４９段落記載の方法に従って合成した。）
　Ｂ－４は、ｐＫａが３以下の酸を発生する光酸発生剤である。
Figure JPOXMLDOC01-appb-C000054
 　Ｂ－５：ＧＳＩＤ－２６－１（商品名、トリアリールスルホニウム塩、下記に示す構造、ＢＡＳＦ社製）
　Ｂ－５は、ｐＫａが３以下の酸を発生する光酸発生剤である。
Figure JPOXMLDOC01-appb-C000055
 　Ｂ－６：４，７－ジ－ｎ－ブトキシ－１－ナフチルテトラヒドロチオフェニウムトリフルオロメタンスルホネート
　Ｂ－６は、ｐＫａが３以下の酸を発生する光酸発生剤である。
　Ｂ－７：下記に示す構造
　Ｂ－７は、ｐＫａが３以下の酸を発生する光酸発生剤である。
Figure JPOXMLDOC01-appb-C000056
 　Ｂ’－１：（下記に示す構造。キノンジアジド化合物）
　Ｂ’－１は、ｐＫａが３を超える酸を発生する化合物である。
Figure JPOXMLDOC01-appb-C000057
 ＜（Ｃ）溶剤＞
　Ｃ－１：プロピレングリコール１－モノメチルエーテル２－アセタート
　Ｃ－２：メチルエチルジグリコール
　Ｃ－３：ジエチルジグリコール
　Ｃ－４：ブチレングリコールジアセテート
　Ｃ－５：シクロヘキサノールアセテート
　Ｃ－６：エチレングリコールモノメチルエーテルアセテート
＜（Ｓ）脂環式エポキシ化合物＞
Ｓ－１：下記化合物（（株）ダイセル製、セロキサイド２０２１Ｐ、分子量２５２）
Figure JPOXMLDOC01-appb-C000058
 Ｓ－２：下記化合物（分子量２６８、合成品）
　丸善ＫＫ出版、第四版実験化学講座２０有機合成ＩＩ、２１３～に記載の方法に従って合成した。
Figure JPOXMLDOC01-appb-C000059
 Ｓ－４：下記化合物（（株）ダイセル製、セロキサイド２０００、分子量３７８）
Figure JPOXMLDOC01-appb-C000060
 Ｓ－５：下記化合物（分子量５２０）
Figure JPOXMLDOC01-appb-C000061
 Ｓ’－１：下記化合物（エポキシ基を有するポリシロキサン、分子量３６２）
温度計、攪拌装置を備えたガラス製反応容器に、トルエン２００ｇに、１，１，３，３－テトラメチルジシロキサン１３４ｇ（１モル）、アリルグリシジルエーテル２２８ｇ（２モル）、及び白金－ジビニルテトラメチルジシロキサン錯体（Ｋａｒｓｔｅｄｔ触媒）９ｍｇを加えて、攪拌しながら５０～６０℃で１５時間反応させた。この反応液から溶媒を６０℃で減圧留去させ、Ｓ‘－１を得た。
Figure JPOXMLDOC01-appb-C000062
 Ｓ’－２：下記化合物（脂環エポキシ基を有するポリシロキサン）
２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン　１７２．２ｇ（０．７モル）、ジメチルジメトキシシラン　１８ｇ（０．１５モル）、メチルトリメトキシシラン　２０．４ｇ（０．１５モル）、ＤＡＡ（ジアセトンアルコール）５００ｇを、三口フラスコに仕込み、室温で攪拌しながら、水５４ｇにリン酸０．１７６ｇを溶かしたリン酸水溶液を、３０分かけて添加した。その後、三口フラスコを４０℃のオイルバスに浸けて３０分攪拌した後、６０℃で８時間反応させた。反応中に副生成物であるメタノールが留出した。得られたポリシロキサンのＤＡＡ溶液を多量の水に注いでポリマーを析出させ、ろ過、乾燥してＳ‘－２を得た。
　ＧＰＣによるポリスチレン換算の重量平均分子量は２５００であった。
Ｓ’－３：下記化合物（（株）ダイセル製、ＥＨＰＥ－３１５０）
Figure JPOXMLDOC01-appb-C000063
 Ｓ’－４：下記化合物３（（株）ダイセル製、セロキサイド２０００、分子量１２４）
Figure JPOXMLDOC01-appb-C000064
 ＜塩基性化合物、その他添加剤＞
　ＴＢＡ：トリブチルアミン
　ＴＰＩ：　トリフェニルイミダゾール
　ＤＢＡ：９，１０－ジブトキシアントラセン
　ＦＡ－６３０：シリコーン系界面活性剤（ＦＡ－６３０、商品名、信越化学製）
　Ｆ－５５４：パーフルオロアルキル基含有ノニオン界面活性剤（メガファック　Ｆ－５５４、商品名、ＤＩＣ製） The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
<(A) Polysiloxane component>
A1-1, A1-2, A1-4, A1-5, A1-6, A2-1, A2-2, A2-4, A3-1, A3-2, A3-3, A1-1 precursor, A′-1: Polysiloxane synthesized according to the above synthesis example <(B) Photoacid generator>
B-1: PAG-103 (trade name, structure shown below, manufactured by BASF)
B-1 is a photoacid generator that generates an acid having a pKa of 3 or less.
Figure JPOXMLDOC01-appb-C000052
 B-2: PAI101 (trade name, structure shown below, manufactured by Midori Chemical Co., Ltd.)
B-2 is a photoacid generator that generates an acid having a pKa of 3 or less.
Figure JPOXMLDOC01-appb-C000053
 B-3: DTS-105 (trade name, triarylsulfonium salt, manufactured by Midori Chemical Co., Ltd.)
B-3 is a photoacid generator that generates an acid having a pKa of 3 or less.
B-4: Structure shown below (synthesized according to the method described in paragraph 249 of WO2011 / 087011 pamphlet)
B-4 is a photoacid generator that generates an acid having a pKa of 3 or less.
Figure JPOXMLDOC01-appb-C000054
 B-5: GSID-26-1 (trade name, triarylsulfonium salt, structure shown below, manufactured by BASF)
B-5 is a photoacid generator that generates an acid having a pKa of 3 or less.
Figure JPOXMLDOC01-appb-C000055
 B-6: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate B-6 is a photoacid generator that generates an acid having a pKa of 3 or less.
B-7: Structure shown below B-7 is a photoacid generator that generates an acid having a pKa of 3 or less.
Figure JPOXMLDOC01-appb-C000056
 B′-1: (Structure shown below. Quinonediazide compound)
B′-1 is a compound that generates an acid having a pKa of more than 3.
Figure JPOXMLDOC01-appb-C000057
 <(C) Solvent>
C-1: Propylene glycol 1-monomethyl ether 2-acetate C-2: Methyl ethyl diglycol C-3: Diethyl diglycol C-4: Butylene glycol diacetate C-5: Cyclohexanol acetate C-6: Ethylene glycol monomethyl Ether acetate <(S) alicyclic epoxy compound>
S-1: The following compound (manufactured by Daicel Corporation, Celoxide 2021P, molecular weight 252)
Figure JPOXMLDOC01-appb-C000058
 S-2: The following compound (molecular weight 268, synthetic product)
It was synthesized according to the method described in Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213-.
Figure JPOXMLDOC01-appb-C000059
 S-4: The following compound (manufactured by Daicel Corporation, Celoxide 2000, molecular weight 378)
Figure JPOXMLDOC01-appb-C000060
 S-5: The following compound (molecular weight 520)
Figure JPOXMLDOC01-appb-C000061
 S′-1: the following compound (polysiloxane having an epoxy group, molecular weight 362)
In a glass reaction vessel equipped with a thermometer and a stirrer, 200 g of toluene, 134 g (1 mol) of 1,1,3,3-tetramethyldisiloxane, 228 g (2 mol) of allyl glycidyl ether, and platinum-divinyltetra 9 mg of methyldisiloxane complex (Karstedt catalyst) was added and reacted at 50-60 ° C. for 15 hours with stirring. The solvent was distilled off from this reaction solution under reduced pressure at 60 ° C. to obtain S′-1.
Figure JPOXMLDOC01-appb-C000062
 S′-2: The following compound (polysiloxane having an alicyclic epoxy group)
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 172.2 g (0.7 mol), dimethyldimethoxysilane 18 g (0.15 mol), methyltrimethoxysilane 20.4 g (0.15 mol), DAA (Diacetone alcohol) 500 g was charged into a three-necked flask, and an aqueous phosphoric acid solution in which 0.176 g of phosphoric acid was dissolved in 54 g of water was added over 30 minutes while stirring at room temperature. Thereafter, the three-necked flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes, and then reacted at 60 ° C. for 8 hours. During the reaction, methanol as a by-product was distilled off. The obtained polysiloxane DAA solution was poured into a large amount of water to precipitate a polymer, filtered and dried to obtain S′-2.
The weight average molecular weight in terms of polystyrene by GPC was 2500.
S′-3: The following compound (manufactured by Daicel Corporation, EHPE-3150)
Figure JPOXMLDOC01-appb-C000063
 S′-4: the following compound 3 (manufactured by Daicel Corporation, Celoxide 2000, molecular weight 124)
Figure JPOXMLDOC01-appb-C000064
 <Basic compounds and other additives>
TBA: Tributylamine TPI: Triphenylimidazole DBA: 9,10-dibutoxyanthracene FA-630: Silicone surfactant (FA-630, trade name, manufactured by Shin-Etsu Chemical)
F-554: Perfluoroalkyl group-containing nonionic surfactant (Megafac F-554, trade name, manufactured by DIC)
＜感度の評価＞
　６８０ｍｍ×８８０ｍｍ角のガラス基板（ＥＡＧＬＥ　ＸＧ、０．７ｍｍ厚（コーニング社製））を、ヘキサメチルジシラザン蒸気下に３０秒曝し、各感光性樹脂組成物をスリット塗布した後、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２．５μｍ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　７８００ＣＦを用いて、直径７μｍホール形状のマスクパターンで露光した。そして、露光後の感光性樹脂組成物層を、アルカリ現像液（０．６％のテトラメチルアンモニウムヒドロキシド水溶液）で２４℃／５５秒間現像した後、超純水で１５秒リンスした。これらの操作により、直径７μｍのホールを解像する時の最適ｉ線露光量（Ｅｏｐｔ）を求め感度とした。以下の基準で評価した。１、２および３が実用レベルである。
１：８０ｍＪ／ｃｍ２未満
２：８０ｍＪ／ｃｍ２以上、１００ｍＪ／ｃｍ２未満
３：１００ｍＪ／ｃｍ２以上、１５０ｍＪ／ｃｍ２未満
４：１５０ｍＪ／ｃｍ２以上、１９０ｍＪ／ｃｍ２未満
５：１９０ｍＪ／ｃｍ２以上 <Evaluation of sensitivity>
A glass substrate having a size of 680 mm × 880 mm (EAGLE XG, 0.7 mm thickness (manufactured by Corning)) was exposed to hexamethyldisilazane vapor for 30 seconds, and each photosensitive resin composition was slit-coated, followed by 90 ° C./120 Pre-baked on a second hot plate to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 2.5 μm.
Next, the obtained photosensitive resin composition layer was exposed with a mask pattern having a hole shape of 7 μm in diameter using MPA 7800CF manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (0.6% tetramethylammonium hydroxide aqueous solution) at 24 ° C./55 seconds, and then rinsed with ultrapure water for 15 seconds. Through these operations, the optimum i-line exposure amount (Eopt) when resolving a hole having a diameter of 7 μm was determined and used as the sensitivity. Evaluation was made according to the following criteria. 1, 2 and 3 are practical levels.
1: 80mJ / cm 2 less than 2: 80mJ / cm 2 or more, 100 mJ / cm 2 less than 3: 100mJ / cm 2 or more and less than 150mJ / cm 2 4: 150mJ / cm 2 or more, 190 mJ / cm 2 less than 5: 190 mJ / cm 2 or more
＜現像性＞
＜＜パターン欠陥の評価＞＞
　３００ｍｍ×４００ｍｍ角のガラス基板（０．７ｍｍ厚（コーニング社製））を、ヘキサメチルジシラザン蒸気下に３０秒曝し、各感光性樹脂組成物をスリット塗布した後、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２．５μｍ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　７８００ＣＦを用いて、直径１５μｍの円形ドットパターンが一辺２００μｍの格子点上に形成された、孤立ドットパターン形状のマスクで最適露光量だけ露光した。そして、露光後の感光性樹脂組成物層を、アルカリ現像液（０．６％のテトラメチルアンモニウムヒドロキシド水溶液）で２４℃／５５秒間現像した後、超純水で２０秒リンスした。このようにして基板全面に孤立ドットパターンを形成した。
　基板全面から満遍なく選んだ任意の１００箇所のドットを光学顕微鏡で観察し、欠陥のあるドットの個数を数えた。なお、パターンの一部に欠けがある状態、または、パターンが剥がれた状態を欠陥とした。
　以下の基準で評価した。１、２および３が実用レベルである。
１：３個未満
２：３個以上、６個未満
３：６個以上、１０個未満
４：１０個以上、２０個未満
５：２０個以上 <Developability>
<< Evaluation of pattern defects >>
A 300 mm × 400 mm square glass substrate (0.7 mm thickness (manufactured by Corning)) was exposed to hexamethyldisilazane vapor for 30 seconds, and each photosensitive resin composition was slit-coated, followed by a hot plate at 90 ° C./120 seconds. Pre-baking was performed to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 2.5 μm was formed.
Next, the obtained photosensitive resin composition layer was used with a mask of an isolated dot pattern in which a circular dot pattern having a diameter of 15 μm was formed on a lattice point having a side of 200 μm by using MPA 7800CF manufactured by Canon Inc. Only the optimum exposure amount was exposed. The exposed photosensitive resin composition layer was developed with an alkali developer (0.6% tetramethylammonium hydroxide aqueous solution) at 24 ° C./55 seconds, and then rinsed with ultrapure water for 20 seconds. In this way, an isolated dot pattern was formed on the entire surface of the substrate.
Arbitrary 100 dots selected from the entire surface of the substrate were observed with an optical microscope, and the number of defective dots was counted. In addition, the state in which a part of the pattern is chipped or the state in which the pattern is peeled is defined as a defect.
Evaluation was made according to the following criteria. 1, 2 and 3 are practical levels.
1: Less than 3 2: 3 or more, less than 6 3: 6 or more, less than 10 4: 10 or more, less than 20 5: 20 or more
＜＜残渣の評価＞＞
　パターン欠陥の評価と同様にして得た孤立ドットパターンサンプルについて、基板全面から満遍なく選んだ任意の１００箇所のドットとその周辺を光学顕微鏡で観察し、残渣のあるドットの個数を数えた。
　以下の基準で、１、２および３が実用レベルである。
１：１個未満
２：１個以上、３個未満
３：３個以上、６個未満
４：６個以上、１０個未満
５：１０個以上 << Evaluation of residue >>
With respect to the isolated dot pattern sample obtained in the same manner as the evaluation of the pattern defect, 100 arbitrary dots selected uniformly from the entire surface of the substrate and the periphery thereof were observed with an optical microscope, and the number of dots with residues was counted.
Based on the following criteria, 1, 2 and 3 are practical levels.
Less than 1: 1, 2: 1 or more, less than 3, 3: 3 or more, less than 6, 4: 6 or more, less than 10, 5:10 or more
＜保存安定性の評価＞
　感光性樹脂組成物の調製直後の、粘度Ｎ０（単位：Ｐａ・ｓ）と、５℃で３０日間保存した後の粘度Ｎ１（単位：Ｐａ・ｓ）とを測定し、以下の式の値を算出した。
　｜（Ｎ１－Ｎ０）｜／Ｎ０
　上記数式の値は、経時による粘度変化を表し、数値が小さいほど好ましい。以下の基準で評価した。
Ａ：０．０８未満
Ｂ：０．０８以上 <Evaluation of storage stability>
The viscosity N 0 (unit: Pa · s) immediately after the preparation of the photosensitive resin composition and the viscosity N 1 (unit: Pa · s) after storage at 5 ° C. for 30 days were measured, and The value was calculated.
| (N 1 −N 0 ) | / N 0
The value of the above formula represents the change in viscosity over time, and the smaller the value, the better. Evaluation was made according to the following criteria.
A: Less than 0.08 B: 0.08 or more
Figure JPOXMLDOC01-appb-T000065
Figure JPOXMLDOC01-appb-T000065
Figure JPOXMLDOC01-appb-T000066
Figure JPOXMLDOC01-appb-T000066
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000068
Figure JPOXMLDOC01-appb-T000068
　上記結果より、実施例の感光性樹脂組成物は、感度および現像性に優れていた。また、実施例の感光性樹脂組成物により形成された硬化膜は３００℃に加熱しても透明性に優れており、耐熱性に優れていた。また、実施例の感光性樹脂組成物は、保存安定性にも優れていた。
　これに対し、比較例の感光性樹脂組成物は、感度、現像性のいずれか一方が劣るものであった。 From the above results, the photosensitive resin compositions of the examples were excellent in sensitivity and developability. Moreover, the cured film formed with the photosensitive resin composition of an Example was excellent in transparency even if it heated to 300 degreeC, and was excellent in heat resistance. Moreover, the photosensitive resin composition of an Example was excellent also in storage stability.
On the other hand, the photosensitive resin composition of the comparative example was inferior in either sensitivity or developability.
＜液晶表示装置の作製＞
（実施例１００）
　特許第３３２１００３号公報の図１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、実施例１００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用い、層間絶縁膜として硬化膜１７を形成した。
　特許第３３２１００３号公報の００５８段落の基板と層間絶縁膜１７の濡れ性を向上させる前処理として、基板をヘキサメチルジシラザン（ＨＭＤＳ）蒸気下に３０秒曝し、その後、実施例１の感光性樹脂組成物をスピンコート塗布した後、９０℃で２分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３μｍ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、１０μｍφのホールパターンのマスクを介して４０ｍＪ／ｃｍ２（エネルギー強度：２０ｍＷ／ｃｍ２、ｉ線）となるよう露光した。そして、露光後の感光性樹脂組成物層を、９０℃、２分ホットプレート上で加熱処理した後、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秒間パドル現像した後、超純水で２０秒リンスした。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）となるように全面露光し、その後、この基板をオーブンにて２８０℃で３０分加熱して硬化膜を得た。
　上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。
　得られた液晶表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 <Production of liquid crystal display device>
(Example 100)
In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 100 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film.
As a pretreatment for improving the wettability of the substrate and the interlayer insulating film 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the photosensitive resin of Example 1 is used. After spin-coating the composition, it was prebaked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent, thereby forming a photosensitive resin composition layer having a thickness of 3 μm. Next, the obtained photosensitive resin composition layer is 40 mJ / cm 2 (energy intensity: 20 mW / cm 2 ) through a hole pattern mask of 10 μmφ using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. , I-line). The exposed photosensitive resin composition layer was heat-treated on a hot plate at 90 ° C. for 2 minutes, and then paddled at 23 ° C./60 seconds with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution). After developing, it was rinsed with ultrapure water for 20 seconds. Subsequently, the entire surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and then this substrate was heated in an oven at 280 ° C. for 30 minutes. Thus, a cured film was obtained.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking.
When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
（実施例１０１）
　特開２００７－３２８２１０号公報の図１に記載の液晶表示装置において、有機絶縁膜ＰＡＳを以下の方法で形成し、液晶表示装置を得た。
　先ず、特開２００７－３２８２１０号公報に従って、有機絶縁膜ＰＡＳの直前まで形成したアレイ基板を作製した。
　次に、この基板をヘキサメチルジシラザン蒸気下に３０秒曝し、その後、実施例１の感光性樹脂組成物をスリット塗布した後、９０℃で２分ホットプレート上でプリベークして溶剤を揮発させ、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　７８００ＣＦを用いて、８μｍφのホールパターンのマスクを介して最適露光量ｍＪ／ｃｍ２（エネルギー強度：２０ｍＷ／ｃｍ２、ｉ線）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（０．６％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。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線で計測）となるように全面露光し、その後、この基板をオーブンにて２８０℃で３０分加熱して有機絶縁膜ＰＡＳを得た。
　以降の工程は、特開２００７－３２８２１０号公報に従って液晶表示装置を得た。
　本実施例ではＰＡＳに耐熱性の高い材料を用いているため、層間絶縁膜ＩＮ３を層間絶縁膜ＩＮ２と同等の温度で製膜した。これによりＩＮ３を緻密な膜とすることができた。
　得られた液晶表示装置に対して、駆動電圧を印加したところ、非常に良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 (Example 101)
In the liquid crystal display device described in FIG. 1 of JP-A-2007-328210, the organic insulating film PAS was formed by the following method to obtain a liquid crystal display device.
First, according to Japanese Patent Application Laid-Open No. 2007-328210, an array substrate formed up to just before the organic insulating film PAS was produced.
Next, this substrate was exposed to hexamethyldisilazane vapor for 30 seconds, and then the photosensitive resin composition of Example 1 was slit-coated and then pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent. A photosensitive resin composition layer was formed. Next, the obtained photosensitive resin composition layer was subjected to an optimum exposure dose mJ / cm 2 (energy intensity: 20 mW / cm 2) through a hole pattern mask of 8 μmφ using MPA 7800CF manufactured by Canon Inc. i-line) exposure. The exposed photosensitive resin composition layer was developed with an alkali developer (0.6% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , measured by i-line), and then the substrate was heated at 280 ° C. in an oven at 30 ° C. The organic insulating film PAS was obtained by heating for a few minutes.
In the subsequent steps, a liquid crystal display device was obtained in accordance with Japanese Unexamined Patent Publication No. 2007-328210.
In this embodiment, since a material having high heat resistance is used for PAS, the interlayer insulating film IN3 is formed at the same temperature as the interlayer insulating film IN2. Thereby, IN3 could be made into a dense film.
When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed very good display characteristics and had high reliability.
＜有機ＥＬ表示装置の作製＞
（実施例２０１）
　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３参照）。
　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。 <Production of organic EL display device>
(Example 201)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 3).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.
　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１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（０．４％のＴＭＡＨ水溶液）にて現像してパターンを形成し、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）となるように全面露光し、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。 Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiation with i-line (365 nm) at 45 mJ / cm 2 (energy intensity 20 mW / cm 2 ) using a mercury lamp, development is performed with an alkaline aqueous solution (0.4% TMAH aqueous solution) to form a pattern. Was used to expose the entire surface so that the integrated dose was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and a heat treatment was performed at 230 ° C./30 minutes.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing 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 flattening film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.
　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１６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, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition of Example 16 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.
　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。 Further, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
　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 type organic EL display device in which each organic EL element is connected to the TFT 1 for driving it was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.
＜タッチパネルの作製＞
（実施例３０１）
　以下に述べる方法によりタッチパネルを作製した。
＜第一の透明電極パターンの形成＞
＜＜透明電極層の形成＞＞
　あらかじめ額縁層が形成された強化処理ガラス（３００ｍｍ×４００ｍｍ×０．７ｍｍ）の前面板を、真空チャンバー内に導入し、ＳｎＯ2含有率が１０質量％のＩＴＯターゲット（インジウム：錫＝９５：５（モル比））を用いて、ＤＣマグネトロンスパッタリング（条件：基材の温度２５０℃、アルゴン圧０．１３Ｐａ、酸素圧０．０１Ｐａ）により、厚さ４０ｎｍのＩＴＯ薄膜を形成し、透明電極層を形成した前面板を得た。ＩＴＯ薄膜の表面抵抗は８０Ω／□であった。 <Production of touch panel>
(Example 301)
A touch panel was produced by the method described below.
<Formation of first transparent electrode pattern>
<< Formation of transparent electrode layer >>
A front plate of tempered glass (300 mm × 400 mm × 0.7 mm) with a frame layer formed in advance is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5) with a SnO 2 content of 10% by mass. (Molar ratio)) was used to form an ITO thin film having a thickness of 40 nm by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode layer was formed. A formed front plate was obtained. The surface resistance of the ITO thin film was 80Ω / □.
　次いで、市販のエッチングレジストをＩＴＯ上に塗布・乾燥し、エッチングレジスト層を形成した。露光マスク（透明電極パターンを有す石英露光マスク）面とエッチングレジスト層との間の距離を１００μｍに設定し、露光量５０ｍＪ／ｃｍ2（ｉ線）でパターン露光したのち、現像液で現像を行い、更に１３０℃３０分間のポストベーク処理を行って、透明電極層とエッチング用光感光性樹脂層パターンとを形成した前面板を得た。 Next, a commercially available etching resist was applied onto ITO and dried to form an etching resist layer. The distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the etching resist layer is set to 100 μm, pattern exposure is performed at an exposure amount of 50 mJ / cm 2 (i-line), and development is performed with a developer. Then, a post-baking treatment at 130 ° C. for 30 minutes was performed to obtain a front plate on which a transparent electrode layer and a photosensitive resin layer pattern for etching were formed.
　透明電極層とエッチング用光感光性樹脂層パターンとを形成した前面板を、ＩＴＯエッチャント（塩酸、塩化カリウム水溶液。液温３０℃）を入れたエッチング槽に浸漬し、１００秒処理し、エッチングレジスト層で覆われていない露出した領域の透明電極層を溶解除去し、エッチングレジスト層パターンのついた透明電極層パターン付の前面板を得た。
　次に、エッチングレジスト層パターンのついた透明電極層パターン付の前面板を、専用のレジスト剥離液に浸漬し、エッチング用光感光性樹脂層を除去し、額縁層と第一の透明電極パターンとを形成した前面板を得た。 The front plate on which the transparent electrode layer and the photo-sensitive resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched resist. The exposed transparent electrode layer not covered with the layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern with an etching resist layer pattern.
Next, the transparent electrode layer-patterned front plate with the etching resist layer pattern is immersed in a dedicated resist stripping solution, the etching photosensitive resin layer is removed, and the frame layer and the first transparent electrode pattern A front plate formed was obtained.
＜＜絶縁層の形成＞＞
　額縁層と第一の透明電極パターンとを形成した前面板の上に、実施例１の感光性樹脂組成物を塗布・乾燥（膜厚１μｍ、９０℃１２０秒）し、感光性樹脂組成物層を得た。露光マスク（絶縁層用パターンを有す石英露光マスク）面と感光性樹脂組成物層との間の距離を３０μｍに設定し、感度評価で求めた最適露光量でパターン露光した。
　次に、２．３８質量％のテトラメチルアンモニウムヒドロキシド水溶液により２３℃で１５秒間液盛り法にて現像し、更に超純水で１０秒間リンスした。続いて２２０℃４５分のポストベーク処理を行って、額縁層、第一の透明電極パターン、絶縁層パターンを形成した前面板を得た。 << Formation of insulating layer >>
On the front plate on which the frame layer and the first transparent electrode pattern were formed, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm, 90 ° C., 120 seconds) to form a photosensitive resin composition layer. Got. The distance between the surface of the exposure mask (quartz exposure mask having a pattern for insulating layer) and the photosensitive resin composition layer was set to 30 μm, and pattern exposure was performed with the optimum exposure amount obtained by sensitivity evaluation.
Next, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds and rinsed with ultrapure water for 10 seconds. Subsequently, a post-baking process at 220 ° C. for 45 minutes was performed to obtain a front plate on which a frame layer, a first transparent electrode pattern, and an insulating layer pattern were formed.
＜第二の透明電極パターンの形成＞
＜＜透明電極層の形成＞＞
　上記第一の透明電極パターンの形成と同様にして、絶縁層パターンまで形成した前面板をＤＣマグネトロンスパッタリング処理し（条件：基材の温度５０℃、アルゴン圧０．１３Ｐａ、酸素圧０．０１Ｐａ）、厚さ８０ｎｍのＩＴＯ薄膜を形成し、透明電極層を形成した前面板を得た。ＩＴＯ薄膜の表面抵抗は１１０Ω／□であった。
　更に、第一の透明電極パターンの形成と同様にして、エッチングし、エッチングレジスト層を除去することにより、額縁層、第一の透明電極パターン、実施例１の感光性樹脂組成物用いて形成した絶縁層パターン、第二の透明電極パターンを形成した前面板を得た。 <Formation of second transparent electrode pattern>
<< Formation of transparent electrode layer >>
In the same manner as the formation of the first transparent electrode pattern, the front plate formed up to the insulating layer pattern was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa). An ITO thin film having a thickness of 80 nm was formed to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 110Ω / □.
Furthermore, in the same manner as the formation of the first transparent electrode pattern, etching was performed and the etching resist layer was removed to form the frame layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. A front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was obtained.
＜第一及び第二の透明電極パターンとは別の導電性要素の形成＞
　上記第一、及び、第二の透明電極パターンの形成と同様にして、第一の透明電極パターン、実施例１の感光性樹脂組成物を用いて形成した絶縁層パターン、第二の透明電極パターンを形成した前面板をＤＣマグネトロンスパッタリング処理し、厚さ２００ｎｍのアルミニウム（Ａｌ）薄膜を形成した前面板を得た。
　更に、第一の透明電極パターンの形成と同様にして、エッチングし、エッチングレジスト層を除去することにより、額縁層、第一の透明電極パターン、実施例１の感光性樹脂組成物を用いて形成した絶縁層パターン、第二の透明電極パターン、第一及び第二の透明電極パターンとは別の導電性要素を形成した前面板を得た。 <Formation of Conductive Element Different from First and Second Transparent Electrode Pattern>
Similar to the formation of the first and second transparent electrode patterns, the first transparent electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 1, and the second transparent electrode pattern The front plate on which was formed was subjected to DC magnetron sputtering to obtain a front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed.
Further, etching is performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer is removed to form the frame layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. A front plate on which conductive elements different from the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns were formed was obtained.
＜透明保護層の形成＞
　絶縁層の形成と同様にして、上記第一及び第二の透明電極パターンとは別の導電性要素まで形成した前面板に、実施例１の感光性樹脂組成物を塗布・乾燥（膜厚１μｍ、９０℃１２０秒）し、感光性樹脂組成物膜を得た。更に、露光、加熱処理、現像、ポスト露光（１，０００ｍＪ／ｃｍ2）、ポストベーク処理を行って、額縁層、第一の透明電極パターン、実施例１の感光性樹脂組成物を用いて形成した絶縁層パターン、第二の透明電極パターン、第一及び第二の透明電極パターンとは別の導電性要素の全てを覆うように実施例１の感光性樹脂組成物を用いて形成した絶縁層（透明保護層）を積層した前面板を得た。 <Formation of transparent protective layer>
In the same manner as the formation of the insulating layer, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm) on the front plate formed up to the conductive element different from the first and second transparent electrode patterns. , 90 ° C. for 120 seconds) to obtain a photosensitive resin composition film. Further, exposure, heat treatment, development, post-exposure (1,000 mJ / cm 2 ), and post-bake treatment are performed to form the frame layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. Insulating layer pattern, second transparent electrode pattern, insulating layer formed using the photosensitive resin composition of Example 1 so as to cover all the conductive elements different from the first and second transparent electrode patterns A front plate laminated with a (transparent protective layer) was obtained.
＜タッチパネルの作製＞
　特開２００９－４７９３６号公報に記載の方法で製造した液晶表示素子に、先に製造した前面板を貼り合わせ、公知の方法で静電容量方式のタッチパネルを構成要素として備えたタッチパネルを作製した。 <Production of touch panel>
A liquid crystal display device manufactured by the method described in Japanese Patent Application Laid-Open No. 2009-47936 was bonded to the previously manufactured front plate, and a touch panel including a capacitive touch panel as a constituent element was manufactured by a known method.
＜前面板、及び、タッチパネルの評価＞
　第一の透明電極パターン、第二の透明電極パターン、及び、これらとは別の導電性要素の、各々の導電性には問題がなく、一方で、第一の透明電極パターンと第二の透明電極パターンの間では絶縁性を有しており、タッチパネルとして良好な表示特性が得られた。 <Evaluation of front plate and touch panel>
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and other conductive elements, while the first transparent electrode pattern and the second transparent electrode pattern Between the electrode patterns, there was insulation, and good display characteristics as a touch panel were obtained.
　１：ＴＦＴ、２：配線、３：絶縁膜、４：平坦化膜、５：第一電極、６：ガラス基板、７：コンタクトホール、８：絶縁膜、１０：液晶表示装置、１２：バックライトユニット、１４，１５：ガラス基板、１６：ＴＦＴ、１７：硬化膜、１８：コンタクトホール、１９：ＩＴＯ透明電極、２０：液晶、２２：カラーフィルター、３０：静電容量方式のタッチパネル、３１：前面板、３２：額縁層、３３：第一の透明電極パターン、３３ａ：パッド部分、３３ｂ：接続部分、３４：第二の透明電極パターン、３５：絶縁層、３６：導電性要素、３７：透明保護層、３８：開口部、ＣＴ：対向電極、ＧＩ：ゲート絶縁膜、ＧＴ：ゲート電極、ＩＮ１：第１の層間絶縁膜、ＩＮ２：第２の層間絶縁膜、ＩＮ３：第３の層間絶縁膜、ＰＡＳ：有機絶縁膜、ＰＳ：半導体膜、ＰＸ：画素電極、ＲＡＬ：反射膜、ＳＤ１：ドレイン電極、ＳＤ２：ソース電極、ＳＵＢ１：ガラス基板、ＵＣ：下地膜 1: TFT, 2: wiring, 3: insulating film, 4: planarization film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12: backlight Units 14, 15: glass substrate, 16: TFT, 17: cured film, 18: contact hole, 19: ITO transparent electrode, 20: liquid crystal, 22: color filter, 30: capacitive touch panel, 31: front Face plate, 32: Frame layer, 33: First transparent electrode pattern, 33a: Pad portion, 33b: Connection portion, 34: Second transparent electrode pattern, 35: Insulating layer, 36: Conductive element, 37: Transparent protection Layer, 38: opening, CT: counter electrode, GI: gate insulating film, GT: gate electrode, IN1: first interlayer insulating film, IN2: second interlayer insulating film, IN3: third interlayer insulating film, PAS: Organic Film, PS: semiconductor film, PX: pixel electrode, RAL: reflective film, SD1: drain electrode, SD2: source electrode, SUB1: glass substrate, UC: base film

Claims (15)

  1. 　成分Ａとして下記１および２の少なくとも一方を満たすポリシロキサン成分、
    　１：構成単位ａ１としてカルボキシ基が酸分解性基で保護された基、および、フェノール性水酸基が酸分解性基で保護された基から選ばれる少なくとも１種の基を有する構成単位と、構成単位ａ２として架橋性基を有する構成単位とを有するポリシロキサンを含むポリシロキサン成分、
    　２：構成単位ａ１としてカルボキシ基が酸分解性基で保護された基、および、フェノール性水酸基が酸分解性基で保護された基から選ばれる少なくとも１種の基を有する構成単位を有するポリシロキサンと、構成単位ａ２として架橋性基を有する構成単位を有するポリシロキサンとを含むポリシロキサン成分、
    　成分ＢとしてｐＫａが３以下の酸を発生する光酸発生剤、
    　成分Ｃとして溶剤、ならびに、
    　成分Ｓとして下式ＥＰで表される分子量１５０～１０００の脂環式エポキシ化合物を含む感光性樹脂組成物；
    Figure JPOXMLDOC01-appb-C000001
     　式中、ＲＥＰ１はアルキル基を表し、
    　ｐは０～７の整数を表し、ｐが２以上の場合、複数のＲＥＰ１は同一であってもよく、異なってもよく、
    　Ａは、酸素原子を有していてもよい、ｑ価の炭化水素基を表し、
    　ｑは１～４の整数を表す。     A polysiloxane component satisfying at least one of the following 1 and 2 as component A:
    1: a structural unit having at least one group selected from a group in which a carboxy group is protected by an acid-decomposable group and a group in which a phenolic hydroxyl group is protected by an acid-decomposable group as the structural unit a1, and a structural unit a polysiloxane component including a polysiloxane having a structural unit having a crosslinkable group as a2.
    2: Polysiloxane having a structural unit having at least one group selected from a group in which a carboxy group is protected by an acid-decomposable group and a group in which a phenolic hydroxyl group is protected by an acid-decomposable group as the structural unit a1 And a polysiloxane component comprising a polysiloxane having a structural unit having a crosslinkable group as the structural unit a2.
    A photoacid generator that generates an acid having a pKa of 3 or less as component B;
    A solvent as component C, and
    A photosensitive resin composition comprising, as component S, an alicyclic epoxy compound having a molecular weight of 150 to 1000 represented by the following formula EP;
    Figure JPOXMLDOC01-appb-C000001
     In the formula, R EP1 represents an alkyl group,
    p represents an integer of 0 to 7, and when p is 2 or more, a plurality of R EP1 may be the same or different,
    A represents a q-valent hydrocarbon group which may have an oxygen atom,
    q represents an integer of 1 to 4.
  2. 　感光性樹脂組成物の全固形分に対して、前記脂環式エポキシ化合物を、０．１～１０質量％含有する、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, comprising 0.1 to 10% by mass of the alicyclic epoxy compound with respect to the total solid content of the photosensitive resin composition.
  3. 　前記脂環式エポキシ化合物の分子量が２００～４００である、請求項１又は２に記載の感光性樹脂組成物。 3. The photosensitive resin composition according to claim 1, wherein the alicyclic epoxy compound has a molecular weight of 200 to 400.
  4. 　前記脂環式エポキシ化合物が、下式ＥＰ１で表される化合物である、請求項１～３のいずれか１項に記載の感光性樹脂組成物；
    Figure JPOXMLDOC01-appb-C000002
     　式中、ＲＥＰ２およびＲＥＰ３は、それぞれ独立にアルキル基を表し、
    　ｐは０～７の整数を表し、ｐが２以上の場合、複数のＲＥＰ２およびＲＥＰ３は、同一であってもよく、異なってもよく、
    　Ａ１は、－Ｏ－、－ＣＯＯ－および－ＯＣＯ－から選ばれる少なくとも１種を含む２価の炭化水素基を表す。     The photosensitive resin composition according to any one of claims 1 to 3, wherein the alicyclic epoxy compound is a compound represented by the following formula EP1:
    Figure JPOXMLDOC01-appb-C000002
     In the formula, R EP2 and R EP3 each independently represent an alkyl group,
    p represents an integer of 0 to 7, and when p is 2 or more, the plurality of R EP2 and R EP3 may be the same or different,
    A 1 represents a divalent hydrocarbon group containing at least one selected from —O—, —COO—, and —OCO—.
  5. 　前記ポリシロキサン成分が有する前記酸分解性基は、アセタール基である請求項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-decomposable group of the polysiloxane component is an acetal group.
  6. 　前記構成単位ａ１が、下記一般式ａ１－１で表される構成単位、および、下記一般式ａ１－２で表される構成単位から選ばれる少なくとも１種である、請求項１～５のいずれか１項に記載の感光性樹脂組成物；
    Figure JPOXMLDOC01-appb-C000003
     　一般式ａ１－１、および、一般式ａ１－２中、ａは０または１を表し、
    　Ｒ１およびＲ２は、それぞれ独立に、水素原子、アルキル基またはアリール基を表し、Ｒ１およびＲ２の少なくとも一方は、アルキル基またはアリール基を表し、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、アルキル基、アリール基、または、アラルキル基を表し、
    　Ｌ１は、単結合または２価の連結基を表し、
    　Ｌ２は、単結合または２価の連結基を表し、
    　Ｒｘは、アルキル基またはハロゲン原子を表し、
    　ｍ１は、０～４の整数を表す。     6. The structural unit a1 according to claim 1, wherein the structural unit a1 is at least one selected from a structural unit represented by the following general formula a1-1 and a structural unit represented by the following general formula a1-2. The photosensitive resin composition according to item 1;
    Figure JPOXMLDOC01-appb-C000003
     In general formula a1-1 and general formula a1-2, a represents 0 or 1,
    R 1 and R 2 each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 represents an alkyl group or an aryl group, and R 3 represents an alkyl group or an aryl group. R 1 or R 2 and R 3 may be linked to form a cyclic ether,
    R 4 represents an alkyl group, an aryl group, or an aralkyl group,
    L 1 represents a single bond or a divalent linking group,
    L 2 represents a single bond or a divalent linking group,
    R x represents an alkyl group or a halogen atom,
    m1 represents an integer of 0 to 4.
  7. 　前記ポリシロキサン成分が有する架橋性基が、環状エーテル、および、エチレン性不飽和結合を有する基から選ばれる少なくとも１種である、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 crosslinkable group of the polysiloxane component is at least one selected from a cyclic ether and a group having an ethylenically unsaturated bond. object.
  8. 　前記ポリシロキサンは、カルボキシ基およびフェノール性水酸基から選ばれる少なくとも１種の基を有する構成単位をさらに含む、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 polysiloxane further comprises a structural unit having at least one group selected from a carboxy group and a phenolic hydroxyl group.
  9. 　前記光酸発生剤が、オニウム塩化合物、オキシムスルホネート化合物、および、イミドスルホネート化合物から選ばれる少なくとも１種である、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 photoacid generator is at least one selected from an onium salt compound, an oxime sulfonate compound, and an imide sulfonate compound.
  10. 　請求項１～９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工程、
    　前記基板に塗布された感光性樹脂組成物から溶剤を除去する工程、
    　溶剤が除去された感光性樹脂組成物を露光する工程、
    　露光された感光性樹脂組成物を現像する工程、および、
    　現像された感光性樹脂組成物を熱硬化する工程、
    を含む硬化膜の製造方法。     Applying the photosensitive resin composition according to any one of claims 1 to 9 on a substrate;
    Removing the solvent from the photosensitive resin composition applied to the substrate;
    Exposing the photosensitive resin composition from which the solvent has been removed,
    Developing the exposed photosensitive resin composition; and
    A step of thermosetting the developed photosensitive resin composition;
    The manufacturing method of the cured film containing this.
  11. 　請求項１～９のいずれか１項に記載の感光性樹脂組成物を硬化した硬化膜。 A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 9.
  12. 　層間絶縁膜である、請求項１１に記載の硬化膜。 The cured film according to claim 11, which is an interlayer insulating film.
  13. 　請求項１１または１２に記載の硬化膜を有する、液晶表示装置。 A liquid crystal display device having the cured film according to claim 11 or 12.
  14. 　請求項１１または１２に記載の硬化膜を有する、有機エレクトロルミネッセンス表示装置。 An organic electroluminescence display device having the cured film according to claim 11 or 12.
  15. 　請求項１１または１２に記載の硬化膜を有する、タッチパネル。 A touch panel having the cured film according to claim 11 or 12.
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JP2017198841A (en) * 2016-04-27 2017-11-02 株式会社カネカ Positive photosensitive composition
US11914295B2 (en) 2018-11-21 2024-02-27 Shin-Etsu Chemical Co., Ltd. Thermosetting iodine- and silicon-containing material, composition containing the material for forming resist underlayer film for EUV lithography, and patterning process

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