WO2016052391A1 - Composition de résine photosensible, procédé de production de film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage électroluminescent organique, et panneau tactile - Google Patents

Composition de résine photosensible, procédé de production de film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage électroluminescent organique, et panneau tactile Download PDF

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Publication number
WO2016052391A1
WO2016052391A1 PCT/JP2015/077289 JP2015077289W WO2016052391A1 WO 2016052391 A1 WO2016052391 A1 WO 2016052391A1 JP 2015077289 W JP2015077289 W JP 2015077289W WO 2016052391 A1 WO2016052391 A1 WO 2016052391A1
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group
resin composition
photosensitive resin
structural unit
polysiloxane
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PCT/JP2015/077289
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English (en)
Japanese (ja)
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豪 安藤
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富士フイルム株式会社
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    • 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
    • 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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
    • 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
    • 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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements

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.
  • Paragraph No. 0093 describes that the component (D) is preferably contained in an amount of 1 to 40 parts by mass with respect to 100 parts by mass of the component (A).
  • 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.
  • the photosensitive resin composition disclosed by patent document 1 when this inventor examined the photosensitive resin composition disclosed by patent document 1, the sensitivity was not enough. Moreover, when this inventor examined the positive photosensitive resin composition disclosed by patent document 2, the positive photosensitive resin composition of patent document 2 contains epoxy group containing siloxane compound which is a hardening component. It was found that the solvent resistance was not sufficient due to the small amount. Also. It has been found that when the content of the epoxy group-containing siloxane compound is increased to improve the solvent resistance, the sensitivity is deteriorated. Moreover, when this inventor examined the photosensitive resin composition disclosed by patent document 3, it turned out that solvent tolerance is not enough. Thus, the present condition is that the photosensitive resin composition which can form the cured film which is good in sensitivity and excellent in solvent tolerance is not known.
  • an object of the present invention is to provide a photosensitive resin composition capable of forming a cured film having good sensitivity and excellent solvent resistance. 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 photosensitive resin composition containing a polysiloxane component described later, a photoacid generator that generates an acid having a pKa of 3 or less, and a solvent The inventors have found that a photosensitive resin composition that can form a cured film having good sensitivity and excellent solvent resistance can be obtained, and the present invention has been completed.
  • the present invention provides the following.
  • Component A is Component A1: As the structural unit a1, a structural unit having at least one selected from a group in which a carboxy group is protected with an acetal structure and a group in which a phenolic hydroxyl group is protected with an acetal structure is included in all the structural units in Component A1.
  • Polysiloxane having A photosensitive resin composition in which the mass ratio of the content of each of component A1 and component A2 is component A1: component A2 70: 30 to 30:70.
  • Component A2 contains structural unit a2 in a proportion of 40 mol% or more of all structural units of component A2, and contains structural unit a3 in a proportion of 10 mol% or more of all structural units of component A2.
  • the structural unit a1 is at least one selected from the structural unit represented by the following general formula a1-1 and the structural unit represented by the following general formula a1-2, ⁇ 1> or ⁇ 2 >
  • the photosensitive resin composition as described in> 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.
  • the structural unit a2 is at least one selected from the structural unit represented by the following general formula a2-1 and the structural unit represented by the following general formula a2-2, ⁇ 1> to ⁇ 3 >
  • the photosensitive resin composition in any one of> In general formula a2-1 and general formula 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 of 3 and m3 represents an integer of 0 to 4.
  • the structural unit a3 is at least one selected from a structural unit represented by the following general formula a3-1 and a structural unit represented by the following general formula a3-2: ⁇ 1> to ⁇ 4 >
  • the photosensitive resin composition in any one of> In general formula a3-1 and general formula 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. Represents a linking 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.
  • ⁇ 6> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein 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.
  • ⁇ 8> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>.
  • ⁇ 9> The cured film according to ⁇ 8>, which is an interlayer insulating film.
  • ⁇ 10> A liquid crystal display device having the cured film according to ⁇ 8> or ⁇ 9>.
  • ⁇ 11> An organic electroluminescence display device having the cured film according to ⁇ 8> or ⁇ 9>.
  • ⁇ 12> A touch panel having the cured film according to ⁇ 8> or ⁇ 9>.
  • 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 includes a polysiloxane component, a photoacid generator that generates an acid having a pKa of 3 or less, and a solvent.
  • the polysiloxane component is Component A1 (hereinafter also referred to as polysiloxane (A1)): a structural unit (a1) having at least one selected from a group in which a carboxy group is protected with an acetal structure and a group in which a phenolic hydroxyl group is protected with an acetal structure Polysiloxane having 40 mol% or more of all structural units in component A1, and Component A2 (hereinafter also referred to as polysiloxane (A2)): a structural unit (a2) having at least one selected from an epoxy group and an oxetanyl group, and a structure having at least one selected from a carboxy group and a phenolic hydroxyl group A polysiloxane having a unit (a3),
  • the photosensitive resin composition of the present invention includes the above-described polysiloxane component and a photoacid generator that generates an acid having a pKa of 3 or less, and the polysiloxane component includes polysiloxane (A1) and polysiloxane ( A2) is contained in the above-mentioned predetermined ratio, so that a cured film having good sensitivity and excellent solvent resistance can be formed. Moreover, the cured film excellent in heat resistance can also be formed by including a polysiloxane component.
  • the polysiloxane (A1) includes the structural unit (a1) and the polysiloxane (A2) includes the structural unit (a3)
  • the compatibility between the polysiloxane (A1) and the polysiloxane (A2) is improved.
  • a good film with excellent solvent resistance can be formed.
  • the ratio of the polysiloxane (A1) and the polysiloxane (A2) within the range specified in the present invention, the structural unit (a1), the structural unit (a2), and the structural unit in the entire polysiloxane component are adjusted.
  • the ratio of the unit (a3) can be easily adjusted, and the degree of freedom in material design is high.
  • 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 is Polysiloxane (A1): A structural unit (a1) having at least one selected from a group in which a carboxy group is protected with an acetal structure and a group in which a phenolic hydroxyl group is protected with an acetal structure is added to the polysiloxane (A1).
  • a polysiloxane having 40 mol% or more of all the structural units Polysiloxane (A2): a structural unit (a2) having at least one selected from an epoxy group and an oxetanyl group, and a structural unit (a3) having at least one selected from a carboxy group and a phenolic hydroxyl group
  • the polysiloxane component has a ratio of the total number of moles of the structural unit (a1) and the moles of the structural unit (a3) to the total 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 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 (A1) and the polysiloxane (A2) 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.
  • polysiloxane (A1) and polysiloxane (A2) will be described.
  • the polysiloxane (A1) has a structural unit (structural unit (a1)) having a group in which a carboxy group is protected with an acetal structure and / or a group in which a phenolic hydroxyl group is protected with an acetal structure.
  • structural unit (a1)) having a group in which a carboxy group is protected with an acetal structure and / or a group in which a phenolic hydroxyl group is protected with an acetal structure.
  • the carboxy group and the phenolic hydroxyl group are also referred to as an acid group.
  • the group in which the acid group is protected with an acetal structure causes a deprotection reaction using the acid as a catalyst (or an initiator), thereby generating the above-described acid group, the regenerated acid, and the decomposed structure.
  • the acetal structure is easily deprotected by an acid.
  • the acid group is preferably a carboxy group. That is, in the present invention, the structural unit (a1) preferably has a protected carboxy group in which the carboxy group is protected with an acetal group. According to this aspect, it is preferable from the viewpoints of basic physical properties of the photosensitive resin composition, particularly sensitivity, developability, and storage stability of the photosensitive resin composition.
  • Content of the structural unit (a1) of polysiloxane (A1) is 40 mol% or more with respect to all the structural units of polysiloxane (A1). From the viewpoint of sensitivity and developability, 40 to 95 mol% is preferable.
  • the lower limit is more preferably 50 mol% or more, and even more preferably 55 mol% or more.
  • the upper limit is more preferably 90 mol% or less, and still more preferably 85 mol% or less.
  • 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 polysiloxane (A1) may further have a structural unit (structural unit (a3)) having a carboxy group and / or a phenolic hydroxyl group.
  • structural unit (a3)) having a carboxy group and / or a phenolic hydroxyl group.
  • the acid group is preferably a carboxyl group from the viewpoint of sensitivity.
  • the content of the structural unit (a3) of the polysiloxane (A1) is preferably 1 to 30 mol% with respect to all the structural units of the polysiloxane (A1). The lower limit is more preferably 5 mol% or more.
  • the polysiloxane (A1) includes a structural unit having a group in which a carboxy group is protected with an acetal structure and a structural unit having a carboxy group with respect to a total of 100 moles of the structural unit (a1) and the structural unit (a3). Is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more. If it is the said range, it is excellent in compatibility with polysiloxane (A2), a sensitivity, and developability.
  • the structural unit (a3) include a structure represented by the following general formula (a3-1) and / or a structure represented by the general formula (a3-2). From the viewpoint of sensitivity, the structure represented by the general formula (a3-1) is more preferable.
  • 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 (A1) can contain the structural unit (a4) other than the structural unit (a1), the structural unit (a3), and the structural unit (a2) described later.
  • the content of the structural unit (a4) of the polysiloxane (A1) is preferably 0 to 40 mol% with respect to all the structural units of the polysiloxane (A1).
  • 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 structural unit (a4) for example, structures represented by general formulas (a4-1) and (a4-2) shown below are preferred specific examples.
  • 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 (A2) has a structural unit (structural unit (a2)) having a structural unit having an epoxy group and / or an oxetanyl group.
  • structural unit (a2) structural unit having an epoxy group and / or an oxetanyl group.
  • the epoxy group and the oxetanyl group are collectively referred to as a cyclic ether group.
  • the polysiloxane (A2) has a cyclic ether group, it is possible to carry out a crosslinking reaction by consuming unreacted acid groups remaining in the film after development, and a firm cured film can be formed.
  • the cyclic ether group is particularly preferably an epoxy group. According to this aspect, it is easy to form a cured film having better solvent resistance.
  • the content of the structural unit (a2) of the polysiloxane (A2) is preferably 40 mol% or more, and preferably 40 to 90 mol%, based on all the structural units of the polysiloxane (A2).
  • the lower limit is more preferably 50 mol% or more, and even more preferably 55 mol% or more.
  • the upper limit is more preferably 85 mol% or less.
  • polysiloxane (A2) has 80 structural units having an epoxy group with respect to 100 mol in total of the structural unit having an epoxy group, the structural unit having an oxetanyl group, and the structural unit having an epoxy group and an oxetanyl group.
  • the content is preferably at least mol%, more preferably at least 85 mol%, and even more preferably at least 90 mol%. If it is the said range, it will be easy to form the cured film excellent in heat resistance and solvent tolerance.
  • Specific examples of the cyclic ether group include the following, but are not limited thereto.
  • * represents a connecting portion with another group.
  • the structural unit (a2) may have at least one cyclic ether group in one structural unit, preferably 1 to 3, and more preferably 1.
  • the cyclic ether groups may be of the same type (an embodiment having two or more epoxy groups or two or more oxetanyl groups).
  • One or more epoxy groups and one oxetanyl group may be included.
  • two or more cyclic ether groups are contained in one structural unit, it is preferable that they are the same kind.
  • 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.
  • silane that can be used to obtain the structural unit (a2) include 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.
  • silane compound shown below can also be used.
  • the polysiloxane (A2) has the structural unit (a3) described above.
  • the structural unit (a3) those described for polysiloxane (A1) can be mentioned, and preferred structures are also the same.
  • the polysiloxane (A2) has the structural unit (a3) described above, it is easy to form a cured film having good compatibility with the polysiloxane (A1) and excellent solvent resistance. Furthermore, it is excellent in sensitivity and developability.
  • the content of the structural unit (a3) of the polysiloxane (A2) is preferably 10 mol% or more, more preferably 10 to 30 mol%, more preferably 10 to 20 mol%, based on all the structural units of the polysiloxane (A2). Is more preferable.
  • the polysiloxane (A2) can contain the structural unit (a4) described above.
  • the structural unit (a4) those described for polysiloxane (A1) can be mentioned, and preferred structures are also the same.
  • the content of the structural unit (a4) of the polysiloxane (A2) 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 polysiloxane contained in the polysiloxane component (component A) 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.
  • Polysiloxane (A1) and polysiloxane (A2) are obtained by mixing and reacting silane compounds corresponding to the respective structural units and 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 especially 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 acetal structure of the structural unit (a1) described above may be introduced using a protected silane compound or may be introduced by a polymer reaction.
  • a silane having an alkyl ester of the corresponding carboxylic acid it is preferable to synthesize a polysiloxane using and to hydrolyze the alkyl ester by a general method to obtain a structural unit having a carboxy group.
  • an acetal group or a ketol group is formed by a so-called polymer reaction. It is preferably introduced to protect the carboxy group.
  • an acetal group or a ketol group is formed by a so-called polymer reaction.
  • the polysiloxane (A1) may be a combination of a plurality of polysiloxanes having different structures.
  • the polysiloxane (A2) may be a combination of a plurality of polysiloxanes having different structures.
  • Polysiloxane components other than polysiloxane (A1) and polysiloxane (A2) can be added to the polysiloxane component.
  • the other polysiloxane includes the above-described structural unit (a2), does not include the above-described structural unit (a3), includes the above-described structural unit (a3), and does not include the above-described structural unit (a2). Examples thereof include polysiloxane. These may be included without departing from the spirit of the present invention.
  • the content of other polysiloxane is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and substantially contained with respect to 100 parts by mass in total of polysiloxane (A1) and polysiloxane (A2). It can also be set as the structure which does not. By setting it as such a structure, the solvent tolerance of a cured film can be improved more. “Substantially not contained” is preferably, for example, 1 part by mass or less, more preferably 0.1 part by mass or less, with respect to 100 parts by mass in total of polysiloxane (A1) and polysiloxane (A2). .
  • the content of the (A) polysiloxane component in the photosensitive resin composition of the present invention is preferably 50 to 99% by mass with respect to the total solid content of the photosensitive resin composition.
  • the upper limit is more preferably 95% by mass or less, for example.
  • the lower limit is more preferably 60% by mass or more, and still more preferably 70% by mass or more.
  • the total content of polysiloxane (A1) and polysiloxane (A2) in the polysiloxane component (component A) in the photosensitive resin composition of the present invention is preferably 60% by mass or more, preferably 70% by mass or more, 90 mass% or more is the most preferable.
  • the upper limit is preferably 100% by mass or less.
  • 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 to each other to form a ring, and a ring is formed via a heteroatom.
  • 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 alkylsulfonic acid, a conjugate base of arylsulfonic acid, or a conjugate base of bisperfluorosulfonylamide, and a conjugate base of alkylsulfonic acid or arylsulfonic acid is particularly preferable.
  • a conjugated base a conjugated base of an alkyl sulfonic acid having 1 to 7 carbon atoms is preferable, and a conjugated base having 1 to 4 carbon atoms is more preferable.
  • 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, compounds described in paragraphs 0083 to 0085 of JP2011-232648, JP2012-2012 And compounds described in paragraph No. 0086 of JP-A-155115. Moreover, the following compound is mentioned.
  • 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 an 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 photoacid generator (B) in the photosensitive resin composition of the present invention is preferably 1 to 10% by mass, more preferably 1 to 8% by mass, based on the total solid content of the photosensitive resin composition. More preferably, it is 1 to 5% by mass.
  • the (B) photoacid generator is preferably contained in an amount of 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, and further preferably 1 to 5 parts by weight with respect to 100 parts by weight of the (A) polysiloxane component. 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 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 the present invention can contain a crosslinking agent. 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.
  • crosslinking group a methylol group, an epoxy group, an oxetanyl group, an alkoxymethyl group, a blocked isocyanate 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.
  • a compound having two or more epoxy groups in the molecule can be used as the crosslinking agent.
  • Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and epoxy group containing An acrylic resin having a structural unit can be given. 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.
  • 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 blocked isocyanate groups in the molecule can be used as a crosslinking agent.
  • the blocked isocyanate group in the present invention is a group capable of generating an isocyanate group by heat.
  • a group obtained by reacting a blocking agent with an isocyanate group to protect the isocyanate group can be preferably exemplified.
  • the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
  • the blocked isocyanate compound is available as a commercial product.
  • Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Death Module BL1100, BL1265 MPA / X, B L3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN
  • 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 using 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 the 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.
  • 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.
  • 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 showed that in A1-1, 88 mol% of the carboxy group was tetrahydrofuranylated.
  • the weight average molecular weight in terms of polystyrene by GPC was 7000.
  • the types and molar ratios of the silane compounds used for the synthesis of A1-1 are shown below.
  • 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. .
  • reaction solution neutralized with concentrated aqueous ammonia and neutralized with 5 L of water was added dropwise to obtain a white solid. This was filtered, dissolved in 300 ml of acetone, dropped into 5 L of water, filtered and dried to obtain A1-2.
  • Analysis by 1 H-NMR confirmed that 82 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxyethylated in A1-2.
  • the weight average molecular weight in terms of polystyrene by GPC was 6000.
  • the types and molar ratios of the silane compounds used for the synthesis of A1-2 are shown below.
  • A1-3 synthesis A1-3 was synthesized in the same manner as A1-1 except that the silane compound was used in the following compounds and molar ratio, and the amount was adjusted by changing the protective group to ethoxyethyl group. In analysis by 1 H-NMR, it was confirmed that A1-3 was ethoxyethylated at 90 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.
  • the polysiloxane (A1′-1) precursor has a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 4000, and a dispersity (Mw / Mn (number average molecular weight)) of 2.0. there were.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • polysiloxane (A2′-2) was obtained.
  • Polysiloxane (A2′-2) had a solid content concentration of 30% by mass, a weight average molecular weight (Mw) of 4000, and a dispersity (Mw / Mn) of 2.0.
  • 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 ⁇ basic compound, other additives>
  • OXE di [1-ethyl- (3-oxetanyl) methyl] ether
  • 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
  • the exposed photosensitive resin composition layer was developed with an alkaline developer (0.45% tetramethylammonium hydroxide aqueous solution) at 23 ° C./55 seconds, and then rinsed with ultrapure water for 30 seconds.
  • an alkaline developer (0.45% tetramethylammonium hydroxide aqueous solution) at 23 ° C./55 seconds, and then rinsed with ultrapure water for 30 seconds.
  • the optimum i-line exposure amount (Eopt) when resolving a hole having a diameter of 8 ⁇ m was determined and used as the sensitivity. Evaluation is based on the following criteria, and 1, 2 and 3 are practical levels.
  • ⁇ Developability> A 300 mm ⁇ 400 mm square glass substrate (EAGLE XG, 0.7 mm thickness (manufactured by Corning)) was exposed to hexamethyldisilazane (HMDS) vapor for 45 seconds, and each photosensitive resin composition was slit-coated, then 80 Pre-baked on a hot plate at ° C./160 seconds to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 2.5 ⁇ m. Next, the obtained photosensitive resin composition layer was exposed with an optimum exposure amount obtained by sensitivity evaluation with a 7 ⁇ m line-and-space mask pattern using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc.
  • MPA 5500CF high pressure mercury lamp
  • the exposed photosensitive resin composition layer was developed with an alkaline developer (0.45% tetramethylammonium hydroxide aqueous solution) at 23 ° C./55 seconds, and then rinsed with ultrapure water for 30 seconds.
  • This pattern was observed with an optical microscope and evaluated according to the following criteria. 1 and 2 are practical levels. 1: The edge of the pattern is clean 2: There is a slight backlash at the edge of the pattern 3: There is a backlash at the edge of the pattern Or a pattern is not formed.
  • Each photosensitive resin composition was slit coated on a 300 mm ⁇ 400 mm square glass substrate (EAGLE XG, 0.7 mm thickness (manufactured by Corning)), and then heated on a hot plate at 90 ° C./120 seconds. The solvent was removed to form a photosensitive resin composition layer having a thickness of 3.0 ⁇ m.
  • the substrate on which the obtained photosensitive resin composition layer was formed was subjected to a cumulative irradiation amount of 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i) with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The substrate was heated in an oven at 220 ° C.
  • 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.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention porte sur une composition de résine photosensible présentant une sensibilité favorable et capable de former un film durci ayant une excellente résistance aux solvants, un procédé de production d'un film durci, un film durci, un dispositif d'affichage à cristaux liquides, un dispositif d'affichage électroluminescent organique, et un panneau tactile. Cette composition de résine photosensible contient un constituant polysiloxane, un générateur de photo-acide destiné à générer un acide ayant un pKa de 3 au maximum, et un solvant. Le constituant polysiloxane contient : un polysiloxane (A1) ayant une unité constitutive qui représente au moins 40 % en moles des unités constitutives totales et a un groupe dans lequel un groupe carboxy est protégé par une structure d'acétal et/ou un groupe dans lequel un groupe hydroxyle phénolique est protégé par une structure d'acétal ; et un polysiloxane (A2) ayant une unité constitutive ayant un groupe époxy et/ou un groupe oxétanyle, et une unité constitutive ayant un groupe carboxy et/ou un groupe hydroxyle phénolique. À l'intérieur de ce dernier, le rapport massique du polysiloxane (A1) sur le polysiloxane (A2) est de 70:30-30:70.
PCT/JP2015/077289 2014-09-29 2015-09-28 Composition de résine photosensible, procédé de production de film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage électroluminescent organique, et panneau tactile WO2016052391A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016212350A (ja) * 2015-05-13 2016-12-15 東京応化工業株式会社 絶縁膜形成用感光性組成物、及び絶縁膜パターンの形成方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004111734A1 (fr) * 2003-06-11 2004-12-23 Tokyo Ohka Kogyo Co., Ltd. Composition de resist positive, lamines de resist, et procede de formation de motifs de resist
JP2009263522A (ja) * 2008-04-25 2009-11-12 Shin Etsu Chem Co Ltd ポリオルガノシロキサン化合物、これを含む樹脂組成物及びこれらのパターン形成方法
JP2010039056A (ja) * 2008-08-01 2010-02-18 Sekisui Chem Co Ltd 感光性組成物及びパターン膜の製造方法
JP2013092633A (ja) * 2011-10-25 2013-05-16 Adeka Corp ポジ型感光性組成物
JP2014115438A (ja) * 2012-12-10 2014-06-26 Jsr Corp 表示素子用感放射線性樹脂組成物、硬化膜、硬化膜の製造方法、半導体素子および表示素子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004111734A1 (fr) * 2003-06-11 2004-12-23 Tokyo Ohka Kogyo Co., Ltd. Composition de resist positive, lamines de resist, et procede de formation de motifs de resist
JP2009263522A (ja) * 2008-04-25 2009-11-12 Shin Etsu Chem Co Ltd ポリオルガノシロキサン化合物、これを含む樹脂組成物及びこれらのパターン形成方法
JP2010039056A (ja) * 2008-08-01 2010-02-18 Sekisui Chem Co Ltd 感光性組成物及びパターン膜の製造方法
JP2013092633A (ja) * 2011-10-25 2013-05-16 Adeka Corp ポジ型感光性組成物
JP2014115438A (ja) * 2012-12-10 2014-06-26 Jsr Corp 表示素子用感放射線性樹脂組成物、硬化膜、硬化膜の製造方法、半導体素子および表示素子

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016212350A (ja) * 2015-05-13 2016-12-15 東京応化工業株式会社 絶縁膜形成用感光性組成物、及び絶縁膜パターンの形成方法

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