WO2014003111A1 - Composition de résine photosensible, produit durci, procédé de fabrication d'un produit durci, procédé de production d'un motif de résine, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage électroluminescent organique, et dispositif d'affichage à panneau tactile - Google Patents

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

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Publication number
WO2014003111A1
WO2014003111A1 PCT/JP2013/067634 JP2013067634W WO2014003111A1 WO 2014003111 A1 WO2014003111 A1 WO 2014003111A1 JP 2013067634 W JP2013067634 W JP 2013067634W WO 2014003111 A1 WO2014003111 A1 WO 2014003111A1
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group
acid
resin composition
photosensitive resin
component
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PCT/JP2013/067634
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English (en)
Japanese (ja)
Inventor
中村　秀之
成一 鈴木
藤盛　淳一
史絵 山下
恭平 荒山
久保田　誠
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富士フイルム株式会社
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Priority to CN201380034042.0A priority Critical patent/CN104412161A/zh
Priority to KR1020157000242A priority patent/KR102057483B1/ko
Priority to JP2014522675A priority patent/JP6016918B2/ja
Publication of WO2014003111A1 publication Critical patent/WO2014003111A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, the hardened
  • An object of the present invention is to provide a photosensitive resin composition having a high refractive index and excellent transparency.
  • Component A A polymer component containing a polymer satisfying at least one of the following (1) and (2), (1) (a1) a structural unit having a group in which an acid group is protected with an acid-decomposable group And (a2) a polymer having a structural unit having a crosslinkable group, (2) (a1) a polymer having a structural unit having an acid group protected by an acid-decomposable group, and (a2) crosslinkable A polymer having a structural unit having a group, (component S) a dispersant represented by the following formula (S), having at least one acid group, (component B) a photoacid generator, (component C) a metal oxide Particles, and (Component D) a solvent, a photosensitive resin composition,
  • R 3 represents an (m + n) -valent linking group
  • R 4 and R 5 each independently represents a single bond or a divalent linking group
  • a 2 represents an organic dye structure or a heterocyclic ring.
  • Structure, acid group, group having basic nitrogen atom, urea group, urethane group, group having coordinating oxygen atom, alkoxysilyl group, phenol group, alkyl group, aryl group, group having alkyleneoxy chain, imide group represents a monovalent organic group containing at least one partial structure selected from the group consisting of alkyloxycarbonyl group, alkylaminocarbonyl group, carboxylate group, sulfonamide group, epoxy group, isocyanate group and hydroxyl group
  • n A 2 and R 4 in the formula may be the same or different
  • m represents 0 to 8
  • n represents 2 to 9
  • m + n is 3 to 10
  • P 2 represents a polymer skeleton. the stands, m-number of
  • ⁇ 2> The photosensitive resin composition according to ⁇ 1>, wherein component C is titanium oxide particles or zirconium oxide particles
  • component C is titanium oxide particles or zirconium oxide particles
  • a 2 is a monovalent organic group containing at least one acid group.
  • P 2 is an acrylic resin skeleton.
  • a heat treatment is performed on the developed resin composition.
  • ⁇ 10> The cured product obtained by the method for producing a cured product according to ⁇ 8> or the resin pattern production method according to ⁇ 9>, ⁇ 11> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 7> above, ⁇ 12>
  • the cured film according to ⁇ 11> which is an interlayer insulating film
  • ⁇ 13> A liquid crystal display device having the cured film according to ⁇ 11> or ⁇ 12> above, ⁇ 14>
  • An organic EL display device having the cured film according to ⁇ 11> or ⁇ 12> above, ⁇ 15> A touch panel display device having the cured film according to ⁇ 11> or ⁇ 12>.
  • a photosensitive resin composition having a high refractive index and excellent transparency can be provided.
  • 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
  • the schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.
  • 1 shows a conceptual diagram of a configuration of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • It is sectional drawing which shows the structure of an electrostatic capacitance type input device.
  • component A a polymer component containing a polymer satisfying at least one of the following (1) and (2)
  • component A a polymer component containing a polymer satisfying at least one of the following (1) and (2)
  • component A a polymer component containing a polymer satisfying at least one of the following (1) and (2)
  • component A a polymer component containing a polymer satisfying at least one of the following (1) and (2)
  • component A a polymer component containing a polymer satisfying at least one of the following (1) and (2)
  • component A component A
  • (a1) acid group” A structural unit having a group protected with an acid-decomposable group” or the like
  • structural unit (a1) structural unit
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present invention, a combination of preferred embodiments is more preferred.
  • the photosensitive resin composition of the present invention (hereinafter also simply referred to as “resin composition”) comprises (Component A) a polymer component containing a polymer satisfying at least one of the following (1) and (2), (Component S) A dispersant represented by the following formula (S), containing at least one acid group, (Component B) a photoacid generator, (Component C) metal oxide particles, and (Component D) a solvent. It is characterized by doing.
  • R 3 represents an (m + n) -valent linking group
  • R 4 and R 5 each independently represents a single bond or a divalent linking group
  • a 2 represents an organic dye structure or a heterocyclic ring.
  • Structure, acid group, group having basic nitrogen atom, urea group, urethane group, group having coordinating oxygen atom, alkoxysilyl group, phenol group, alkyl group, aryl group, group having alkyleneoxy chain, imide group represents a monovalent organic group containing at least one partial structure selected from the group consisting of alkyloxycarbonyl group, alkylaminocarbonyl group, carboxylate group, sulfonamide group, epoxy group, isocyanate group and hydroxyl group
  • n A 2 and R 4 in the formula may be the same or different
  • m represents 0 to 8
  • n represents 2 to 9
  • m + n is 3 to 10
  • P 2 represents a polymer skeleton.
  • the photosensitive resin composition of the present invention can be suitably used as a positive resist composition.
  • the photosensitive resin composition of the present invention is preferably a resin composition having a property of being cured by heat.
  • the photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition, and is a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition). Is more preferable.
  • the photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. A 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
  • (Component B) photoacid generator used in the present invention is such that an acid generated in response to actinic light acts as a catalyst for deprotection of the protected acid group in Component A. Therefore, the acid generated by the action of one photon contributes to a number of deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10, which is a result of so-called chemical amplification. As a result, high sensitivity can be obtained.
  • the photosensitive resin composition of the present invention is a resin composition for optical members such as microlenses, optical waveguides, antireflection films, LED sealing materials, and LED chip coating materials, or wiring used for touch panels.
  • a resin composition for reducing the visibility of an electrode is preferable.
  • the composition for reducing the visibility of the wiring electrode used for the touch panel is a composition for a member that reduces the visibility of the wiring electrode used for the touch panel, that is, makes the wiring electrode difficult to see. Examples thereof include an interlayer insulating film between ITO (indium tin oxide) electrodes, and the photosensitive resin composition of the present invention can be suitably used for the application.
  • a chemically amplified positive photosensitive resin composition is exposed to an action with a photoacid generator to remove a leaving group of a polymer contained therein and dissolve in a developing solution, and an unexposed portion becomes a pattern. It is formed.
  • a resin composition containing inorganic particles, a dispersant, and a polymer containing a leaving group and a crosslinking group is used as a positive photosensitive resin composition, the dispersibility of the inorganic particles is very important and the dispersion is not successful.
  • the compatibility between the dispersion liquid and the binder in the photosensitive resin composition is also important.
  • the present inventors have improved the dispersibility of metal oxide particles and reduced the average particle size by using a photosensitive resin composition containing component A to component D and component S. It was found that a photosensitive resin composition capable of forming a cured product having no coarse particles, good compatibility with the binder, excellent transparency (low haze) and high refraction can be obtained.
  • the composition of the present invention will be described in detail.
  • Component A Polymer component containing a polymer satisfying at least one of (1) and (2)
  • the photosensitive resin composition of the present invention satisfies (Component A) at least one of the following (1) and (2).
  • the composition of the present invention may further contain a polymer other than these. .
  • Component A in the present invention means, in addition to the above (1) and / or (2), including other polymers added as necessary, unless otherwise specified. It is preferable that the photosensitive resin composition of this invention contains the component which satisfy
  • Component A is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof.
  • a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
  • the “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”.
  • (meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.
  • Component A includes (a1) a polymer having at least a structural unit having a group in which an acid group is protected with an acid-decomposable group.
  • component A contains a polymer having the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
  • group in which the acid group is protected with an acid-decomposable group those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
  • Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
  • Examples of the acid-decomposable group include groups that are relatively easily decomposed by an acid (for example, an ester structure of a group represented by the formula (a1-10) described later, a tetrahydropyranyl ester group, a tetrahydrofuranyl ester group, etc. Acetal-based functional groups) and groups that are relatively difficult to decompose with acid (for example, tertiary alkyl groups such as tert-butyl ester groups and tertiary alkyl carbonate groups such as tert-butyl carbonate groups) can be used. .
  • a structural unit having a group in which an acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group in which a carboxyl group is protected with an acid-decomposable group (“protection protected with an acid-decomposable group” Or a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected by an acid-decomposable group (having a protected phenolic hydroxyl group protected by an acid-decomposable group). It is also preferably referred to as a “structural unit”.
  • the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
  • a structural unit having a group is not particularly limited, and a known structural unit can be used.
  • a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid
  • a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
  • the structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.
  • ⁇ (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>
  • the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those listed below. . That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyl.
  • Examples include loxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl phthalic acid.
  • Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
  • the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
  • the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
  • the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ⁇ -carboxypolycaprolactone monoacrylate and ⁇ -carboxypolycaprolactone monomethacrylate.
  • unsaturated carboxylic acid acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
  • the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, anhydride of unsaturated polyvalent carboxylic acid, etc. It is preferable to use acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
  • the structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.
  • a structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride.
  • a unit derived from the obtained monomer is preferred.
  • the acid anhydride known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc.
  • phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
  • the reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.
  • the above-mentioned acid-decomposable groups can be used.
  • these acid-decomposable groups it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. It is preferable from the viewpoint of the storage stability of the composition.
  • the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10) from the viewpoint of sensitivity.
  • the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10)
  • the entire protected carboxyl group is — (C ⁇ O) —O—CR 101 R
  • the structure is 102 (OR 103 ).
  • R 101 and R 102 each independently represents a hydrogen atom or an alkyl group, except that R 101 and R 102 are both hydrogen atoms, and R 103 represents an alkyl group.
  • R 101 or R 102 and R 103 may be linked to form a cyclic ether.
  • R 101 to R 103 each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic.
  • both R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
  • R 101 , R 102 and R 103 represent an alkyl group
  • the alkyl group may be linear, branched or cyclic.
  • the linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
  • the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms.
  • Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
  • the alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group.
  • R 101 , R 102 and R 103 When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms.
  • Specific examples include a phenyl group, an ⁇ -methylphenyl group, a naphthyl group, and the like, and examples of the entire alkyl group substituted with an aryl group, that is, an aralkyl group include a benzyl group, an ⁇ -methylbenzyl group, a phenethyl group, A naphthylmethyl group etc. can be illustrated.
  • the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.
  • the alkyl group is a cycloalkyl group
  • the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is a linear chain. Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent. These substituents may be further substituted with the above substituents.
  • R 101 , R 102 and R 103 represent an aryl group
  • the aryl group preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.
  • the aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
  • R 101 , R 102 and R 103 can be bonded together to form a ring together with the carbon atom to which they are bonded.
  • Examples of the ring structure when R 101 and R 102 , R 101 and R 103 or R 102 and R 103 are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
  • any one of R 101 and R 102 is preferably a hydrogen atom or a methyl group.
  • radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the above formula (a1-10) a commercially available one may be used, or one synthesized by a known method Can also be used. For example, it can be synthesized by the synthesis method described in paragraphs 0037 to 0040 of JP2011-212494A.
  • a first preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following formula.
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is an alkyl group. Or R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. .
  • R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R 1 and R 2 are aryl groups, a phenyl group is preferred. R 1 and R 2 are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. X represents a single bond or an arylene group, and a single bond is preferable.
  • a second preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following formula.
  • R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • L 1 represents a carbonyl group or a phenylene group
  • R 122 to R 128 each independently represents a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group of
  • R 121 is preferably a hydrogen atom or a methyl group.
  • L 1 is preferably a carbonyl group.
  • R 122 to R 128 are preferably hydrogen atoms.
  • R represents a hydrogen atom or a methyl group.
  • the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below.
  • ⁇ (a1-2-1) Structural unit having phenolic hydroxyl group Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene-based structural unit and a structural unit in a novolac-based resin. Among these, a structural unit derived from hydroxystyrene or ⁇ -methylhydroxystyrene is sensitive. From the viewpoint of In addition, as a structural unit having a phenolic hydroxyl group, a structural unit represented by the following formula (a1-20) is also preferable from the viewpoint of sensitivity.
  • R 220 represents a hydrogen atom or a methyl group
  • R 221 represents a single bond or a divalent linking group
  • R 222 represents a halogen atom or a linear or branched group having 1 to 5 carbon atoms.
  • R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
  • R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved.
  • the divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among these, R 221 is preferably a single bond, a methylene group, or an ethylene group.
  • the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.
  • A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production.
  • the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
  • R 222 each independently represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.
  • a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
  • B represents 0 or an integer of 1 to 4;
  • the acid-decomposable group that can be used in the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group includes a structure having a protected carboxyl group protected by the acid-decomposable group Similar to the acid-decomposable group that can be used for the unit (a1-1), known ones can be used and are not particularly limited.
  • a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability.
  • the phenolic hydroxyl group is more preferably a protected phenolic hydroxyl group protected in the form of an acetal represented by the above formula (a1-10) from the viewpoint of sensitivity.
  • the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above formula (a1-10)
  • the entire protected phenolic hydroxyl group is —Ar—O—CR 101 R 102.
  • the structure is (OR 103 ).
  • Ar represents an arylene group.
  • Examples of the radical polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include, for example, paragraph 0042 of JP2011-215590A And the like.
  • a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
  • acetal protecting group for the phenolic hydroxyl group examples include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group.
  • 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.
  • the radical polymerizable monomer used for forming the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group a commercially available one may be used, or a known method may be used. What was synthesize
  • combined by can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.
  • R represents a hydrogen atom or a methyl group.
  • the structural unit (a1) is 20 to 100 mol% in the polymer having the structural unit (a1). It is preferably 30 to 90 mol%.
  • the single structural unit (a1) is sensitive to the polymer having the structural unit (a1) and the structural unit (a2). From this viewpoint, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
  • the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, 20 to 50 mol% is preferable.
  • the “structural unit” is synonymous with the “monomer unit”.
  • the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
  • the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, when it is desired to develop quickly, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
  • the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, when it is desired to develop quickly, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
  • Component A contains a polymer having a structural unit (a2) having a crosslinkable group.
  • the crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment.
  • Preferred embodiments of the structural unit having a crosslinkable group are represented by an epoxy group, an oxetanyl group, and —NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
  • the component A includes a structural unit containing at least one of an epoxy group and an oxetanyl group.
  • Component A preferably contains a polymer having a structural unit (structural unit (a2-1)) having an epoxy group and / or an oxetanyl group.
  • the 3-membered cyclic ether group is also called an epoxy group, and the 4-membered cyclic ether group is also called an oxetanyl group.
  • the structural unit (a2-1) having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, one or more epoxy groups and one It may have an oxetanyl group, two or more epoxy groups, or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, It is more preferable to have one or two epoxy groups and / or oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.
  • radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, and glycidyl ⁇ -n-propyl acrylate.
  • radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Examples include acid esters.
  • radical polymerizable monomer used for forming the structural unit (a2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. It is preferable that it is a monomer to contain.
  • These structural units can be used individually by 1 type or in combination of 2 or more types.
  • R represents a hydrogen atom or a methyl group.
  • (a2-2) Structural unit having an ethylenically unsaturated group is a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as “structural unit (a2-2)”).
  • the structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms.
  • a structural unit having a side chain is more preferred, and a structural unit having a side chain represented by the following formula (a2-2-1) is still more preferred.
  • R 301 represents a divalent linking group having 1 to 13 carbon atoms
  • R 302 represents a hydrogen atom or a methyl group
  • the wavy line part represents a structural unit having a crosslinkable group ( It represents a site linked to the main chain of a2).
  • R 301 is a divalent linking group having 1 to 13 carbon atoms, and includes an alkenyl group, a cycloalkenyl group, an arylene group, or a combination thereof, and includes an ester bond, an ether bond, an amide bond, a urethane bond, and the like. Bonds may be included.
  • the divalent linking group may have a substituent such as a hydroxy group or a carboxyl group at an arbitrary position. Specific examples of R 301 include the following divalent linking groups.
  • an aliphatic side chain including the divalent linking group represented by R 301 is preferable.
  • the copolymer used in the present invention is a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Is also preferable.
  • a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained.
  • R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • the structural unit (a2) is more preferably a structural unit having a group represented by the following formula (a2-30).
  • R 31 represents a hydrogen atom or a methyl group
  • R 32 represents an alkyl group having 1 to 20 carbon atoms.
  • R 32 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • Specific examples of R 32 include methyl group, ethyl group, n-butyl group, i-butyl group, cyclohexyl group, and n-hexyl group. Of these, i-butyl group, n-butyl group and methyl group are preferable.
  • the structural unit (a2) is 5 to 90 mol% in the polymer having the structural unit (a2). Is preferable, and 20 to 80 mol% is more preferable.
  • the polymer having the structural unit (a2) has the structural unit (a1)
  • the single structural unit (a2) has chemical resistance in the polymer having the structural unit (a1) and the structural unit (a2). From this viewpoint, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
  • the structural unit (a2) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol% in all the structural units of the component (A), regardless of any embodiment. preferable.
  • the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.
  • component A may have another structural unit (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer component (1) and / or (2).
  • the polymer component has another structural unit (a3) substantially free from the structural unit (a1) and the structural unit (a2). It may be.
  • the blending amount of the polymer component is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.
  • a monomer used as another structural unit (a3) For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to.
  • the monomer which becomes another structural unit (a3) can be used individually by 1 type or in combination of 2 or more types.
  • any polymer includes a structural unit containing at least an acid group as the other structural unit (a3).
  • -Fifth embodiment- In addition to the polymer component (1) or (2), an embodiment having a polymer having another structural unit (a3) substantially not having the structural unit (a1) and the structural unit (a2). .
  • -Sixth embodiment- A mode comprising a combination of two or more of the first to fifth embodiments.
  • the structural unit (a3) specifically includes styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid.
  • compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.
  • a structural unit derived from a monomer having a styrene or an aliphatic cyclic skeleton is preferable from the viewpoint of electrical characteristics.
  • styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.
  • the other structural unit (a3) a structural unit derived from (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
  • the content of the structural unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less.
  • 0 mol% may be sufficient, it is preferable to set it as 1 mol% or more, for example, and it is more preferable to set it as 5 mol% or more.
  • various properties of the cured film obtained from the photosensitive resin composition are improved.
  • the polymer contained in Component A preferably has a structural unit having an acid group as the other structural unit (a3).
  • the acid group in the present invention means a proton dissociable group having a pKa of less than 10.5.
  • the acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
  • Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Examples include amide groups, sulfonylimide groups, and the like, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
  • the structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. . In the present invention, it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.
  • the structural unit having an acid group is preferably from 1 to 80 mol%, more preferably from 1 to 50 mol%, still more preferably from 5 to 40 mol%, particularly preferably from 5 to 30 mol%, based on the structural units of all polymer components. 5 to 20 mol% is particularly preferable.
  • the acid value of the resin is preferably 20 to 100 mgKOH / g, more preferably 30 to 80 mgKOH / g, and further 40 to 70 mgKOH / g. preferable.
  • a polymer having another structural unit (a3) substantially not including the structural unit (a1) and the structural unit (a2) is included. You may go out.
  • a resin having a carboxyl group in the side chain is preferable.
  • methacrylic acid copolymer acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc.
  • side chain examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.
  • benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid
  • Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used. These polymers may contain only 1 type and may contain 2 or more types.
  • SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), JONCRYL 690, JONCRYL 678, JONCRYL 67, JONCRYL 586 (above, manufactured by BASF), etc. are used. You can also.
  • the molecular weight of the polymer in Component A is a polystyrene-reduced weight average molecular weight, preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value.
  • the ratio (dispersity, Mw / Mn) between the number average molecular weight Mn and the weight average molecular weight Mw is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
  • radicals used to form at least the structural unit (a1) and the structural unit (a3) can be synthesized by polymerizing a radical polymerizable monomer mixture containing a polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
  • the content of component A in the photosensitive resin composition of the present invention is preferably 20 to 99.9% by mass, and preferably 50 to 98% by mass, based on the total solid content of the photosensitive resin composition. More preferred is 70 to 95% by mass. When the content is within this range, the pattern formability upon development is good.
  • the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
  • Component S Dispersant represented by formula (S) and having at least one acid group
  • the resin composition of the present invention is represented by (Component S) represented by the following formula (S), and has at least one acid group. Containing a dispersant. Since the resin composition of the present invention contains the component S, there are few coarse particles when the metal oxide particles are dispersed, and there is no aggregation when the dispersion and the polymer component are mixed. A cured product having excellent transparency can be formed.
  • R 3 represents an (m + n) -valent linking group
  • R 4 and R 5 each independently represents a single bond or a divalent linking group
  • a 2 represents an organic dye structure or a heterocyclic ring.
  • Structure, acid group, group having basic nitrogen atom, urea group, urethane group, group having coordinating oxygen atom, alkoxysilyl group, phenol group, alkyl group, aryl group, group having alkyleneoxy chain, imide group represents a monovalent organic group containing at least one partial structure selected from the group consisting of alkyloxycarbonyl group, alkylaminocarbonyl group, carboxylate group, sulfonamide group, epoxy group, isocyanate group and hydroxyl group
  • n A 2 and R 4 in the formula may be the same or different
  • m represents 0 to 8
  • n represents 2 to 9
  • m + n is 3 to 10
  • P 2 represents a polymer skeleton. the stands, m-number of
  • Component S is a dispersant having at least one acid group.
  • an acid group By having an acid group, it is presumed to act as an adsorbing group for the metal oxide particles, and the dispersibility of the metal oxide particles is excellent.
  • the acid group include a carboxylic acid group (carboxy group), a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like. From the viewpoint of adsorbing power and dispersibility on metal oxide particles, a carboxylic acid group, a sulfone group, and the like. It is preferably at least one selected from the group consisting of an acid group and a phosphate group, and a carboxylic acid group is particularly preferable.
  • the acid groups in the dispersant may have one of these alone or in combination of two or more.
  • the acid group in component S may have any structure of formula (S). Specifically, for example, acid groups, both of the above formulas may be included in the A 2 in (S), also it may be included in the polymer backbone represented by P 2, A 2 and P 2 it may be included in, from the viewpoint of effect, it is preferably included in a 2.
  • a 2 represents an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, an alkoxysilyl group, a phenol Selected from the group consisting of a group, an alkyl group, an aryl group, a group having an alkyleneoxy chain, an imide group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an epoxy group, an isocyanate group, and a hydroxyl group Represents a monovalent organic group containing at least one of the prepared partial structures.
  • n A 2 present in the formula (S) may be the same or different.
  • the above A 2 is a structure having an adsorption ability for metal oxide particles such as an organic dye structure or a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, or a coordinating oxygen.
  • the partial structure having the ability to adsorb to the metal oxide particles (the above structure and functional group) will be collectively referred to as “adsorption site” as appropriate.
  • the adsorption sites are in one A 2, it may be contained at least one, may contain two or more kinds.
  • the “monovalent organic group containing at least one kind of adsorption site” means the aforementioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 To 100 oxygen atoms, 1 to 400 hydrogen atoms, and a linking group consisting of 0 to 40 sulfur atoms are monovalent organic groups.
  • adsorption sites themselves may constitute a monovalent organic group
  • adsorption sites itself may be a monovalent organic group represented by A 2.
  • the adsorption site constituting A 2 will be described below.
  • organic dye structure examples include, for example, phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavan.
  • preferable dye structures of throne, perinone, perylene, and thioindigo are phthalocyanine, azo lake, anthraquinone, dioxazine, and diketopyrrolopyrrole, and phthalocyanine and anthraquinone.
  • a diketopyrrolopyrrole dye structure is particularly preferred.
  • the “heterocyclic structure” may be a group having at least one heterocyclic ring.
  • the heteroatom in the “heterocyclic structure” preferably contains at least one of O (oxygen atom), N (nitrogen atom), or S (sulfur atom), and more preferably contains at least one nitrogen atom. preferable.
  • heterocyclic ring in the “heterocyclic structure” examples include, for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, Pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, and Preferred examples include a heterocyclic ring selected from the group consisting of acridone, a
  • the “organic dye structure” or “heterocyclic structure” may further have a substituent.
  • substituents include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group.
  • Acyl groups having 1 to 6 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., such as aryl groups, phenyl groups, naphthyl groups, etc.
  • Alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine atom and bromine atom, alkoxy having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group
  • carbonic acid ester groups such as a carbonyl group, a cyano group, and a t-butyl carbonate group.
  • these substituents may be bonded to the organic dye structure or the heterocyclic structure through the following structural unit or a linking group constituted by combining the structural units.
  • Examples of the “acid group” include carboxylic acid group, sulfonic acid group, monosulfate group, phosphoric acid group, monophosphate group, and boric acid group.
  • Preferred examples include carboxylic acid group, sulfonic acid group, A monosulfate group, a phosphate group, and a monophosphate group are more preferable, a carboxylic acid group, a sulfonic acid group, and a phosphate group are more preferable, and a carboxylic acid group is particularly preferable.
  • Examples of the “group having a basic nitrogen atom” include an amino group (—NH 2 ), a substituted imino group (—NHR 8 , —NR 9 R 10 , wherein R 8 , R 9 and R 10 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms.
  • Preferred examples include an aryl group, an aralkyl group having 7 to 20 carbon atoms, a guanidyl group represented by the following formula (a1), an amidinyl group represented by the following formula (a2), and the like.
  • R 11 and R 12 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • R 13 and R 14 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
  • an amino group (—NH 2 ), a substituted imino group (—NHR 8 , —NR 9 R 10 , wherein R 8 , R 9 and R 10 are each independently an alkyl having 1 to 10 carbon atoms.
  • Examples of the “urea group” include —NR 15 CONR 16 R 17 (wherein R 15 , R 16 and R 17 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon number of 6 It represents the above aryl group or an aralkyl group having 7 or more carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • -NR 15 CONHR 17 wherein R 15 and R 17 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms).
  • an aralkyl group having 7 to 20 carbon atoms is more preferable, and —NHCONHR 17 (wherein R 17 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 6 or more carbon atoms).
  • R 17 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 6 or more carbon atoms.
  • Examples of the “urethane group” include —NHCOOR 18 , —NR 19 COOR 20 , —OCONHR 21 , —OCONR 22 R 23 (here, R 18 , R 19 , R 20 , R 21 , R 22 and R 23).
  • Preferred examples thereof include —NHCOOR 18 , —OCONHR 21 (wherein R 18 and R 21 are each independently a carbon atom), or an aryl group having a carbon number of 7 to 20 is preferred.
  • -NHCOOR 18, -OCONHR 21 wherein each R 18 and R 21 are independently from 1 to 10 carbon atoms And an alkyl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms is particularly preferable.
  • Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a group having a crown ether structure.
  • alkoxysilyl group examples include a trimethoxysilyl group and a triethoxysilyl group.
  • the alkyl group represented by the substituent A 2 may be linear or branched and is preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 4 to 30 carbon atoms. An alkyl group having 10 to 18 carbon atoms is more preferable.
  • the aryl group represented by the substituent A 2 is preferably an aryl group having 6 to 10 carbon atoms.
  • the “group having an alkyleneoxy chain” is preferably a group having a polyalkyloxy group at the terminal, and more preferably having 2 to 20 carbon atoms in the alkyloxy group.
  • the alkyleneoxy chain is not particularly limited as long as it has at least one alkyleneoxy group, but is preferably composed of an alkyleneoxy group having 2 to 6 carbon atoms.
  • Examples of the alkyleneoxy group include —CH 2 CH 2 O—, —CH 2 CH 2 CH 2 O— and the like.
  • the alkyl group moiety in the “alkyloxycarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group moiety in the “alkylaminocarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms.
  • Examples of the “carboxylate group” include groups such as ammonium salts of carboxyl groups.
  • the hydrogen atom bonded to the nitrogen atom of the sulfonamide structure may be substituted with an alkyl group (such as a methyl group) or an acyl group (such as an acetyl group or a trifluoroacetyl group).
  • a 2 is a monovalent substituent having at least one functional group of pKa5 or higher. It is preferably a monovalent substituent having at least one functional group of pKa5 to 14.
  • pKa has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
  • the functional group having a pKa of 5 or more includes a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, a urea group, a urethane group, an alkyl group, an aryl group, an alkyloxycarbonyl group, and an alkylaminocarbonyl group.
  • the functional group having a pKa of 5 or more include, for example, a phenol group (about pKa 8 to 10), an alkyl group (about pKa 46 to 53), an aryl group (about pKa 40 to 43), and a urea group (pKa 12 to 14). Degree), urethane group (about pKa 11 to 13), —COCH 2 CO— (about pKa 8 to 10) as a coordinating oxygen atom, sulfonamide group (about pKa 9 to 11), hydroxyl group (pKa 15 to 17) Degree), a heterocyclic group (pKa about 12 to 30) and the like.
  • a 2 at least one group selected from the group consisting of an acid group, a urea group, a urethane group, a phenol group, a sulfonamide group, an imide group, and a group having a coordinating oxygen atom is included.
  • a monovalent substituent is preferred.
  • the linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200.
  • a linking group comprising up to 0 hydrogen atoms and 0 to 20 sulfur atoms is preferred, and this linking group may be unsubstituted or may further have a substituent.
  • Specific examples of this linking group include the following structural units or groups formed by combining the structural units.
  • examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group.
  • halogen atom such as a chlorine atom or a bromine atom, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group, a carbonate group such as a cyano group or a t-butyl carbonate group Is mentioned.
  • a 2 a group consisting of an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a phenol group, an alkyl group, an aryl group, and an alkyloxycarbonyl group It is preferably a monovalent organic group containing at least one partial structure selected from the above, and particularly preferably a monovalent organic group containing at least one acid group.
  • Compound A 2 is only monovalent organic group containing at least one acid group, or, as A 2, and a monovalent organic group containing at least one acid group, an organic dye structure ,
  • a monovalent structure including at least one partial structure selected from the group consisting of a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a phenol group, an alkyl group, an aryl group, and an alkyloxycarbonyl group it is preferably a compound having an organic group, compounds wherein a 2 is only a monovalent organic group containing at least one acid group are particularly preferred.
  • a 2 is more preferably a monovalent organic group represented by the following formula (4).
  • B 1 represents the adsorption site (that is, an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, A partial structure selected from the group consisting of a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group), and R 24 represents a single bond or a (a + 1) -valent linking group.
  • a represents an integer of 1 to 10
  • B 1 existing in the formula (4) may be the same or different.
  • Examples of the adsorption site represented by B 1 include those similar to the adsorption site constituting A 2 of the above formula (S), and preferred examples are also the same.
  • a partial structure selected from the group consisting of an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a phenol group, an alkyl group, an aryl group, and an alkyloxycarbonyl group is preferable. Acid groups are particularly preferred.
  • R 24 represents a single bond or a (a + 1) -valent linking group
  • a represents an integer of 1 to 10, preferably an integer of 1 to 7, more preferably an integer of 1 to 5, An integer of 1 to 3 is particularly preferable.
  • (A + 1) valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, In addition, a group composed of 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.
  • (a + 1) -valent linking group examples include the following structural units or groups formed by combining the structural units (which may form a ring structure).
  • R 24 may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, And a (a + 1) -valent linking group consisting of 0 to 10 sulfur atoms, preferably a single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 More preferred are (a + 1) -valent linking groups consisting of from 1 to 15 oxygen atoms, from 1 to 50 hydrogen atoms, and from 0 to 7 sulfur atoms, a single bond or from 1 to 10 Consisting of up to 5 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms ( The a + 1) -valent linking group is particularly preferable.
  • examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group.
  • Carbons having 1 to 6 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc. having 6 to 16 carbon atoms, methoxy groups, ethoxy groups, etc.
  • R 4 and R 5 each independently represents a single bond or a divalent linking group.
  • n R 4 s may be the same or different.
  • m R 5 s may be the same or different.
  • Examples of the divalent linking group in R 4 and R 5 include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200. And a group consisting of 0 to 20 sulfur atoms, may be unsubstituted or may further have a substituent.
  • divalent linking group examples include the following structural units or groups formed by combining the structural units.
  • R 4 and R 5 are each independently a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 Divalent linking groups consisting of up to 10 hydrogen atoms and 0 to 10 sulfur atoms are preferred, single bonds or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms More preferred are divalent linking groups consisting of atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond or 1 From 0 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms. Particularly preferred are divalent linking groups.
  • examples of the substituent include carbon numbers such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxy group, sulfonamido group, N-sulfonylamido group, acetoxy group and the like having 6 to 16 carbon atoms, methoxy group, ethoxy group, etc.
  • alkoxy groups such as chlorine and bromine atoms
  • alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, and t-butyl carbonate group
  • carbonic acid ester groups such as chlorine and bromine atoms
  • R 3 represents a (m + n) -valent linking group.
  • m + n satisfies 3 to 10.
  • the (m + n) -valent linking group represented by R 3 includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups comprising up to 100 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.
  • (M + n) -valent linking group includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And preferred are groups consisting of 0 to 10 sulfur atoms, preferably 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to More preferred are groups consisting of up to 100 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 atoms. Particularly preferred are groups consisting of up to oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms.
  • examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group.
  • Carbons having 1 to 6 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc. having 6 to 16 carbon atoms, methoxy groups, ethoxy groups, etc.
  • the (m + n) -valent linking group represented by R 3 is preferably a group represented by any of the following formulas.
  • L 3 represents a trivalent group.
  • T 3 represents a single bond or a divalent linking group, and three T 3 s may be the same or different from each other.
  • L 4 represents a tetravalent group.
  • T 4 represents a single bond or a divalent linking group, and four T 4 s may be the same or different from each other.
  • L 5 represents a pentavalent group.
  • T 5 represents a single bond or a divalent linking group, and five T 5 s may be the same or different from each other.
  • L 6 represents a hexavalent group.
  • T 6 represents a single bond or a divalent linking group, and six T 6 s may be the same as or different from each other.
  • L 3 to L 6 are each 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And preferably a trivalent to hexavalent group consisting of 0 to 10 sulfur atoms, preferably 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 More preferred are trivalent to hexavalent groups consisting of oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 sulfur atoms, preferably 1 to 40 carbon atoms, 0 to Particularly preferred are trivalent to hexavalent groups consisting of up to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms. . L 3 to L 6 may have a substituent, and preferred examples of the substituent include the substituents that the (m + n) -valent linking group may have.
  • T 3 to T 6 are each independently a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to Divalent linking groups consisting of up to 100 hydrogen atoms and 0 to 10 sulfur atoms are preferred, single bonds or 1 to 30 carbon atoms, 0 to 6 More preferred is a divalent linking group comprising a nitrogen atom, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond, or 1 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms.
  • a divalent linking group consisting of is particularly preferred.
  • T 3 to T 6 may have a substituent, and preferred examples of the substituent include the substituent that the above divalent linking group may have.
  • the most preferable (m + n) -valent linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.
  • n 2 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.
  • P 2 in the formula (S) represents a polymer skeleton and can be selected from known polymers according to the purpose and the like.
  • M P 2 present in the formula (S) may be the same or different.
  • P 2 is preferably a monovalent group.
  • Polymer chains constituting the polymer skeleton include homopolymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and these Modified products or copolymers [for example, polyether / polyurethane copolymers, copolymers of polyether / vinyl monomers, etc. (any of random copolymers, block copolymers, graft copolymers, etc.
  • the polymer is preferably soluble in an organic solvent.
  • Component S is preferably soluble in an organic solvent.
  • the polymer skeleton in P 2 may have at least one acid group, but preferably does not have an acid group.
  • the polymer having an acid group constituting the polymer skeleton include, for example, a polyamidoamine and salt thereof, a polycarboxylic acid and salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, and a modified polymer having an acid group.
  • a (meth) acrylic acid copolymer is preferable.
  • the means for introducing an acid group into the polymer skeleton is not particularly limited.
  • a means for introducing an acid group with a vinyl monomer, a means for introducing an acid group using a crosslinkable side chain, and the like are adopted.
  • the mode in which the acid group is introduced by the constitution of the polymer skeleton including a structural unit derived from a vinyl monomer having an acid group makes it easy to control the amount of acid group introduced.
  • the “acid group” may be the same as those mentioned as the “acid group” in the description of A 2 above, and is preferably a carboxy group.
  • vinyl monomer For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acid group, and the like are preferable.
  • acrylic acid esters crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters
  • (meth) acrylamides Styrenes vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acid group, and the like are preferable.
  • preferable examples of these vinyl monomers will be described.
  • Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-Methylhexyl acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, (meth
  • Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.
  • Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
  • Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
  • Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
  • Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
  • (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Le acrylamide, N- hydroxy
  • styrenes examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl
  • styrene examples include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-butoxycarbonyl group (t-Boc), etc.), methyl vinylbenzoate, and ⁇ -methylstyrene.
  • Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
  • Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
  • Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
  • Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.
  • (meth) acrylonitrile heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. it can.
  • vinyl groups eg, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.
  • N-vinylformamide N-vinylacetamide
  • N-vinylimidazole N-vinylimidazole
  • vinylcaprolactone etc. it can.
  • vinyl monomers include paragraphs 0089 to 0094, 0096 and 0097 of JP-A-2007-277514 (paragraphs 0105 to 0117 and 0119 to 0120 in the corresponding US 2010/233595). ), The contents of which are incorporated herein.
  • vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used.
  • a monomer having a urethane group or urea group can be appropriately synthesized by utilizing an addition reaction between an isocyanate group and a hydroxyl group or an amino group, for example.
  • an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group, or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer, primary or It can be appropriately synthesized by an addition reaction between a secondary amino group-containing monomer and monoisocyanate.
  • vinyl monomer having an acid group used for introducing an acid group into the polymer skeleton P 2
  • vinyl monomer having an acid group examples include a vinyl monomer having a carboxy group and a vinyl monomer having a sulfonic acid group.
  • vinyl monomer having a carboxy group examples include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
  • an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxypolycaprolactone mono (Meth) acrylate and the like can also be used.
  • a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxypolycaprolactone mono (Meth) acrylate and the like
  • anhydride containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group.
  • (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
  • Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.
  • the vinyl monomer having an acid group a vinyl monomer containing a phenolic hydroxy group or a vinyl monomer containing a sulfonamide group can be used.
  • the polymer skeleton P 2 includes a monomer unit derived from a vinyl monomer containing an acid group
  • the content of the monomer unit derived from a vinyl monomer having an acid group in the polymer skeleton is expressed in terms of mass in the entire polymer skeleton.
  • the content is preferably 3% by mass to 40% by mass, and more preferably in the range of 5% by mass to 20% by mass.
  • the polymer skeleton in P 2 preferably has at least a structure represented by the following formula (L), formula (M), or formula (N), and has at least a structure represented by the following formula (L). More preferably.
  • X 1 represents a hydrogen atom or a monovalent organic group. From the viewpoint of synthesis constraints, X 1 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
  • R 10 represents a hydrogen atom or a monovalent organic group and is not particularly limited in terms of structure, but is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. preferable.
  • R 10 is an alkyl group
  • the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
  • a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
  • It may also have the formula (L) with different R 10 structurally more in.
  • R 11 and R 12 each represent a branched or straight chain alkylene group (having preferably 1 to 10, preferably 2 to 8, more preferably 3 to 6 carbon atoms).
  • Different R 11 or R 12 of the structure may have two or more in each formula.
  • k1, k2 and k3 each independently represents a number of 5 to 140.
  • P 2 preferably contains at least one structural repeating unit.
  • the number k of the at least one structural repeating unit in P 2 is preferably 3 or more from the viewpoint of exhibiting steric repulsion, improving dispersibility, and achieving high refractive index and low viscosity. More preferably, it is 5 or more. Further, from the viewpoint of suppressing the bulk of the component S and achieving a low viscosity, and further allowing the metal oxide particles to be densely present in the cured film (transparent film) to achieve a high refractive index, the above-mentioned at least one constitutional repetition
  • the number k of repeating units is preferably 50 or less, more preferably 40 or less, and still more preferably 30 or less.
  • Component S is preferably soluble in an organic solvent. When the affinity with the organic solvent is high, the affinity with the dispersion medium is sufficient, and sufficient adsorption power for stabilizing the dispersion of the metal oxide particles can be secured.
  • R 3 Specific example (1), (2), (10), (11), (16) or (17) above
  • R 4 a single bond, or the following structural unit or a combination of the structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10”
  • a divalent linking group comprising an oxygen atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent,
  • an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group
  • an aryl group having 6 to 16 carbon atoms such as a phenyl group or a naphthyl group, a hydroxyl group, an amino group, a carboxy group, a sulfonamide group, N— C1-C
  • R 5 single bond, ethylene group, propylene group, the following group (a) or the following group (b)
  • R 12 represents a hydrogen atom or a methyl group
  • L represents 1 or 2.
  • P 2 a copolymer of a vinyl monomer having a carboxy group and another vinyl monomer; a polymer or copolymer of a vinyl monomer having no acid group; an ester-based polymer, an ether-based polymer, and a urethane-based polymer; and A polymer m selected from the group consisting of these modified products and may contain at least one acid group: 0.5-3 n: 3-6
  • the content of acid groups in the component S is appropriately determined depending on the acid value of the component S.
  • the acid value of component S is preferably 20 to 300 (mgKOH / g), more preferably 50 to 250 (mgKOH / g), and particularly preferably 50 to 210 (mgKOH / g).
  • the acid value is 20 (mgKOH / g) or more, sufficient alkali developability of the photosensitive resin composition is obtained, and when the acid value is 300 (mgKOH / g) or less, the dispersibility of the metal oxide particles, And it is excellent in dispersion stability.
  • the acid value of component S is the solid content acid value of component S.
  • the acid value of component S can be calculated from the average content of acid groups in component S, for example.
  • the acid value of component S can be adjusted by appropriately adjusting the amount of the acid group in component S and the amount of the functional group having a pKa of 5 or more.
  • the amount of the compound having an acid group and an ethylenically unsaturated bond used as a raw material the amount of the compound having a pKa5 or higher functional group and an ethylenically unsaturated bond, and a vinyl monomer having an acid group
  • the component S having a desired acid value can be synthesized by appropriately adjusting the amount charged.
  • the method for synthesizing component S is not particularly limited, but paragraphs 0114 to 0140 and 0266 to 0348 and 0266 to 0348 of JP-A-2007-277514 (paragraphs 0145 to 0173 and 0289 in the corresponding US Patent Application Publication No. 2010/233595).
  • To 0429) can be synthesized.
  • the component S is preferably synthesized by a method of radical polymerization of a vinyl monomer in the presence of a mercaptan compound having a plurality of the adsorption sites.
  • the above vinyl monomers may be polymerized by only one kind, or may be copolymerized by using two or more kinds in combination.
  • preferred specific examples (M-1) to (M-12) of vinyl monomers are shown below, but the present invention is not limited thereto.
  • the method for synthesizing component S is preferably a method in which a vinyl monomer is radically polymerized in the presence of a compound represented by the following formula (S ′).
  • R 6 , R 7 , A 3 , m, and n have the same meanings as R 3 , R 4 , A 2 , m, and n in the above formula (S), respectively.
  • the aspect is also the same.
  • a method for synthesizing component S a method of adding a compound represented by the above formula (S ′) and a macromonomer having an ethylenically unsaturated bond (ene-thiol reaction method) is also preferable. It is preferable to use a radical generator or a base as a catalyst for the reaction. Specific examples of the macromonomer having an ethylenically unsaturated bond are shown below, but the present invention is not limited thereto. In the following specific examples, the number k of repeating units represents an integer of 3 to 50.
  • a method for synthesizing component S a method in which a thioester group is formed by a dehydration condensation reaction between the compound represented by the above formula (S ′) and a polymer compound having a carboxylic acid group is also preferable.
  • Specific examples of the polymer compound having a carboxylic acid group are shown below, but the present invention is not limited thereto.
  • the number k of repeating units represents an integer of 3 to 50.
  • a method for synthesizing component S a method in which a thioether group is formed by a nucleophilic substitution reaction between the compound represented by the above formula (S ′) and a polymer compound having a leaving group is also preferable.
  • the leaving group is preferably a halogen atom such as an iodine atom, bromine atom or chlorine atom, or a sulfonate group such as a tosylate group, mesylate group or trifluoromethanesulfonate group.
  • Specific examples of the polymer compound having a leaving group are shown below, but the present invention is not limited thereto. In the following specific examples, the number k of repeating units represents an integer of 3 to 50.
  • the component S is preferably synthesized by the following method. Method for addition reaction of a compound having 3 to 10 mercapto groups in one molecule and a compound having an adsorption site and having an ethylenically unsaturated bond capable of reacting with a mercapto group
  • the addition reaction is a radical addition reaction.
  • the ethylenically unsaturated bond is more preferably a mono- or di-substituted vinyl group in terms of reactivity with the mercapto group.
  • Specific examples of the compound having 3 to 10 mercapto groups in one molecule include the following compounds.
  • a compound having the above-mentioned adsorption site and having an ethylenically unsaturated bond (specifically, organic dye structure, heterocyclic structure, acid group, group having basic nitrogen atom, urea group, urethane group, coordination) Group having a reactive oxygen atom, alkoxysilyl group, phenol group, alkyl group, aryl group, group having an alkyleneoxy chain, imide group, alkyloxycarbonyl group, alkylaminocarbonyl group, carboxylate group, sulfonamide group, epoxy group
  • the compound having at least one partial structure selected from the group consisting of an isocyanate group and a hydroxyl group and having an ethylenically unsaturated bond is not particularly limited, but includes the following.
  • the radical addition reaction product of the above “compound having 3 to 10 mercapto groups in one molecule” and “the compound having the above-mentioned adsorption site and having an ethylenically unsaturated bond” is, for example, The “compound having 3 to 10 mercapto groups in one molecule” and “the compound having the above-mentioned adsorption site and having an ethylenically unsaturated bond” are dissolved in an appropriate solvent, and radicals are generated therein. It is obtained by using a method of adding an agent and adding at about 50 ° C. to 100 ° C. (ene-thiol reaction method).
  • suitable solvents used in the ene-thiol reaction method include “compound having 3 to 10 mercapto groups in one molecule”, “having the above adsorption site, and ethylenically unsaturated bond” It can be arbitrarily selected according to the solubility of the “compound having a” and “the radical addition reaction product to be produced”.
  • solvents may be used as a mixture of two or more.
  • radical generator examples include 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2,4′-dimethylvaleronitrile), and dimethyl 2,2′-azobisisobutyrate [ V-601, manufactured by Wako Pure Chemical Industries, Ltd.], peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate can be used.
  • Component S is preferably obtained by polymerizing these vinyl monomers and the compound represented by the above formula (S ′) by a known method according to a conventional method.
  • the compound represented by the above formula (S ′) in the present invention functions as a chain transfer agent, and may be simply referred to as “chain transfer agent” hereinafter.
  • chain transfer agent a method in which these vinyl monomers and the above chain transfer agent are dissolved in an appropriate solvent, a radical polymerization initiator is added thereto, and polymerization is performed in a solution at about 50 ° C. to 220 ° C. (solution polymerization method) Can be obtained using
  • suitable solvents used in the solution polymerization method can be arbitrarily selected according to the monomers used and the solubility of the resulting copolymer.
  • Examples include acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.
  • radical polymerization initiator known radical polymerization initiators can be used.
  • the above-mentioned azo compounds, peroxides, persulfates and the like can be suitably used as the radical generator.
  • the molecular weight of component S is preferably 2,000 to 200,000, more preferably 2,000 to 15,000, and particularly preferably 2,500 to 10,000 in terms of weight average molecular weight.
  • the component S contained in the resin composition of the present invention may be only one type or two or more types. In the case of two or more types, the total is preferably in the above range.
  • exemplary compounds of component S will be listed, but the present invention is not limited thereto, and can take any structure as long as it is included in formula (S).
  • P1 and P2 can take arbitrary values in terms of mass.
  • the sulfur atom bonded to the polymer chain may be bonded to any monomer unit, and the other terminal not bonded to the sulfur atom of the polymer chain indicated by Poly is marked in the following chemical formula.
  • any atom or group that is usually allowed at the terminal of the polymer skeleton may be used.
  • R3 in (S-1-14) to (S-1-19) is the following group.
  • the content ratio (P1: P2) of the monomer unit having a carboxylic acid ester and the monomer unit having a carboxy group in the polymer skeleton is in the range of 100: 0 to 80:20 in terms of mass. It is preferable that Component S can be synthesized, for example, with reference to the method described in JP-A-2008-96678.
  • the content of component S in the photosensitive resin composition of the present invention is preferably in the range of 5 to 70% by mass and more preferably in the range of 10 to 50% by mass with respect to the total solid content of the photosensitive resin composition.
  • the photosensitive resin composition of the present invention contains a dispersant other than the component S (hereinafter sometimes referred to as “other dispersant”) for the purpose of adjusting the dispersibility of the metal oxide particles. May be.
  • Other dispersants that can be used in the present invention include known dispersants, but polymer dispersants other than Component S [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight Unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine Preferable examples include alkanolamine and pigment derivatives.
  • Other polymer dispersants can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
  • the other dispersing agent is adsorbed on the surface of the metal oxide particles and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the surface of the metal oxide particles can be cited as preferred structures. On the other hand, other dispersants may have an effect of promoting adsorption of the dispersed resin by modifying the surface of the metal oxide particles.
  • polymer dispersants include BYDIS Chemie's “DISPERBYK101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110, 180 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, 4165 (manufactured by EFKA) Polyurethane), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative).
  • polymer obtained by polymerizing the compound represented by the formula (ED) as an essential monomer component include the compound represented by the formula (ED) described later in the section of the binder polymer as an essential monomer.
  • ED the compound represented by the formula (ED) described later in the section of the binder polymer as an essential monomer.
  • the thing similar to the specific example of the polymer polymerized as a component is mentioned.
  • These other dispersants may be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention may or may not contain other dispersion resin, but when it is contained, the content of the other dispersant with respect to the total solid content of the photosensitive resin composition is 1 to The range of 20% by mass is preferable, and the range of 1 to 10% by mass is more preferable.
  • the photosensitive resin composition of the present invention contains (Component B) a photoacid generator.
  • the photoacid generator (also referred to as “component B”) used in the present invention is preferably a compound that generates an acid in response to an active ray having a wavelength of 300 nm or more, preferably 300 to 450 nm.
  • the structure is not limited.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • the photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less. Most preferred is a photoacid generator that generates an acid.
  • photoacid generator examples include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation.
  • photoacid generators can be used singly or in combination of two or more.
  • trichloromethyl-s-triazines diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP2011-212494A. It can be illustrated.
  • 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 formula (B1).
  • R 21 represents an alkyl group or an aryl group, and a wavy line represents a bonding site with another group.
  • 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 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like). It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
  • aryl group for R 21 an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.
  • the aryl group of R 21 may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
  • the above compound containing an oxime sulfonate structure represented by the above formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B2).
  • R 42 represents an alkyl group or an aryl group
  • X represents an alkyl group, an alkoxy group, or a halogen atom
  • m4 represents an integer of 0 to 3
  • m4 is 2 or 3. In some cases, multiple 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. In the above formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl A compound having a -2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.
  • the compound containing an oxime sulfonate structure represented by the above formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B3).
  • R 43 has the same meaning as R 42 in the formula (B2), and X 1 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and n4 represents an integer of 0 to 5.
  • R 43 in the above formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
  • X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
  • n4 is preferably an integer of 0 to 2, particularly preferably 0 or 1.
  • Specific examples of the compound represented by the above formula (B3) include ⁇ - (methylsulfonyloxyimino) benzyl cyanide, ⁇ - (ethylsulfonyloxyimino) benzyl cyanide, ⁇ - (n-propylsulfonyloxyimino) Benzyl cyanide, ⁇ - (n-butylsulfonyloxyimino) benzyl cyanide, ⁇ - (4-toluenesulfonyloxyimino) benzyl cyanide, ⁇ -[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(n-propylsulfonyloxyimino) -4-methoxyphenyl]
  • preferable oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used singly or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.
  • the compound containing an oxime sulfonate structure represented by the above formula (B1) is also preferably a compound represented by the following formula (OS-1).
  • R 101 represents a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, aryl group, or hetero Represents an aryl group.
  • R102 represents an alkyl group or an aryl group.
  • X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups. Or an aryl group.
  • R 121 to R 124 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or Represents an aryl group.
  • Two of R 121 to R 124 may be bonded to each other to form a ring.
  • R 121 to R 124 are each independently preferably a hydrogen atom, a halogen atom or 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 preferable. Can be mentioned. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the aforementioned functional groups may further have a substituent.
  • the compound represented by the above formula (OS-1) is more preferably a compound represented by the following formula (OS-2).
  • R 101 , R 102 and R 121 to R 124 have the same meanings as those in the formula (OS-1), and preferred examples thereof are also the same.
  • an embodiment in which R 101 in the above formula (OS-1) and the above formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the above formula (OS-2), wherein R 101
  • the embodiment in which is a cyano group, a phenyl group or a naphthyl group is most preferred.
  • the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
  • the compound having an oxime sulfonate structure represented by the above formula (B1) is represented by the following formula (OS-3), the following formula (OS-4) or the following formula (OS-5). It is preferably an oxime sulfonate compound.
  • 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 alkoxy 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 0 Represents an integer of ⁇ 6)
  • the alkyl group, aryl group or heteroaryl group in R 22 , R 25 and R 28 may have a substituent.
  • the alkyl group in R 22 , R 25 and R 28 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
  • the aryl group in R 22 , R 25 and R 28 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent. .
  • the heteroaryl group in R 22 , R 25 and R 28 is a heteroaryl group having a total of 4 to 30 carbon atoms which may have a substituent. Is preferred.
  • at least one of the heteroaryl groups in R 22 , R 25 and R 28 may be a heteroaromatic ring, such as a heteroaromatic ring and a benzene ring. And may be condensed.
  • R 23 , R 26 and R 29 are preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
  • one or two of R 23 , R 26 and R 29 present in the compound may be an alkyl group, an aryl group or a halogen atom. More preferably, one is an alkyl group, an aryl group or a halogen atom, more preferably one is an alkyl group and the rest is a hydrogen atom.
  • the alkyl group for R 23 , R 26 and R 29 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.
  • the aryl group for R 23 , R 26 and R 29 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
  • X 1 to X 3 each independently represents O or S, and is preferably O.
  • the ring containing X 1 to X 3 as a ring member is a 5-membered ring or a 6-membered ring.
  • n 1 to n 3 each independently represents 1 or 2, and when X 1 to X 3 are O, n 1 to n 3 are each independently In addition, it is preferably 1, and when X 1 to X 3 are S, n 1 to n 3 are each independently preferably 2.
  • R 24 , R 27 and R 30 each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group.
  • R 24 , R 27 and R 30 are preferably each independently an alkyl group or alkyloxy group.
  • the alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R 24 , R 27 and R 30 may have a substituent.
  • the alkyl group in R 24 , R 27 and R 30 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
  • the alkyloxy group in R 24 , R 27 and R 30 is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. It is preferable.
  • m 1 to m 3 each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.
  • substitution of (OS-3) to (OS-5) described in paragraphs 0092 to 0109 of JP2011-221494A The preferred range of groups is likewise preferred.
  • the compound containing an oxime sulfonate structure represented by the above formula (B1) is particularly preferably an oxime sulfonate compound represented by any of the following formulas (OS-6) to (OS-11).
  • R 301 to R 306 represent an alkyl group, an aryl group, or a heteroaryl group
  • R 307 represents a hydrogen atom or a bromine atom
  • R 308 to R 310 , R 313 , R 316 and R 318 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group.
  • R 311 and R 314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group
  • R 312 , R 315 , R 317 and R 319 each independently represent a hydrogen atom or a methyl group.
  • oxime sulfonate compounds represented by the above formulas (OS-3) to (OS-5) include the compounds described in paragraphs 0114 to 0120 of JP2011-221494A. The invention is not limited to these.
  • the photoacid generator is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of Component A in the photosensitive resin composition. It is more preferable to use 5 to 10 parts by mass.
  • the component B may be used individually by 1 type and can also use 2 or more types together.
  • Component C Metal oxide particles
  • the resin composition of the present invention contains metal oxide particles for the purpose of adjusting the refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a positive photosensitive resin composition having a high refractive index and excellent transparency can be obtained.
  • Component C preferably has a refractive index higher than that of the resin composition made of the material excluding the particles. Specifically, the refractive index in light having a wavelength of 400 to 750 nm is 1.50.
  • the above particles are more preferable, particles having a refractive index of 1.70 or more are further preferable, and particles having a refractive index of 1.90 or more are particularly preferable. Further, particles having a refractive index of 2.80 or less are preferable.
  • the refractive index of light having a wavelength of 400 to 750 nm being 1.50 or more means that the average refractive index of light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more.
  • the average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.
  • the metal of the metal oxide particles in the present invention includes semimetals such as B, Si, Ge, As, Sb, and Te.
  • the light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb.
  • Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable.
  • Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide and zirconium oxide are more preferable, titanium oxide and zirconium oxide are particularly preferable, and titanium dioxide is most preferable. Titanium dioxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.
  • the average primary particle size of Component C is preferably 1 to 200 nm, particularly preferably 3 to 80 nm.
  • the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. Moreover, when the shape of the particle was not spherical, the maximum diameter was taken as the particle diameter.
  • the component C may be used individually by 1 type and can also use 2 or more types together.
  • the content of the metal oxide particles in the resin composition of the present invention may be appropriately determined in consideration of the refractive index required for the optical member obtained from the resin composition, light transmittance, etc.
  • the total solid content of the resin composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.
  • the photosensitive resin composition of the present invention contains (Component D) a solvent.
  • the photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and optional components described below are further dissolved in (Component D) solvent.
  • solvent used in the photosensitive resin composition of the present invention known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl.
  • Ethers propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like. Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraphs 0174 to 0178 of JP2011-22214A.
  • Component D 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 (component D) solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, and preferably 60 to 90 parts by mass per 100 parts by mass of component A in the photosensitive resin composition. More preferably.
  • the photosensitive resin composition of the present invention preferably contains a crosslinking agent as required. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
  • the crosslinking agent is not limited as long as it causes a crosslinking reaction by heat (except for component A).
  • a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, or a blocked isocyanate compound, etc. Can be added.
  • the addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, and preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition.
  • the amount is more preferably part by mass, and further preferably 0.5 to 20 parts by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained.
  • a plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.
  • bisphenol A type epoxy resins bisphenol F type epoxy resins, phenol novolac type epoxy resins and aliphatic epoxy resins are more preferable, and bisphenol A type epoxy resins are particularly preferable.
  • Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX manufactured by Toagosei Co., Ltd.
  • the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.
  • alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A, compounds having at least one ethylenically unsaturated double bond, and the like are also preferably used. be able to.
  • alkoxymethyl group-containing crosslinking agent alkoxymethylated glycoluril is preferable.
  • a blocked isocyanate compound can also be preferably employed as a crosslinking agent.
  • the blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
  • the blocked isocyanate group in this invention is a group which can produce
  • the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
  • the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
  • the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic.
  • Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
  • Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to.
  • a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
  • Examples of the oxime compound include aldoxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
  • Examples of the lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
  • Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
  • Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
  • Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
  • Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
  • Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
  • Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
  • the blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available.
  • Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL
  • the photosensitive resin composition of the present invention preferably contains 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, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives.
  • phenol-based antioxidants amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used individually by 1 type and may mix 2 or more types. Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO.
  • ADK STAB AO-51 ADK STAB AO-60
  • ADK STAB AO-70 ADK STAB AO-80
  • ADK STAB AO-330 ADK STAB AO-412S
  • ADK STAB AO-503 ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 13510, ADK STAB 3010, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS-90 -91 (above, manufactured by ADEKA Corporation), Irga
  • 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, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
  • additives other than antioxidants various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.
  • the photosensitive resin composition of the present invention includes (Component G) a sensitizer, (Component H) an alkoxysilane compound, (Component I) a basic compound, and (Component J) as necessary.
  • a surfactant can be preferably added.
  • the photosensitive resin composition of the present invention includes the ultraviolet absorber, metal deactivator, acid multiplier, development accelerator, plasticizer, thermal radical generator, thermal acid generator, thickener, and Known additives such as organic or inorganic suspending agents can be added.
  • the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (Component B) a 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
  • Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
  • Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene
  • xanthenes Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone
  • cyanines eg, thiacarbocyanine, oxacarbocyanine
  • merocyanines For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, to
  • polynuclear aromatics polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
  • polynuclear aromatics anthracene derivatives are most preferred.
  • the addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition.
  • the amount is more preferably part by mass, and further preferably 50 to 200 parts by mass.
  • a sensitizer may be used individually by 1 type and can also use 2 or more types together.
  • the photosensitive resin composition of the present invention may contain (Component H) an alkoxysilane compound.
  • an alkoxysilane compound When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do.
  • the (component H) alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, gold, copper, molybdenum, titanium, A compound that improves the adhesion between a metal such as aluminum and the insulating film is preferable. Specifically, a known silane coupling agent or the like is also effective.
  • silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, and ⁇ -methacrylic acid.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable.
  • These can be used alone or in combination of two or more.
  • the following compounds can also be preferably employed.
  • Ph represents a phenyl group.
  • the alkoxysilane compound in the photosensitive resin composition of this invention is not specifically limited to these, A well-known thing can be used.
  • the content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, and preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition. Is more preferable.
  • the photosensitive resin composition of the present invention may contain (Component I) 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 paragraphs 0204 to 0207 of JP2011-221494A.
  • aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
  • examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, 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 basic compounds that can be used in the present invention may be used singly or in combination of two or more.
  • the content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, 0.005 More preferred is 1 part by mass.
  • the photosensitive resin composition of the present invention may contain (Component J) a surfactant.
  • a surfactant any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • F-Top manufactured by JEMCO
  • MegaFac manufactured by DIC Corporation
  • Florard Suditomo 3M
  • Surflon manufactured by Asahi Glass Co., Ltd.
  • PolyFox manufactured by OMNOVA
  • SH-8400 manufactured by Toray Dow Corning Co., Ltd.
  • the surfactant includes a structural unit A and a structural unit B represented by the following formula (J-1), and the weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
  • Preferred examples include copolymers having an 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 a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is 10 mass% to 80 mass%.
  • a numerical value is represented, q represents a numerical value of 20% by mass or more and 90% by mass or less, 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 formula (J-2).
  • R 405 in formula (J-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • the addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, and 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 amount is 0.01 to 3 parts by mass.
  • the photosensitive resin composition of the present invention can use an acid proliferating agent for the purpose of improving sensitivity.
  • the acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here.
  • the strength of the acid is preferably 3 or less, particularly preferably 2 or less, as the acid dissociation constant, pKa.
  • pKa is preferably ⁇ 15 or more.
  • Specific examples of the acid proliferating agent include paragraphs 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39, line 12 of JP-A-9-512498. Examples of the compounds described on page 47, line 2 are listed.
  • Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids. Specific examples include the following compounds.
  • the content of the acid proliferating agent in the photosensitive composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator, from the viewpoint of dissolution contrast between the exposed and unexposed parts. It is preferably 20 to 500 parts by mass.
  • the photosensitive resin composition of the present invention may contain a development accelerator.
  • a development accelerator any compound having a development acceleration effect can be used, but a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group is preferable.
  • a compound having a carboxyl group or a phenolic hydroxyl group is more preferred, and a compound having a phenolic hydroxyl group is most preferred.
  • the development accelerator the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
  • a development accelerator may be used individually by 1 type, and can also use 2 or more types together.
  • the addition amount of the development accelerator in the photosensitive resin composition of the present invention is 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition from the viewpoint of sensitivity and the remaining film ratio of the unexposed part.
  • 0.1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
  • the thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, and the nitrogen-containing compounds and thermal acid generators described in International Publication No. 2011-136004 may be used. it can.
  • the method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
  • the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. It is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning before applying the photosensitive resin resin composition to the substrate, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesion of the photosensitive resin composition to the substrate is improved.
  • 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.
  • the substrate examples include inorganic substrates, resins, resin composite materials, ITO, Cu substrates, polyethylene terephthalate, and plastic substrates such as cellulose triacetate (TAC).
  • 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 resin, cyclic polyolefin, Is it a synthetic resin such as aromatic ether resin, maleimide-olefin resin, cellulose, episulfide resin, etc.
  • These substrates include a substrate made of the is less if used while the above embodiment, depending on the form of the final product, for example, when the multi-layered structure such as a TFT element is formed is usually.
  • the coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
  • the coating film thickness is not particularly limited, and can be applied with a film thickness according to the application, but it is preferably used in the range of 0.5 to 10 ⁇ m.
  • the solvent removal step (2) the solvent is removed from the applied film by reducing pressure (vacuum) and / or heating to form a dry coating film on the substrate.
  • the heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are within the above ranges, the pattern adhesion is good and the residue can be reduced.
  • the substrate provided with the coating film is irradiated with actinic rays through a mask 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 produce an acid group, for example, a carboxyl group or a phenolic hydroxyl group.
  • an exposure light source using actinic light a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc.
  • g-line (436 nm), i-line (365 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 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.
  • various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
  • 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.
  • the acid-decomposable group in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group.
  • a positive image can be formed by development without performing PEB.
  • a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer.
  • a positive image is formed by removing an exposed area containing a resin composition having an acid group that easily dissolves in an alkaline developer, such as a carboxyl group or a phenolic hydroxyl group.
  • the developer used in the development step preferably contains a basic compound.
  • Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used.
  • 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.
  • Preferred examples of the developer include a 0.4% by mass aqueous solution, a 0.5% by mass aqueous solution, a 0.7% by mass aqueous solution, or a 2.38% by mass aqueous solution of tetraethylammonium hydroxide.
  • 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 either a liquid piling method or a dipping method. After development, washing with running water can be performed for 30 to 300 seconds to form a desired pattern.
  • 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, a shower rinse, a dip rinse, etc. can be mentioned.
  • the obtained positive image is heated to thermally decompose the acid-decomposable group to generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group, and a crosslinkable group
  • a cured film can be formed by crosslinking with a crosslinking agent or the like.
  • This heating is performed using a heating device such as a hot plate or oven at a predetermined temperature, for example, 180 ° C. to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven.
  • a protective film and an interlayer insulating film having excellent heat resistance, hardness, and the like can be formed.
  • the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.
  • heat treatment is preferably performed at 80 to 140 ° C. for 5 to 120 minutes.
  • the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step).
  • middle baking it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes.
  • middle baking and post baking can be heated in three or more stages.
  • the taper angle of the pattern can be adjusted by devising such middle baking and post baking.
  • These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
  • post-exposure 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 processing such as ashing, plasma etching, ozone etching, or the like can be performed as the etching processing.
  • the cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
  • the cured film of the present invention can be suitably used as an interlayer insulating film.
  • the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
  • an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for applications of organic EL display devices, liquid crystal display devices, and touch panel display devices.
  • the cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.
  • the shape does not have to be a film, and may be any shape.
  • the production method of the cured product of the present invention is not particularly limited, but preferably includes at least the following steps (a) to (c) in this order.
  • Step (c) is the same step as the heat treatment step except that the heat treatment target is a resin composition from which the solvent obtained in step (b) has been removed. Preferred embodiments such as time and heating means are also preferred.
  • the cured product or cured film of the present invention is for reducing the visibility of wiring members used for optical members such as microlenses, optical waveguides, antireflection films, LED sealing materials and LED chip coating materials, or touch panels. It can be suitably used as a cured product.
  • the cured product or cured film of the present invention is, for example, a flattening film or interlayer insulating film in a liquid crystal display device or an organic EL device as described later, a protective film for a color filter, and a thickness of a liquid crystal layer in a liquid crystal display device.
  • the liquid crystal display device of the present invention comprises the cured film of the present invention.
  • the liquid crystal display device of the present invention is not particularly limited except that it has a 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 TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtical Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (OCB). Optical Compensated Bend) method.
  • the cured film of the present invention can also be used in a COA (Color Filter on Allay) type liquid crystal display device.
  • the organic insulating film (115) described in JP-A-2005-284291 It can be used as the organic insulating film (212) described in Japanese Unexamined Patent Publication No. 2005-346054.
  • 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 Japanese Patent Application Laid-Open 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, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
  • FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10.
  • the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
  • the elements of the TFT 16 corresponding to are arranged.
  • Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
  • an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
  • the light source of the backlight is not particularly limited, and a known light source can be used.
  • the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interphase insulating film (48) described in JP2011-145686A or the interphase insulating film (520) described in JP2009-258758A. Can do.
  • the organic EL display device of the present invention comprises the cured film of the present invention.
  • the organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic materials having various structures.
  • An EL display device and a liquid crystal display device can be given.
  • specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • FIG. 2 is a conceptual diagram of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • a bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3.
  • the wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
  • a planarizing layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
  • a bottom emission type organic EL element is formed on the planarizing film 4 on the planarizing film 4. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • the first electrode 5 corresponds to the anode of the organic EL element.
  • An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do. Further, although not shown in FIG.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a 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.
  • a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part.
  • MEMS devices include, for example, SAW (surface acoustic wave) filters, BAW (bulk acoustic wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, biochips, sealants. And the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
  • the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. Partition wall (12) and planarization film (102) shown in FIG. 4 (a) of JP-A-9793, and bank layer (221) and third interlayer insulating film (FIG. 10 of JP 2010-27591A). 216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and the configuration described in FIG. 3 of JP-A-2010-182638. It can also be used to form a planarization film (12), a pixel isolation insulating film (14), and the like.
  • the touch panel display device of the present invention includes a capacitive input device having the cured product of the present invention. Moreover, the capacitance-type input device of the present invention is characterized by having the film of the present invention.
  • the capacitance-type input device of the present invention has at least the following elements (1) to (5) on the front plate and the non-contact side of the front plate. (4) is the heat-treated product of the present invention. Preferably there is.
  • (1) Mask 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) The first transparent electrode pattern and the electric
  • a plurality of second transparent electrode patterns comprising a plurality of pad portions which are insulated and extend in a direction intersecting the first direction.
  • a transparent protective layer is further provided so as to cover all or part of the elements (1) to (5).
  • the transparent protective layer is preferably And more preferably the cured film.
  • FIG. 3 is a cross-sectional view showing the configuration of the capacitive input device.
  • the capacitive input device 30 includes a front plate 31, a mask 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 composed of a light-transmitting substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. Moreover, in FIG. 3, the side in which each element of the front plate 31 is provided is called a non-contact surface. In the capacitive input device 30 of the present invention, input is performed by bringing a finger or the like into contact with the contact surface (the surface opposite to the non-contact surface) of the front plate 31.
  • the front plate may be referred to as a “base material”.
  • a mask layer 32 is provided on the non-contact surface of the front plate 31.
  • the mask layer 32 is a frame-like pattern around the display area formed on the non-contact side of the touch panel front plate, and is formed so as not to show the lead wiring and the like.
  • a mask layer 32 is provided so as to cover a part of the front plate 31 (a region other than the input surface in FIG. 4).
  • the front plate 31 can be provided with an opening 38 in a part thereof 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 34 each including a plurality of pad portions that are electrically insulated from one transparent electrode pattern 33 and extend in a direction crossing the first direction; An insulating layer 35 that electrically insulates the electrode pattern 33 and the second transparent electrode pattern 34 is formed.
  • the first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 to be described later are translucent conductive materials such as ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide). It can be made of a conductive metal oxide film.
  • metal films examples include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO 2 .
  • the film thickness of each element can be set to 10 to 200 nm.
  • the first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 described later use a photosensitive transfer material having a photosensitive resin composition using the conductive fibers. Can also be manufactured.
  • paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to.
  • 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 opposite to the front plate 31 of the mask layer 32. Can be installed.
  • FIG. 3 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 mask layer 32. Yes.
  • FIG. 5 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention.
  • the first transparent electrode pattern 33 is formed such that a pad portion 33a extends in a first direction via a 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. 5). It is constituted by a plurality of pad portions that are formed.
  • the pad portion 33a and the connection portion 33b may be manufactured as one body, or only the connection portion 33b is manufactured, and the pad portion 33a and the second portion 33b are formed.
  • the transparent 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. 5, 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 provided on the surface of the mask 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. 3 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 capacitance-type input device obtained by the manufacturing method of the present invention and the touch panel display device including the capacitance-type input device as a constituent element are “latest touch panel technology” (issued July 6, 2009 (stock) ) Techno Times), supervised by Yuji Mitani, “Technology and Development of Touch Panels”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. Can be applied.
  • the touch panel of the present invention is a touch panel in which all or a part of the insulating layer is made of a heat-treated product of the resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an ITO electrode, and an insulating 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.
  • the manufacturing method of the touchscreen of this invention is a manufacturing method of the touchscreen which has a transparent substrate, an ITO electrode, and an insulating layer, Comprising: Inkjet application
  • a transparent substrate in the touch panel of this invention a glass substrate, a quartz substrate, a transparent resin substrate, etc. are mentioned preferably.
  • Ink-jet application in the step of applying the photosensitive resin composition for ink-jet application of the present invention by the ink-jet application method so as to be in contact with the ITO electrode can be performed in the same manner as the above-described application step, and the preferred embodiment is also the same. .
  • coated photosensitive resin composition of this invention should just be in contact with the ITO electrode.
  • the step of placing a mask having an opening pattern of a predetermined shape on the resin composition, irradiating with exposure to active energy rays, and the step of developing the resin composition after exposure are performed in the same manner as the exposure step described above.
  • the preferred embodiment is also the same.
  • the step of heating the resin composition after development to produce an insulating layer can be performed in the same manner as the heat treatment step described above, and the preferred embodiment is also the same.
  • the pattern shown in FIG. 5 mentioned above is mentioned preferably.
  • MATHF 2-tetrahydrofuranyl methacrylate (synthetic product)
  • OXE-30 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
  • GMA Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • NBMA n-butoxymethylacrylamide (Mitsubishi Rayon Co., Ltd.)
  • HEMA Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
  • MAA Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MMA Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
  • St Styrene (Wako Pure Chemical Industries, Ltd.)
  • DCPM Dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
  • BzMA 2-tetrahydr
  • the sulfur atom bonded to the polymer chain may be bonded to the P1 monomer unit or may be bonded to the P2 monomer unit.
  • the polymer chain is a random copolymer skeleton composed of two types of monomer units indicated by parentheses with P1 and P2 as subscripts.
  • Dispersions D2 to D17 were obtained in the same manner as in the preparation of the dispersion D1, except that TTO-51 (C) and Compound 1 were changed to those shown in Table 1, respectively.
  • TTO-55 (C): Titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd., average primary particle size: 30-50 nm RC-100: Zirconium dioxide, manufactured by Daiichi Elemental Chemical Co., Ltd., D 50 : 1.5-4 ⁇ m DISPERBYK-111: Dispersant other than Component S, manufactured by Big Chemie Japan, Ltd. DISPERBYK-2001: Dispersant other than Component S, manufactured by Big Chemie Japan, Inc. Solsperse 41000: Dispersant other than Component S, Compound manufactured by Lubrizol 2: The following compound, Mw 8,200, 30% PGMEA solution
  • the sulfur atom bonded to the polymer chain may be bonded to the P1 monomer unit or may be bonded to the P2 monomer unit.
  • the polymer chain is a random copolymer composed of two types of monomer units indicated by parentheses with P1 and P2 as subscripts.
  • the PGMEA solution of polymer P1 was obtained by reacting at 70 ° C. for 2 hours. Further, PGMEA was added to adjust the solid content concentration to 40% by mass.
  • the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained polymer P1 was 15,000. The acid value was 45 mg KOH / g.
  • the amount described in Table 2 is a molar ratio and represents a copolymerization ratio of structural units derived from each monomer described in the type column.
  • “-” indicates that the structural unit is not included.
  • Example 1 Preparation of photosensitive resin composition> After mixing and mixing with the following composition to make a uniform solution, the mixture was filtered using a polyethylene filter having a pore size of 0.2 ⁇ m to prepare a photosensitive resin composition of Example 1. Various evaluations described later were performed using the obtained photosensitive resin composition. The evaluation results are shown in Table 3 described later.
  • PGMEA solution 191.1 parts-0.2% PGMEA solution of the following compound I-1 (manufactured by Toyo Kasei Kogyo Co., Ltd., CMTU): 25.7 parts-30% PGMEA solution of polymer P1: 263.3 parts
  • Photoacid generator B-1 (compound below): 5.1 parts JER157S65 (epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 200 to 220 g / eq: 17.9 parts, 3- Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 4.5 parts ⁇ Irganox 1726 (Antioxidant, manufactured by BASF): 3.0 parts ⁇ Nonion containing perfluoroalkyl group Surfactant (F-554, manufactured by DIC Corporation) 2.0% PGMEA solution: 11.0 parts Dispersion D1: 478.4 parts
  • oxime compound (2.4 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature (25 ° C.). The reaction was allowed to warm for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain 2.3 g of B-1.
  • the obtained photosensitive resin composition was applied on a 100 mm ⁇ 100 mm glass substrate (trade name: XG, manufactured by Corning) with a spin coater so as to have a film thickness of 1.0 ⁇ m, and then on a 90 ° C. hot plate. And dried for 120 seconds (pre-baked). Next, the film was developed with a 0.5% by mass aqueous KOH solution at 23 ° C. for 15 seconds by immersion, and further rinsed with ultrapure water for 10 seconds. Thereafter, the film thickness was further measured to determine the remaining film ratio after development relative to the case where the original film thickness (1.0 ⁇ m) was 100%.
  • the evaluation criteria are as shown below. 1 or 2 is a practical range. 1: The residual film ratio after development is 90% or more. 2: The remaining film ratio after development is 80% or more and less than 90%. 3: The residual film ratio after development is less than 80%.
  • the resulting photosensitive resin composition has a thickness of 2.0 ⁇ m on a 100 mm ⁇ 100 mm glass substrate (trade name: XG, manufactured by Corning) treated with hexamethyldisilazane (HMDS) for 3 minutes.
  • HMDS hexamethyldisilazane
  • the coating was applied by a spin coater and dried (prebaked) for 120 seconds on a hot plate at 90 ° C.
  • a ghi-line high-pressure mercury lamp exposure machine exposure was performed through a 1% to 60% gradation mask with a line and space of 1: 1 at an energy intensity of 20 mW / cm 2 and 200 mJ / cm 2 .
  • the film was developed with a 0.5% KOH aqueous solution at 23 ° C. for 15 seconds, and rinsed with ultrapure water for 10 seconds. Subsequently, a pattern was obtained by heating at 220 ° C. for 45 minutes. This pattern was observed with an optical microscope. This operation is started from the width of the mask line and space of 50 ⁇ m, and until 10 ⁇ m, the width is reduced by 5 ⁇ m by 10 ⁇ m, and the width is reduced by 1 ⁇ m. . 1 or 2 is a practical range. 1: The resolution was 5 ⁇ m or less. 2: The resolution was more than 5 ⁇ m and 10 ⁇ m or less. 3: The resolution was more than 10 ⁇ m and 50 ⁇ m or less. 4: A pattern could not be formed with a mask line and space width of 50 ⁇ m.
  • the obtained photosensitive resin composition was applied on a 100 mm ⁇ 100 mm glass substrate (trade name: XG, manufactured by Corning) with a spin coater so as to have a film thickness of 1.0 ⁇ m, and then on a 90 ° C. hot plate. And dried for 120 seconds (pre-baked). Further, the coating film was subjected to a heat treatment (post-bake) for 245 minutes in an oven at 220 ° C., and the spectrum after post-bake was measured with MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. It was evaluated by. 1 or 2 is a practical range.
  • 2 The transmittance at 400 nm was 85% or more and less than 90%.
  • 3 The transmittance at 400 nm was less than 85%.
  • An ITO pattern is formed in advance on a 100 mm ⁇ 100 mm glass substrate (trade name: XG, manufactured by Corning), and the resulting photosensitive resin composition is applied to a spin coater so as to have a film thickness of 1.0 ⁇ m. And then dried (prebaked) on a hot plate at 90 ° C. for 120 seconds. Next, the entire surface of the substrate was exposed with an energy intensity of 20 mW / cm 2 and 200 mJ / cm 2 using a ghi-line high pressure mercury lamp exposure machine. Subsequently, it was heated at 220 ° C. for 45 minutes to provide a dry film of the photosensitive resin composition on the ITO pattern.
  • the obtained substrate was observed with the naked eye in the bright room while tilting, and the visibility was evaluated as compared with the case where the photosensitive resin composition was not provided on the ITO pattern.
  • the evaluation standard is so good that the ITO pattern is difficult to see. 1 or 2 is a practical range. 1: The ITO pattern is almost invisible. 2: The ITO pattern appears faint. 3: The ITO pattern is clearly visible.
  • ⁇ Evaluation of haze (transparency)> On a 100 mm ⁇ 100 mm glass substrate (trade name: XG, manufactured by Corning), the obtained photosensitive resin composition was applied with a spin coater so that the dry film thickness was 2.0 ⁇ m, and hot at 80 ° C. The plate was dried (pre-baked) for 120 seconds. Furthermore, the coated film was heat-treated in an oven at 120 ° C. for 15 minutes (post-baking), and the haze after the post-baking was tested with a NDH-5000 made by Nippon Denshoku Industries Co., Ltd. The haze (haze value) was measured according to the method (JIS K7136, JIS K7361, ASTM D1003). In addition, a haze value refers to the value represented by the ratio (%) of the diffuse transmitted light with respect to all the light transmitted light. The smaller the haze value, the higher the transparency.
  • the obtained photosensitive resin composition was applied onto a silicon wafer substrate using a spinner, and dried at 80 ° C. for 120 seconds to form a film having a thickness of 0.5 ⁇ m.
  • This substrate was exposed to 200 mJ / cm 2 (measured with i-line) using an ultrahigh pressure mercury lamp, and then 220 ° C. in an oven. Heat at 45 ° C. for 45 minutes.
  • the refractive index of the cured film at 589 nm was measured using an ellipsometer VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.). A higher refractive index is preferable, and 1.70 or more is more preferable.
  • Example 2 to 35 and Comparative Examples 1 to 5 a photosensitive resin composition was prepared in the same manner as in Example 1, except that the dispersion and component A (polymer) were changed to those shown in Table 3, respectively. Each evaluation was performed. In Examples 20 to 24, as shown below, components other than the dispersion and Component A were further changed to prepare photosensitive resin compositions.
  • Example 21 5.1 parts of the photoacid generator B-1 was added to 2.55 parts of the following B-2 and 2.55 parts of 9,10-dibutoxyanthracene (DBA, manufactured by Kawasaki Kasei Kogyo Co., Ltd.) changed.
  • the photosensitive resin composition of the present invention had a low haze and maintained a high transmittance even after heating.
  • the photosensitive resin composition of the comparative example it turned out that the transmittance
  • Dispersions D18 to D45 were obtained in the same manner as in the preparation of Dispersion D1, except that TTO-51 (C) and Compound 1 were changed to those described in Table 4, respectively.
  • the ratio of the total amount of MEDG and other components was set to 70:30. That is, a polymer solution having a solid content concentration of 30% was prepared.
  • Polymers P12 to P15 were respectively synthesized in the same manner as the synthesis of the polymer P11 except that the types of monomers used, the polymerization initiator, and the like were changed as shown in the following table.
  • the numerical values without particular units are in mol%.
  • the numerical value of a polymerization initiator is mol% when a monomer component is 100 mol%.
  • the solid content concentration can be calculated by the following equation. Solid content concentration: monomer weight / (monomer weight + solvent weight) ⁇ 100 (unit: mass%) When V-601 was used as an initiator, the reaction temperature was 90 ° C., and when V-65 was used, the reaction temperature was 70 ° C.
  • Example 36 ⁇ Preparation of photosensitive resin composition> After blending and mixing in the following composition to make a uniform solution, the mixture was filtered using a polyethylene filter having a pore size of 0.2 ⁇ m to prepare a photosensitive resin composition of Example 36. Various evaluations described later were performed using the obtained photosensitive resin composition. The evaluation results are shown in Tables 9 to 11 described later.
  • Photoacid generator B-1 1.9 parts JER157S65: 6.9 parts
  • KBM-403 1.7 parts
  • F-554 0.08 parts
  • dispersion D18 181.7 parts
  • Photosensitive resin compositions were prepared in the same manner as in Example 36, except that the polymers, photoacid generators, sensitizers, and other components shown in Tables 6 to 8 below were used. In Tables 6 to 8, the amount of each component added represents mass% or parts by mass.
  • Example 136 In the active matrix liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 136 was obtained. That is, the photosensitive resin composition of Example 5 was spin-coated on a substrate, pre-baked on a hot plate (90 ° C./120 seconds), and then i-line (365 nm) was 45 mJ / mm from the mask using a high-pressure mercury lamp.
  • liquid crystal display device When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 137 An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
  • a bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3. .
  • the wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
  • the flattening film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
  • the planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 5 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating 45 mJ / cm 2 (energy intensity 20 mW / cm 2 ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C./30 minutes.
  • the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
  • 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 5 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.
  • Example 138 A touch panel display device was prepared by using the high refractive index curable resin material of the present invention by the method described below.
  • ⁇ Formation of first transparent electrode pattern> [Formation of transparent electrode layer]
  • a formed front plate was obtained.
  • the surface resistance of the ITO thin film was 80 ⁇ / ⁇ .
  • 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 then a dedicated developer And a post-bake treatment at 130 ° C. for 30 minutes to obtain a front plate on which a transparent electrode layer and a photocurable resin layer pattern for etching were formed.
  • the front plate on which the transparent electrode layer and the photocurable 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 front plate with the transparent electrode layer pattern with the etching resist layer pattern is immersed in a dedicated resist stripping solution, the photocurable resin layer for etching is removed, and the mask layer and the first transparent electrode pattern A front plate formed was obtained.
  • the photosensitive resin composition of Example 36 was applied and dried (film thickness: 1 ⁇ m, 90 ° C., 120 seconds) to form a photosensitive resin composition layer.
  • the distance between the exposure mask (quartz exposure mask having an insulating layer pattern) surface and the photosensitive resin composition layer was set to 30 ⁇ m, and pattern exposure was performed at an exposure amount of 50 mJ / cm 2 (i-line).
  • the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds by immersion and further rinsed with ultrapure water for 10 seconds.
  • a post-bake treatment at 220 ° C. for 45 minutes was performed to obtain a front plate on which a mask layer, a first transparent electrode pattern, and an insulating layer pattern were formed.
  • the first transparent electrode pattern, an insulating layer pattern formed using the photosensitive resin composition of Example 36, a transparent electrode layer, A front plate on which an etching resist pattern was formed was obtained (post-baking treatment; 130 ° C. for 30 minutes). Further, etching was performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer was removed to form the mask layer, the first transparent electrode pattern, and the curable resin composition of Example 36. 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 36 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.
  • the front exposure is performed with an exposure amount of 50 mJ / cm 2 (i-line) without using an exposure mask, development, post-exposure (1,000 mJ / cm 2 ), and post-bake treatment are performed to obtain a mask layer and a first transparent Cover the electrode pattern, the insulating layer pattern formed by using the photosensitive resin composition of Example 36, the second transparent electrode pattern, and all the conductive elements different from the first and second transparent electrode patterns.
  • stacked the insulating layer (transparent protective layer) formed using the photosensitive resin composition of Example 36 was obtained.
  • a liquid crystal display device manufactured by the method described in Japanese Patent Application Laid-Open No. 2009-47936 is bonded to the previously manufactured front plate, and an image display device including a capacitive input device as a constituent element is manufactured by a known method. did.
  • TFT thin film transistor
  • 2 wiring
  • 3 insulating film
  • 4 planarization film
  • 5 first electrode
  • 6 glass substrate
  • 7 contact hole
  • 8 insulating film
  • 10 liquid crystal display device
  • 12 Backlight unit
  • 14 15: Glass substrate
  • 16 TFT
  • 17 Cured film
  • 18 Contact hole
  • 19 ITO transparent electrode
  • 20 Liquid crystal
  • 22 Color filter
  • 30 Capacitive input device 31: front plate, 32: mask layer, 33: first transparent electrode pattern, 33a: pad portion, 33b: connection portion, 34: second transparent electrode pattern, 35: insulating layer
  • 36 conductive element
  • 37 Transparent protective layer
  • 38 Opening

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Abstract

La présente invention a pour but de proposer une composition de résine photosensible qui a un indice de réfraction élevé et une excellente transparence. Une composition de résine photosensible de la présente invention est caractérisée en ce qu'elle contient : (composant A) un composant polymère qui contient un polymère qui satisfait (1) et/ou (2) décrits ci-après ; (composant S) un dispersant qui est représenté par la formule (S) et a au moins un groupe acide ; (composant B) un générateur de photoacide ; (composant C) des particules d'oxyde métallique ; et (composant D) un solvant. (1) Un polymère qui a (a1) une unité constitutive ayant un groupe dans lequel un groupe acide est protégé par un groupe décomposable par un acide et (a2) une unité constitutive ayant un groupe réticulable (2) (a1) Un polymère qui a une unité constitutive ayant un groupe dans lequel un groupe acide est protégé par un groupe décomposable par un acide et (a2) un polymère qui a une unité constitutive ayant un groupe réticulable
PCT/JP2013/067634 2012-06-28 2013-06-27 Composition de résine photosensible, produit durci, procédé de fabrication d'un produit durci, procédé de production d'un motif de résine, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage électroluminescent organique, et dispositif d'affichage à panneau tactile WO2014003111A1 (fr)

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CN201380034042.0A CN104412161A (zh) 2012-06-28 2013-06-27 感光性树脂组合物、硬化物及其制造方法、树脂图案制造方法、硬化膜、液晶显示装置、有机el显示装置以及触摸屏显示装置
KR1020157000242A KR102057483B1 (ko) 2012-06-28 2013-06-27 감광성 수지 조성물, 경화물과 그 제조 방법, 수지 패턴 제조 방법, 경화막, 액정 표시 장치, 유기 ｅｌ 표시 장치, 및 터치패널 표시 장치
JP2014522675A JP6016918B2 (ja) 2012-06-28 2013-06-27 感光性樹脂組成物、硬化物の製造方法、樹脂パターン製造方法、硬化膜、液晶表示装置、有機ｅｌ表示装置、並びに、タッチパネル表示装置

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WO2015133357A1 (fr) * 2014-03-05 2015-09-11 富士フイルム株式会社 Composition de résine photosensible, procédé de production de film durci, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage el organique et dispositif d'affichage à écran tactile
WO2018061891A1 (fr) * 2016-09-27 2018-04-05 富士フイルム株式会社 Dispersion, composition, film, procédé de production de film, et dispersant
JP2018106201A (ja) * 2018-03-22 2018-07-05 東洋インキＳｃホールディングス株式会社 感光性樹脂組成物、ならびにそれを用いた塗膜
TWI645010B (zh) * 2014-03-17 2018-12-21 日商住友化學股份有限公司 附黏著劑之樹脂膜及使用該樹脂膜之光學積層體
TWI702470B (zh) * 2015-12-25 2020-08-21 日商富士軟片股份有限公司 感光化射線性或感放射線性樹脂組成物、感光化射線性或感放射線性膜、圖案形成方法及電子元件的製造方法
WO2021039253A1 (fr) 2019-08-30 2021-03-04 富士フイルム株式会社 Composition, film, filtre optique et procédé de production associé, élément d'imagerie à semi-conducteurs, capteur infrarouge et module de capteur
WO2021039205A1 (fr) 2019-08-29 2021-03-04 富士フイルム株式会社 Composition, film, filtre éliminateur d'infrarouge proche, procédé de formation de motif, stratifié, élément d'imagerie à semi-conducteurs, capteur infrarouge, dispositif d'affichage d'image, module de caméra et composé

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TWI802540B (zh) * 2017-05-12 2023-05-21 丹尼爾 Ｊ 納羅奇 聚磺醯胺重分佈組合物及其用途
KR20200022473A (ko) * 2017-08-03 2020-03-03 쇼와 덴코 가부시키가이샤 공중합체 및 컬러 필터용 감광성 수지 조성물
MY193800A (en) * 2018-01-18 2022-10-27 Asahi Chemical Ind Photosensitive resin laminate and method for manufacturing same
KR102510303B1 (ko) * 2019-03-28 2023-03-15 동우 화인켐 주식회사 착색 감광성 수지 조성물, 이를 사용하여 제조된 컬러필터, 및 상기 컬러필터를 포함하는 화상표시장치
WO2021060338A1 (fr) * 2019-09-26 2021-04-01 富士フイルム株式会社 Polymère à alignement optique, film d'alignement optique et corps optique multicouche

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