WO2014084190A1 - Photocurable composition, transfer material, cured product, method for producing cured product, method for producing resin pattern, cured film, liquid crystal display device, organic el display device, and touch panel display device - Google Patents

Photocurable composition, transfer material, cured product, method for producing cured product, method for producing resin pattern, cured film, liquid crystal display device, organic el display device, and touch panel display device Download PDF

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WO2014084190A1
WO2014084190A1 PCT/JP2013/081709 JP2013081709W WO2014084190A1 WO 2014084190 A1 WO2014084190 A1 WO 2014084190A1 JP 2013081709 W JP2013081709 W JP 2013081709W WO 2014084190 A1 WO2014084190 A1 WO 2014084190A1
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group
component
photocurable composition
carbon atoms
acid
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PCT/JP2013/081709
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French (fr)
Japanese (ja)
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藤盛　淳一
中村　秀之
成一 鈴木
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富士フイルム株式会社
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Priority to CN201380061691.XA priority Critical patent/CN104813231B/en
Priority to JP2014550188A priority patent/JP6045603B2/en
Publication of WO2014084190A1 publication Critical patent/WO2014084190A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations

Definitions

  • the present invention relates to a photocurable composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, the transfer material which has the layer of the said photocurable composition, the hardened
  • the present invention relates to a cured film obtained by curing an adhesive composition, and various image display devices using the cured film.
  • a photocurable composition suitable for forming a planarizing film, a protective film or an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, a touch panel display device, an integrated circuit element, and a solid-state imaging device and a method for producing a cured film using the same.
  • An object of the present invention is to provide a photocurable composition that can form a pattern with high resolution and high refractive index and high transmittance.
  • ⁇ 1> (Component A) containing a heterocyclic compound having two or more nitrogen atoms, (Component B) metal oxide particles, (Component C) solvent, and (Component X) a curable component A photocurable composition
  • component A is a compound having a heterocyclic structure having at least a nitrogen atom at the 1,3-position.
  • ⁇ 3> The photocurable composition according to ⁇ 1> or ⁇ 2>, wherein the component A is a compound having a 5-membered or 6-membered heterocyclic structure having at least a nitrogen atom at the 1,3-position.
  • ⁇ 4> The photocurable composition according to any one of ⁇ 1> to ⁇ 3>, wherein the ring member of the heterocyclic ring of component A is composed of a carbon atom and a nitrogen atom, ⁇ 5>
  • component A is a compound represented by the following formula (1):
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and even if R 1 and R 2 are bonded to form a divalent organic group
  • R 3 and R 4 each independently represents a hydrogen atom or a monovalent organic group
  • L 1 represents a divalent linking group forming a 5-membered ring or a 6-membered ring
  • R 3 or R 4 and L 1 may be bonded to form a ring
  • the dotted bond indicates that when the nitrogen-containing double bond described by the dotted line is present, R 2 and R 4 are not present; (If the nitrogen-containing double bond indicated by the dotted line is not present, it represents that R 2 and R 4 are present.)
  • the monovalent organic group represented by R 1 and R 2 is an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 1 to 8 carbon atoms). 6), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an aryl group (preferably having 2 to 20 carbon atoms, more preferably 6 carbon atoms).
  • the monovalent organic groups represented by 3 and R 4 are alkyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 4 carbon atoms), alkenyl groups (preferably having 2 carbon atoms).
  • the photocurable composition according to ⁇ 5> which has 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms, or a heterocyclic group,
  • R 1 and R 2 each independently represent a hydrogen atom or a mercapto group, or R 1 and R 2 are bonded to each other to represent a thioxo group, ⁇ 5> or ⁇ 6 >
  • the photocurable composition as described in> ⁇ 8> The photocurable composition according to any one of ⁇ 5> to ⁇ 7>, wherein in formula (1), R 3 and R 4 are each independently a hydrogen atom, an alkyl group, or an aryl group. , ⁇ 9>
  • R 6 to R 8 each independently represents a hydrogen atom or a monovalent organic group
  • L 2 and L 3 each independently represents a 5-membered ring. Or a divalent linking group forming a 6-membered ring, wherein R 6 and L 2 may be combined to form a ring, and R 7 or R 8 and L 3 are combined to form a ring. You may do it.
  • the monovalent organic group represented by R 6 to R 8 is an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms). More preferably 1 to 4 carbon atoms), an alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an alkynyl group (preferably 2 to 2 carbon atoms).
  • R 6 to R 8 are each independently a hydrogen atom, an alkyl group, or an aryl group.
  • Curable composition ⁇ 14>
  • R 6 to R 8 each independently represents a hydrogen atom, a morpholinomethyl group, or a phenyl group, ⁇ 11> to ⁇ 13>
  • the photocurable composition according to any one of
  • ⁇ 15> The photocurable composition according to any one of ⁇ 1> to ⁇ 14>, wherein the molecular weight of component A is 1,000 or less, ⁇ 16>
  • the photocurable composition according to any one of ⁇ 1> to ⁇ 17> which comprises (Component E) a polymerizable compound and (Component F) a polymerization initiator as Component X.
  • 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.
  • the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
  • 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).
  • “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
  • the photocurable composition of the present invention comprises (Component A) a heterocyclic compound having two or more nitrogen atoms, (Component B) metal oxide particles, (Component C) a solvent, and (Component X) a curable component. It is characterized by containing.
  • the photocurable composition of the present invention can be suitably used as a negative resist composition.
  • the photocurable composition of the present invention is a composition having a property of being cured by light.
  • the photocurable composition of the present invention is a composition for an optical member such as a microlens, an optical waveguide, an antireflection film, an LED sealing material, and an LED chip coating material, or a wiring electrode used for a touch panel.
  • the composition is for reducing visibility.
  • 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 include an interlayer insulating film between ITO (indium tin oxide) electrodes, and the photocurable composition of the present invention can be suitably used for the application.
  • the appearance of the insulating layer (photo insulator, PI) in the bridge-type ITO wiring and the wiring appearance due to indium tin oxide (ITO) have been problems.
  • the difference in refractive index between the ITO and the insulating layer, or the refractive index difference between the ITO and the surrounding glass substrate, overcoat layer, etc. causes a difference in the reflectance of the light. Or it is a phenomenon in which the insulating layer is visible.
  • the refractive index of ITO is as large as about 1.9, and the refractive index of the glass substrate is about 1.5. Therefore, it is estimated that a difference in refractive index occurs and the glass substrate can be visually recognized.
  • metal oxide particles are used as a material having a high refractive index, but in order to increase the refractive index, the metal oxide particles are filled into a composition such as an insulating film, in particular, a high filling of 40 mass% or more
  • a composition such as an insulating film, in particular, a high filling of 40 mass% or more
  • the present inventors have found that, when applied in such a manner, there are many metal oxide particles, and aggregation of the particles cannot be prevented only by the dispersant, so-called aggregation of the metal oxide particles during application occurs. This is somewhat improved by increasing the amount of the dispersant, but it has not been achieved for the purpose of haze of 1% or less as the haze value in the film thickness of the insulating layer.
  • the photocurable composition of the present invention contains (Component A) a heterocyclic compound having two or more nitrogen atoms.
  • Component A adsorbs on the surface of the metal oxide particles to cause electrostatic repulsion and steric repulsion between the metal oxide particles, and in particular to prevent aggregation of the metal oxide when the composition is applied and dried. It is estimated that haze is reduced.
  • Component A is not particularly limited except that it has two or more nitrogen atoms, but is preferably a heterocyclic compound having two or more nitrogen atoms as a ring member of the heterocyclic ring, and nitrogen at the 1,3-position.
  • it is a compound having a heterocyclic structure having at least atoms, more preferably a compound having a 5-membered or 6-membered heterocyclic structure having at least a nitrogen atom at the 1,3-positions, and at 1,3-positions.
  • a compound having a 5-membered heterocyclic structure having at least a nitrogen atom is particularly preferable. If it is the said aspect, the hardened
  • the “heterocyclic structure having at least a nitrogen atom at positions 1 and 3” may be a structure in which nitrogen atoms are bonded to both sides of a carbon atom in the heterocyclic ring.
  • the ring member of the heterocyclic ring in component A is preferably composed of at least a carbon atom and a nitrogen atom, and may further contain an oxygen atom or a sulfur atom as a ring member, but consists of a carbon atom and a nitrogen atom. Is particularly preferred.
  • Component A has 2 or more nitrogen atoms, preferably 2 to 6, and more preferably 2 to 4.
  • Component A preferably has 2 to 4 nitrogen atoms as ring members of the heterocyclic ring, more preferably has 2 or 3 nitrogen atoms, and preferably has 2 nitrogen atoms. Further preferred.
  • the heterocyclic ring in component A may be a saturated heterocyclic ring, an unsaturated heterocyclic ring, or an aromatic heterocyclic ring. Moreover, the heterocyclic ring in Component A may be further condensed with other rings. Moreover, as said other ring, not only a heterocyclic ring but an aliphatic ring or an aromatic ring may be sufficient.
  • Component A may have a nitrogen atom other than the ring member of the heterocyclic ring, but the number of nitrogen atoms other than the ring member of the heterocyclic ring is preferably 0 to 3, preferably 0 to 2. It is preferably 0, more preferably 0, and particularly preferably no nitrogen atoms other than the ring members of the heterocyclic ring.
  • heterocyclic structure of component A include imidazole structure, benzimidazole structure, 1,2,4-triazole structure, 4,5-dihydro-1,2,4-triazole structure, tetrazole structure, 2-imidazoline Preferred examples thereof include a ring structure selected from the group consisting of a structure, 4-imidazoline structure (2,3-dihydroimidazole structure), imidazolidine structure, pyrimidine structure, quinoxaline structure, purine structure, pteridine structure, and perimidine structure, Imidazole structure, benzimidazole structure, 1,2,4-triazole structure, 4,5-dihydro-1,2,4-triazole structure, tetrazole structure, 2-imidazoline structure, 4-imidazoline structure, imidazolidine structure, and A ring structure selected from the group consisting of pyrimidine structures Mentioned
  • benzimidazole structure or imidazolidine structure are exemplified
  • Component A preferably has a mercapto group (—SH) or a thioxo group ( ⁇ S). If it is the said aspect, the hardened
  • Component A is preferably a compound represented by the following formula (1).
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and even if R 1 and R 2 are bonded to form a divalent organic group
  • R 3 and R 4 each independently represents a hydrogen atom or a monovalent organic group
  • L 1 represents a divalent linking group forming a 5-membered ring or a 6-membered ring
  • R 3 or R 4 and L 1 may be bonded to form a ring
  • the dotted bond indicates that when the nitrogen-containing double bond described by the dotted line is present, R 2 and R 4 are not present; (If the nitrogen-containing double bond indicated by the dotted line is not present, it represents that R 2 and R 4 are present.)
  • Examples of the monovalent organic group in R 1 to R 4 include an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, Aryl group, heterocyclic group (also called heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group , Alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonyl Amino group, sulf Mo
  • R 1 and R 2 are each independently preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, or a mercapto group, and preferably a hydrogen atom, a halogen atom, or an alkyl group (preferably having a carbon number of 1 To 20, more preferably 1 to 8, more preferably 1 to 4, and an alkenyl group (preferably 2 to 20, more preferably 2 to 8, more preferably 2 to 4 carbon atoms). ), An aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and still more preferably 6 to 10 carbon atoms), or a mercapto group.
  • the alkyl group, alkenyl group and aryl group may be further substituted with a substituent, for example, an aralkyl group in which the alkyl group is substituted with an aryl group.
  • R 3 and R 4 are each independently preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, preferably a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20 More preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms), an alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), Alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon
  • alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group may be further substituted with a substituent, for example, an aralkyl group in which the alkyl group is substituted with an aryl group.
  • a mercapto group is particularly preferable as the monovalent organic group for R 1 and R 2 .
  • the carbon number of the monovalent organic group in R 1 and R 2 is preferably 0 to 20, more preferably 0 to 8, and particularly preferably 0.
  • the divalent organic group formed by combining R 1 and R 2 include an oxo group, a thioxo group, and an alkylidene group. Of these, a thioxo group is particularly preferable.
  • R 1 and R 2 are each independently preferably a hydrogen atom or a mercapto group, and when R 1 and R 2 are combined to form a divalent organic group, they are thioxo groups. Is particularly preferred.
  • the monovalent organic group in R 3 and R 4 is preferably an alkyl group or an aryl group, and more preferably a morpholinomethyl group or a phenyl group.
  • the alkyl group or aryl group may be substituted with a substituent.
  • the carbon number of the monovalent organic group in R 3 and R 4 is preferably 0 to 20, more preferably 1 to 10, and still more preferably 4 to 8.
  • R 3 and R 4 are each independently preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, a morpholinomethyl group or a phenyl group, and a hydrogen atom or a phenyl group. Further preferred.
  • L 1 represents a divalent linking group forming a 5-membered ring or a 6-membered ring, and forms a heterocyclic ring together with the carbon atom and the two nitrogen atoms in the formula (1).
  • the divalent linking group is not particularly limited as long as it is a group that forms a 5-membered heterocyclic ring or a 6-membered heterocyclic ring with the carbon atom and the two nitrogen atoms in the formula (1).
  • a group formed from a carbon atom and / or a nitrogen atom is preferable, and a group forming a specific example of the heterocyclic structure described above is more preferable.
  • a group that forms a benzimidazole structure, that is, a 1,2-phenylene group, or a group that forms an imidazolidine structure, that is, a 1,2-ethylene group is particularly preferable.
  • component A is more preferably a compound represented by the following formula (1-1) or formula (1-2).
  • R 6 to R 8 each independently represents a hydrogen atom or a monovalent organic group
  • L 2 and L 3 each independently represents a 5-membered ring. Or a divalent linking group forming a 6-membered ring, wherein R 6 and L 2 may be combined to form a ring, and R 7 or R 8 and L 3 are combined to form a ring. You may do it.
  • R 6 to R 8 in formula (1-1) or formula (1-2) have the same meanings as R 3 and R 4 in formula (1), and the preferred embodiments are also the same.
  • L 2 and L 3 in formula (1-1) or formula (1-2) have the same meaning as L 1 in formula (1), and the preferred embodiments are also the same.
  • Preferred specific examples (F-1 to F-14) of component A are shown below. However, the present invention is not limited to these.
  • F-3 to F-11 are preferable, F-3, F-5, F-6 or F-9 is more preferable, and F-5 or F-9 is particularly preferable.
  • the molecular weight of component A is preferably in the range of 68 to 2,000, more preferably 68 to 1,000, still more preferably 100 to 800, and particularly preferably 100 to 500. Various characteristics are favorable in the range of said numerical value.
  • the component A may be used individually by 1 type, and can also use 2 or more types together.
  • the content of Component A in the photocurable composition of the present invention is preferably 0.1 to 20% by mass, based on the total solid content of the photocurable composition of the present invention, preferably 0.5 to 15 More preferably, it is more preferably 0.5 to 10% by mass.
  • the total solid content of the photocurable composition means a component obtained by removing volatile components such as a solvent from the photocurable composition.
  • Component B Metal Oxide Particles
  • the photocurable 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 negative photocurable composition having a high refractive index and excellent transparency can be obtained.
  • Component B preferably has a refractive index higher than the refractive index of a photocurable composition made of a material excluding the particles, and specifically has a refractive index of 1 for light having a wavelength of 400 to 750 nm. More preferably, the particles have a refractive index of 1.70 or more, more preferably 1.90 or more.
  • the upper limit of the refractive index is not particularly limited, but is preferably 4.0 or less, more preferably 3.5 or less, and still more preferably 3.0 or less from the viewpoint of availability.
  • 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 diameter of the metal oxide particles is preferably 1 to 200 nm, more preferably 1 to 100 nm, still more preferably 1 to 80 nm, and particularly preferably 1 to 50 nm. Within the above range, a cured product having excellent particle dispersibility, a high refractive index, and excellent transparency can be obtained.
  • the average primary particle diameter of the metal oxide particles can be obtained from a photograph obtained by observing the dispersed metal oxide particles with a transmission electron microscope. Specifically, the projected area of the metal oxide particles is obtained, and the corresponding equivalent circle diameter is defined as the average primary particle diameter of the metal oxide particles.
  • the average primary particle diameter in this invention be the arithmetic mean value of the equivalent circle diameter calculated
  • the number average particle diameter can also be used as an index of the average primary particle diameter.
  • the number average particle diameter of the metal oxide particles in the present invention is obtained by diluting a mixed solution or dispersion containing the metal oxide particles 80 times with propylene glycol monomethyl ether acetate, and using the obtained diluted solution, a dynamic light scattering method. It means the value obtained by measuring using. This measurement is preferably the number average particle diameter obtained by using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd.
  • the refractive index of the metal oxide particles is not particularly limited, but is preferably 1.70 to 2.70, more preferably 1.90 to 2.70 from the viewpoint of obtaining a high refractive index. .
  • the specific surface area of the metal oxide particles is preferably 10 ⁇ 400m 2 / g, more preferably from 20 ⁇ 200m 2 / g, and most preferably 30 ⁇ 150m 2 / g.
  • the metal oxide particles may have been surface-treated with an organic compound.
  • organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, stearic acid is preferred.
  • the surface treatment may be carried out by using a single surface treatment agent or a combination of two or more surface treatment agents. It is also preferable that the surface of the metal oxide particles is covered with an oxide such as aluminum, silicon, or zirconia. Thereby, a weather resistance improves more.
  • metal oxide particles in the present invention commercially available particles can be preferably used. Specifically, for example, TTO series (TTO-51 (A), TTO-51 (C), etc.), TTO-S, V series (TTO-S-1, TTO) manufactured by Ishihara Sangyo Co., Ltd. are used as titanium oxide particles.
  • MT series (MT-01, MT-05, etc.) manufactured by Teika Co., Ltd.
  • the component B 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 photocurable composition of the present invention may be appropriately determined in consideration of the refractive index required for the optical member obtained from the photocurable composition, light transmittance, and the like. However, it is preferable that it is 10 mass% or more with respect to the total solid of the photocurable composition of this invention, It is more preferable that it is 30 mass% or more, It is still more preferable that it is 40 mass% or more. Moreover, it is preferable that it is 80 mass% or less, and it is more preferable that it is 70 mass% or less.
  • the particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill.
  • a mixing device such as a ball mill or a rod mill.
  • the dispersant will be described later.
  • the solvent used in the preparation of the dispersion include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, in addition to the (Component C) solvent described below.
  • -Alcohols such as pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol, etc. Can be mentioned.
  • solvent can be used individually by 1 type or in mixture of 2 or more types.
  • the photocurable composition of the present invention contains (Component C) a solvent.
  • the photocurable composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in the (component C) solvent.
  • 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. Further, specific examples of the solvent used in the photocurable composition of the present invention include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A.
  • Component C 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 C) solvent in the photocurable composition of the present invention is preferably 50 to 95 parts by mass, preferably 60 to 90 parts by mass, per 100 parts by mass of the solid content in the photocurable composition. More preferably it is.
  • the photocurable composition of the present invention preferably contains (Component D) a dispersant.
  • a dispersing agent By containing a dispersing agent, the dispersibility in the composition of the component B can be improved more.
  • the (Component D) dispersant for example, a known pigment dispersant can be appropriately selected and used.
  • (Component S) A dispersion represented by the formula (S) described later and having at least one acid group Agents are particularly preferred.
  • a polymer dispersant can be preferably used.
  • the polymer dispersant is a dispersant having a molecular weight (weight average molecular weight) of 1,000 or more.
  • Component D As the dispersant, many types of compounds can be used. Specifically, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) Polymer Polyflow No. 75, no. 90, no.
  • Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl
  • Nonionic surfactants such as ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester
  • anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), DE Polymer dispersing agents such as Sparse Aid 6, Disperse Aid
  • the photocurable composition of the present invention preferably contains (Component S) a dispersant represented by the following formula (S) and having at least one acid group as (Component D) a dispersant. Since the photocurable 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 at a high rate.
  • 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, hydrocarbon group having 4 or more carbon atoms, alkoxysilyl group, epoxy group, isocyanate group and hydroxyl group Represents a monovalent organic group containing at least one partial structure selected from the group, n A 2 and R 4 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, and m P 2 and R 5 may be the same or different.
  • 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, or a group having 4 or more carbon atoms.
  • 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.
  • a monovalent containing at least one functional group capable of adsorbing to metal oxide particles such as a group having an atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. Represents an organic group.
  • 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. It is a monovalent organic group formed by bonding together oxygen atoms, 1 to 400 hydrogen atoms, and a linking group consisting of 0 to 40 sulfur atoms.
  • the adsorption sites themselves may constitute a monovalent organic group, the 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 contains at least one nitrogen atom. More preferred.
  • 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, acridone And a heterocyclic ring selected from the group consisting of anthraquinon
  • the “organic dye structure” or “heterocyclic structure” may further have a substituent.
  • substituents include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, An aryl group having 6 to 16 carbon atoms such as phenyl group and naphthyl group, an acyloxy group having 1 to 6 carbon atoms such as hydroxyl group, amino group, carboxy group, sulfonamide group, N-sulfonylamide group and acetoxy group, methoxy group, An alkoxy group having 1 to 20 carbon atoms such as an ethoxy group, a halogen atom such as a chlorine atom and a bromine atom, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a cyano group, and carbonic acid este
  • 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, an aryl group having 6 to 20 carbon atoms, Preferred examples include aralkyl groups having 7 to 20 carbon atoms.), Guanidyl groups represented by the following formula (a1), amidinyl groups 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 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and an alkyl having 1 to 20 carbon atoms Group, aryl group having 6 to 20 carbon atoms, and other aralkyl groups having 7 to 20 carbon atoms are preferable.
  • 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, and an alkyl having 1 to 20 carbon atoms Group, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms are preferable.
  • 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 group having 1 to 10 carbon atoms.
  • a phenyl group and a benzyl group and a guanidyl group represented by the above formula (a1) (in the formula (a1), R 11 and R 12 are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group.
  • Amidinyl group represented by the above formula (a2) (in the formula (a2), R 13 and R 14 are each independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, a benzyl group). And the like are more preferable.
  • 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 group having 1 to 5 carbon atoms, phenyl A benzyl group), a guanidyl group represented by the above formula (a1) (in the formula (a1), R 11 and R 12 are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group, benzyl Amidinyl group represented by the above formula (a2) (in the formula (a2), R 13 and R 14 each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group).
  • Etc. are preferably used.
  • urea group examples 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, 6 or more carbon atoms). Or an aryl group having 7 or more carbon atoms, 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 is preferable.
  • R 15 and R 17 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or 7 or more carbon atoms) More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms), and —NHCONHR 17 (where R 17 is hydrogen source Represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or And an aralkyl group having 7 to 12 carbon atoms is preferred).
  • 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).
  • Group, an aralkyl group having 7 to 20 carbon atoms is preferred) and the like.
  • R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms).
  • R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms.
  • R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms.
  • R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms.
  • R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms.
  • R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms.
  • R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms.
  • R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms.
  • R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms.
  • R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms.
  • R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms.
  • -NHCOOR 18, -OCONHR 21 are each independently an alkyl group having 6 or more aryl group having a carbon number of 1 to 10 carbon atoms, or, to 7 carbon atoms
  • R 18 and R 21 are each independently an alkyl group having 6 or more aryl group having a carbon number of 1 to 10 carbon atoms, or, to 7 carbon atoms
  • the above aralkyl groups are preferred, and an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms are preferred.
  • Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a group having a crown ether structure.
  • hydrocarbon group having 4 or more carbon atoms include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferably, an alkyl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and 6 to 15 carbon atoms. Particularly preferred are aryl groups such as phenyl group and naphthyl group, and aralkyl groups having 7 to 15 carbon atoms (such as benzyl group).
  • alkoxysilyl group examples include a trimethoxysilyl group and a triethoxysilyl group.
  • the linking group bonded to the adsorption site is a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms.
  • a linking group consisting of 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, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, and a hydroxyl group.
  • An acyloxy group having 1 to 6 carbon atoms such as amino group, carboxy group, sulfonamido group, N-sulfonylamide group and acetoxy group, alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group, chlorine atom, bromine
  • alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group
  • Examples thereof include halogen atoms such as atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, and cyclohexyloxycarbonyl group, and carbonate ester groups such as cyano group and t-butyl carbonate group.
  • an organic dye structure an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, and carbonization of 4 or more carbon atoms (preferably 4 to 20 carbon atoms)
  • a monovalent organic group containing at least one partial structure selected from the group consisting of hydrogen groups is preferred, and a monovalent organic group containing at least one acid group is particularly preferred.
  • a 2 and 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, and a hydrocarbon group having 4 or more carbon atoms is preferable, and an acid group is particularly preferable preferable.
  • 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.
  • the (a + 1) -valent linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 Groups comprised of up to 20 sulfur atoms are included and may be unsubstituted or further substituted.
  • (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 is 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 0 (A + 1) -valent linking groups consisting of ⁇ 10 sulfur atoms are preferred, a single bond, or 1-30 carbon atoms, 0-6 nitrogen atoms, 0-15 oxygen atoms, (A + 1) -valent linking group consisting of 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms is more preferred, a single bond or 1 to 10 carbon atoms, 0 to 5 (A + 1) -valent linking group consisting of 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms is particularly preferred.
  • 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 6 to 16 aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., C1-C6 acyloxy groups, methoxy groups, ethoxy groups, etc.
  • Alkoxy groups such as chlorine atoms and bromine atoms, C2-C7 alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexyloxycarbonyl groups, carbonate esters such as cyano groups and t-butyl carbonate groups Group, and the like.
  • 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.
  • the divalent linking group for R 4 and R 5 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 consisting of 0 to 20 sulfur atoms is included, which 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 hydrogen atoms.
  • a divalent linking group consisting of an atom and 0 to 10 sulfur atoms is preferred, a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 And more preferably a divalent linking group comprising 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms, a single bond, or 1 to 10 carbon atoms, 0 to Particularly preferred is a divalent linking group consisting of 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms.
  • the divalent linking group has a substituent
  • substituents include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and 6 to 6 carbon atoms such as a phenyl group and a naphthyl group.
  • R 3 represents a (m + n) -valent linking group.
  • m + n satisfies 3 to 10.
  • Examples of the (m + n) -valent linking group represented by R 3 include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100 carbon atoms.
  • a group consisting of a hydrogen atom and 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.
  • (m + n) -valent linking group examples include the following structural units or groups formed by combining the structural units (which may form a ring structure).
  • the (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 0 Preferred are groups consisting of ⁇ 10 sulfur atoms, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and More preferred are groups consisting of 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, and 1 to 80 hydrogen atoms. And groups consisting of 0 to 5 sulfur atoms are particularly preferred.
  • examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon number such as a phenyl group and a naphthyl group. 1 to 6 carbon atoms such as 6 to 16 aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., C1-C6 acyloxy groups, methoxy groups, ethoxy groups, etc.
  • Alkoxy groups halogen atoms such as chlorine atoms and bromine atoms, C2-C7 alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexyloxycarbonyl groups, carbonate esters such as cyano groups and t-butyl carbonate groups Groups and the like.
  • 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 polymer skeleton.
  • 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 one or more acid groups, for example, a carboxy 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 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.
  • 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 oxygen atoms
  • an alkyl group having 1 to 20 carbon atoms such as a group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxy group, a sulfonamido group, an N-s
  • C1-C6 acyloxy group C1-C6 alkoxy group such as methoxy group, ethoxy group, halogen atom such as chlorine atom, bromine atom, methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl Alkoxycarbonyl group having 2 to 7 carbon atoms like, a cyano group, or the like carbonate group such as t- butyl carbonate group.
  • 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 photocurable composition is obtained, and when the acid value is 300 mgKOH / g or less, the dispersibility and dispersion stability of the metal oxide particles are improved. Excellent.
  • 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 photocurable composition of the present invention may be one type or two or more types. In the case of two or more types, the total is preferably in the above range.
  • the exemplary compound of the component S is mentioned below, this invention is not limited to this, As long as it is included by Formula (S), it can take arbitrary structures. Moreover, in the following exemplary compound, P1 and P2 can take arbitrary values, respectively.
  • the sulfur atom bonded to the polymer skeleton (P 2 ) composed of a monomer unit having a carboxylic acid ester and a monomer unit having a carboxy group may be bonded to any monomer unit,
  • the other terminal that is not bonded to the sulfur atom of the polymer skeleton is not described in the following chemical formula, but may be any atom or group that is usually allowed at the terminal of the polymer skeleton.
  • the content ratio of the monomer unit having a carboxylic acid ester to the monomer unit having a carboxy group in the polymer skeleton (P1 : P2) is preferably in the range of 100: 0 to 80:20 in terms of mass.
  • Component S can be synthesized, for example, with reference to the method described in Japanese Patent No. 5036269.
  • a dispersing agent may be used individually by 1 type, or may be used together 2 or more types.
  • the content of the dispersant in the photocurable 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 photocurable composition.
  • the photocurable composition of the present invention contains (Component X) a curable component.
  • the photocurable composition of the present invention is suitable as a negative resist composition, and (1) a polymerization reaction or (2) a crosslinking reaction occurs upon irradiation with light (active light). It is preferable to cure.
  • a case where the photocurable composition is cured by a polymerization reaction is referred to as a “polymerization system”
  • a case where the photocurable composition is cured by a crosslinking reaction is referred to as a “crosslinking system”.
  • the photocurable composition of the present invention may be either a polymerization system or a crosslinking system, and both may be generated at the same time, but is preferably a polymerization system photocurable composition.
  • the photocurable composition contains (Component E) a polymerizable compound and (Component F) a polymerization initiator as (Component X) a curable component.
  • Component M an alkali-soluble resin
  • Component N a crosslinking agent
  • Component O an acid generator
  • the photocurable composition of the present invention generates a polymerization initiation species such as a radical or a cation by irradiation with actinic rays, and curing occurs due to a polymerization reaction caused thereby.
  • a polymerization initiation species such as a radical or a cation by irradiation with actinic rays
  • curing occurs due to a polymerization reaction caused thereby.
  • an acid is generated from the acid generator upon irradiation with actinic rays, and the action of this acid forms a bridge between the alkali-soluble resin and the crosslinking agent and cures.
  • each component will be described separately for a polymerization system and a crosslinking system.
  • (Component E) Polymerizable Compound when the photocurable composition is a polymerization system, (Component X) a polymerizable compound is contained as the (Component X) curable component.
  • the polymerizable compound any of a radical polymerizable compound and a cationic polymerizable compound can be used. From the viewpoint of curability and resolution, a radical polymerizable compound is preferable.
  • the (Component E) polymerizable compound in the present invention is preferably an addition polymerizable compound having at least one ethylenically unsaturated double bond, and preferably has at least one terminal ethylenically unsaturated bond, preferably two. More preferably, it is selected from the compounds having the above. Such compounds are widely known in the technical field, and can be used without particular limitation in the present invention.
  • monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters and amides thereof for example, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.
  • an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and A dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid is also preferably used.
  • a substitution reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a leaving group such as a halogen group or a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. It is.
  • ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol.
  • Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxyp Epoxy) phenyl] dimethyl methane, bis - [p- (me
  • Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
  • crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
  • isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
  • maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
  • esters examples include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are preferably used. Furthermore, the ester monomers described above can also be used as a mixture.
  • amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
  • examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.
  • urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708.
  • a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer having a hydroxyl group represented by the following formula (V) to a polyisocyanate compound having two or more isocyanate groups: Etc.
  • R 7 and R 8 each independently represents a hydrogen atom or a methyl group.
  • urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable.
  • polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a photo-curable composition having an excellent photosensitive speed.
  • polyester acrylates examples include polyester acrylates, epoxy resins and (meth) acrylic acid described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reaction. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol.
  • photocurable monomers and oligomers described on pages 300 to 308 (1984) can also be used.
  • a monomer having a fluorene skeleton is also preferably used.
  • 9,9-bisphenoxyfluorene skeleton is preferable.
  • Specific examples include, for example, EA-0200, EA-F5003, EA-F5503, EA-F5510 (manufactured by Osaka Gas Chemical Co., Ltd.), NK ester A-BPEF, NK ester A-BPEF-4E (Shin Nakamura Chemical). Kogyo Co., Ltd.).
  • the details of the usage method such as the structure, single use or combination, addition amount and the like can be arbitrarily set according to the final performance design of the photocurable composition.
  • it is selected from the following viewpoints.
  • a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable.
  • those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound).
  • a method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
  • the selection and use method of the polymerizable compound is important for the compatibility and dispersibility with other components (for example, polymerization initiator, metal oxide particles, etc.) contained in the photocurable composition.
  • compatibility may be improved by using a low-purity compound or using two or more other components in combination.
  • a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a substrate.
  • the content of the (Component E) polymerizable compound in the total solid content of the photocurable composition is preferably in the range of 5% by mass to 90% by mass, and in the range of 10% by mass to 85% by mass. Is more preferable, and the range of 20% by mass to 80% by mass is even more preferable. Within this range, both adhesion sensitivity and developability are good and preferable without lowering the refractive index.
  • (Component F) Polymerization initiator when a photocurable composition is a polymerization system, it is preferable to contain (Component F) a polymerization initiator as (Component X) curable component.
  • the (component F) polymerization initiator used in the present invention is a compound that is decomposed by light and initiates and accelerates polymerization of the (component E) polymerizable compound, and has an absorption in a wavelength region of 300 nm to 500 nm. Preferably there is.
  • a polymerization initiator can be used individually or in combination of 2 or more types.
  • Component F examples of the polymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds. , Hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.
  • Examples of the compound and the disulfonic acid compound include compounds described in paragraphs 0135 to 0149 of JP 2010-106268 A.
  • Examples of the onium salt compound and the acylphosphine (oxide) compound include compounds described in paragraphs 0220 to 0224 of JP-A-2010-106268.
  • an oxime compound is preferable from the viewpoints of sensitivity, stability over time, and coloring during post-heating.
  • oxime compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.
  • a compound represented by the following formula (1) (hereinafter also referred to as “specific oxime compound”) is preferable.
  • the specific oxime compound is a mixture of the (E) isomer and the (Z) isomer, regardless of whether the oxime N—O bond is an (E) oxime compound or a (Z) oxime compound. It may be.
  • R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
  • Phosphinoyl group heterocyclic group, alkylthiocarbonyl group, arylthiocarbonyl group, dialkylaminocarbonyl group, dialkylaminothiocarbonyl group and the like. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
  • substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group , Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group or aryloxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, Acyl groups such as methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfany
  • the alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a decyl group.
  • the aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specifically includes a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-anthryl group.
  • 9-phenanthryl group 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, Anthracenyl group, quarter anthracenyl group, anthraquinolyl group,
  • the alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and specific examples include a vinyl group, an allyl group, and a styryl group.
  • the alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and specific examples include an ethynyl group, a propynyl group, and a propargyl group.
  • the alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specifically includes a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group.
  • hexylsulfinyl group cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, and methoxymethylsulfinyl group.
  • the arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2- Chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitro Phenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methyls
  • the alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specifically includes a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group.
  • alkylsulfonyl group hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, and perfluoro An alkylsulfonyl group can be illustrated.
  • the arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, 2- Chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitro Phenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group
  • the acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenz
  • the alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specifically includes a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.
  • the phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, specifically, a dimethylphosphinoyl group, a diethylphosphinoyl group, a dipropylphosphinoyl group, a diphenyl group.
  • Examples thereof include a phosphinoyl group, a dimethoxyphosphinoyl group, a diethoxyphosphinoyl group, a dibenzoylphosphinoyl group, and a bis (2,4,6-trimethylphenyl) phosphinoyl group.
  • the heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
  • thienyl group benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, pur
  • alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group.
  • Examples thereof include a group and a trifluoromethylthiocarbonyl group.
  • dialkylaminocarbonyl group examples include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.
  • dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.
  • R is more preferably an acyl group, and specifically, an acetyl group, a propanoyl group, a benzoyl group, and a toluoyl group are more preferable.
  • the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent. Among them, the structure shown below is particularly preferable. In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.
  • Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent. Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating.
  • an alkylene substituted with an unsubstituted alkylene group or an alkyl group for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group
  • alkylene group substituted with alkenyl group for example, vinyl group, allyl group
  • aryl group for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group
  • alkylene group substituted with alkenyl group for example, vinyl group, allyl group
  • aryl group for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group
  • the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.
  • substituents include the above-described substituents. Specifically, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group , 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group , Quarternaphthalenyl group, heptalenyl group, biphenylenyl group, ind
  • the structure of “SAr” formed by the Ar and the adjacent S is the following structure.
  • Me represents a methyl group
  • Et represents an ethyl group.
  • the specific oxime compound in the present invention is preferably a compound represented by the following formula (2).
  • R and X each independently represent a monovalent substituent
  • a and Y each independently represent a divalent organic group
  • Ar represents an aryl group
  • n represents 0-5.
  • R, A, and Ar in the formula (2) have the same meanings as R, A, and Ar in the formula (1), and preferred examples are also the same.
  • Examples of the monovalent substituent represented by X include an alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, acyloxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group. Group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, amino group, phosphinoyl group, heterocyclic group and halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
  • the group is an alkyl group of R in the above formula (1), an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group.
  • Phosphinoyl group and heterocyclic group and the preferred range is also the same.
  • the alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, and specifically includes a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.
  • Pentyloxy isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, dodecyloxy, octadecyloxy, ethoxycarbonylmethyl, 2-ethylhexyloxycarbonylmethyl Oxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethylo group Shi group, N- methyl -N- benzylaminocarbonyl methyl group, a benzyl group, and a cyano methyl group can be exemplified.
  • the aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms, and specifically includes a phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-chlorophenyloxy group, 2-methylphenyloxy group.
  • the acyloxy group is preferably an acyloxy group having 2 to 20 carbon atoms, and specifically includes an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, a trifluoromethylcarbonyloxy group, a benzoyloxy group. , 1-naphthylcarbonyloxy group and 2-naphthylcarbonyloxy group.
  • the alkylsulfanyl group is preferably an alkylsulfanyl group having 1 to 20 carbon atoms, and specifically includes a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, and a cyclohexylsulfanyl group.
  • Octylsulfanyl group 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, and methoxymethylsulfanyl group.
  • the arylsulfanyl group is preferably an arylsulfanyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group.
  • the carbamoyl group is preferably a carbamoyl group having 1 to 30 carbon atoms, and specifically includes an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, an N-butylcarbamoyl group, and an N-hexylcarbamoyl group.
  • the sulfamoyl group is preferably a sulfamoyl group having 0 to 30 carbon atoms, specifically, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an N, N-dialkylsulfamoyl group. N, N-diarylsulfamoyl group and N-alkyl-N-arylsulfamoyl group.
  • N-methylsulfamoyl group More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group.
  • Famoyl group N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4
  • the amino group is preferably an amino group having 0 to 50 carbon atoms, and specifically includes an amino group (—NH 2 ), an N-alkylamino group, an N-arylamino group, an N-acylamino group, an N-sulfonyl group.
  • an amino group —NH 2
  • N-alkylamino group an N-arylamino group
  • N-acylamino group an N-sulfonyl group.
  • Examples thereof include an amino group, an N, N-dialkylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, and an N, N-disulfonylamino group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • X is an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylsulfanyl group, an arylsulfanyl group, from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region, An amino group is preferred.
  • n represents an integer of 0 to 5, and an integer of 0 to 2 is preferable.
  • Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “*” represents the bonding position between Y and the adjacent carbon atom in the above formula (2).
  • the specific oxime compound in the present invention is preferably a compound represented by the following formula (3).
  • R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5.
  • R, X, A, Ar, and n in the formula (3) have the same meanings as R, X, A, Ar, and n in the formula (2), respectively, and preferred examples are also the same.
  • the specific oxime compound is decomposed by light and has a function as a photopolymerization initiator that initiates and accelerates the polymerization of the photopolymerizable compound.
  • the oxime compound has excellent sensitivity to a light source of 365 nm or 405 nm.
  • trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of methyltriazine compounds, ⁇ -aminoketone compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds.
  • the photocurable composition of the present invention when used for the production of an optical member such as a solid-state imaging device or a liquid crystal display device, it is necessary to form a fine pattern with a sharp shape. It is important that the unexposed area is developed without residue. From such a viewpoint, an oxime compound is particularly preferable.
  • a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of a polymerization initiator low.
  • an oxime compound as the polymerization initiator (Component F) in order to form a fine pattern such as a solid-state imaging device.
  • the content of (Component F) polymerization initiator contained in the photocurable composition of the present invention is preferably 0.1% by mass or more and 50% by mass or less with respect to the total solid content of the photocurable composition. More preferably, they are 0.5 mass% or more and 30 mass% or less, More preferably, they are 1 mass% or more and 20 mass% or less. Within this range, good sensitivity and pattern formability can be obtained.
  • the photocurable composition of the present invention contains (Component G) a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. You may do it.
  • the sensitizer that can be used in the present invention those that sensitize the above-described (Component F) polymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.
  • sensitizer examples include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm. That is, for example, polynuclear aromatics (eg, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), Thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, Toluidine blue), acridines (eg
  • a sensitizer may be used individually by 1 type and may use 2 or more types together.
  • the content of the sensitizer in the photocurable composition is 0.1% by mass or more and 20% by mass or less in terms of solid content from the viewpoint of light absorption efficiency in the deep part and decomposition efficiency of the initiator. Preferably, it is 0.5 mass% or more and 15 mass% or less.
  • the photocurable composition of the present invention preferably further contains (Component I) a co-sensitizer.
  • the co-sensitizer further improves the sensitivity of (component F) polymerization initiator and (component G) sensitizer to active radiation, or suppresses inhibition of polymerization of (component E) polymerizable compound by oxygen. It has an effect such as.
  • co-sensitizers examples include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.
  • co-sensitizers include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- And a hydrogen donor described in JP 34414 and a sulfur compound (eg, trithiane) described in JP-A-6-308727.
  • amino acid compounds eg, N-phenylglycine
  • organometallic compounds described in JP-B-48-42965 eg, tributyltin acetate
  • a hydrogen donor described in JP 34414
  • a sulfur compound eg, trithiane
  • the content of these co-sensitizers is 0.1% by mass or more and 30% by mass with respect to the mass of the total solid content of the photocurable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer.
  • the following ranges are preferable, the range of 1% by mass to 25% by mass is more preferable, and the range of 1.5% by mass to 20% by mass is more preferable.
  • (Component J) Polymerization inhibitor in the present invention, (Component J) a polymerization inhibitor may be added in order to prevent unnecessary polymerization of the polymerizable compound during the production or storage of the photocurable composition.
  • Polymerization inhibitors that can be used in the present invention include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium Examples include compounds, and cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, and transition metal compounds such as FeCl 3 and CuCl 2 .
  • polymerization inhibitor hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol) phenolic hydroxyl group-containing compound, piperidine 1-oxyl free radical compound, or 2,2,6,6-tetramethylpiperidine 1-oxyl free radical 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2 , 6,6-Tetramethylpiperidine 1-oxyl free radical, 4- Piperidine 1-oxyl free radical compound of maleimide-2,2,6,6-tetramethylpiperidine 1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl
  • a preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.01 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the (Component F) polymerization initiator. It is more preferable that it is 0.05 to 5 parts by mass.
  • (Component K) Binder Polymer When the photocurable composition of the present invention is a polymerization system, it is preferable that it further contains (Component K) at least one binder polymer from the viewpoint of improving resolution and film properties. .
  • a linear organic polymer As the (component K) binder polymer, a linear organic polymer is preferably used. As such a linear organic polymer, a well-known thing can be used arbitrarily.
  • a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development.
  • the linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer.
  • a water-soluble organic polymer when used, water development becomes possible.
  • linear organic polymer examples include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. No.
  • a monomer having a carboxyl group alone or Copolymerized resin acid anhydride monomer alone or copolymerized, acid anhydride unit hydrolyzed, half esterified or half amidated, epoxy resin unsaturated monocarboxylic acid and acid anhydride
  • Examples include modified epoxy acrylate.
  • Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene.
  • the monomer having an acid anhydride include maleic anhydride. It is done.
  • there is an acidic cellulose derivative having a carboxylic acid group in the side chain there is an acidic cellulose derivative having a carboxylic acid group in the side chain.
  • those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
  • a monomer other than the monomers listed above can also be used as the compound to be copolymerized.
  • examples of other monomers include the following compounds (1) to (12).
  • Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
  • Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
  • Styrenes such as styrene, ⁇ -methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
  • Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
  • Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.
  • N-vinylpyrrolidone (10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
  • Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
  • a methacrylic acid monomer having a hetero atom bonded to the ⁇ -position For example, compounds described in JP-A-2002-309057 and JP-A-2002-311569 can be mentioned.
  • a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain, and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled.
  • An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.
  • Japanese Patent Publication No. 7-12004 Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication No. 63-287947.
  • Urethane binder polymers containing acid groups as described in JP-A-1-271741 and the like, and urethane binders having acid groups and double bonds in side chains as described in JP-A-2002-107918 Since the polymer is excellent in strength, it is advantageous in terms of film strength and suitability for low exposure.
  • Japanese Patent Application Laid-Open No. 2001-318463 has an excellent balance of film strength and developability. Is preferred.
  • polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer.
  • alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin are also useful.
  • the weight average molecular weight of the binder polymer that can be used in the photocurable composition of the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably Is 1,000 or more, and more preferably 2,000 or more and 250,000 or less.
  • the polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.
  • These binder polymers may be any of random polymers, block polymers, graft polymers and the like.
  • the binder polymer that can be used in the present invention can be synthesized by a conventionally known method.
  • the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy.
  • Examples include -2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.
  • Examples of the radical polymerization initiator used when synthesizing the binder polymer that can be used in the photocurable composition of the present invention include known compounds such as an azo initiator and a peroxide initiator.
  • the content of the binder polymer is preferably 1% by mass or more and 40% by mass or less, more preferably 3% by mass or more and 30% by mass or less, and more preferably 4% by mass. More preferably, it is 20 mass% or less.
  • (Component L) Adhesion Improving Agent In the photocurable composition of the present invention, (Component L) an adhesion improving agent can be added in order to improve the adhesion to a hard surface such as a substrate.
  • the adhesion improving agent include a silane coupling agent and a titanium coupling agent.
  • silane coupling agents include ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropyldimethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxy.
  • Silane ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyl Triethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride, ⁇ -glycidoxyp Propyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, aminosilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltrie
  • ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferred, and ⁇ -methacryloxypropyltrimethoxysilane is most preferred.
  • the addition amount of the adhesion improver is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 0.7% by mass or more and 20% by mass or less in the total solid content of the photocurable composition.
  • additives such as ultraviolet absorbers, plasticizers, surfactants, and sensitizers may be added to the photocurable composition.
  • the photocurable composition of the present invention may contain 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.
  • fluorine surfactants and silicone surfactants include JP-A Nos. 62-36663, 61-226746, 61-226745, and 62-170950.
  • 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 (K-1), and the weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
  • K-1 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 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.
  • L is preferably a branched alkylene group represented by the following formula (K-2).
  • R 405 in formula (K-2) represents an alkyl group having 1 to 3 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 photocurable 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 photocurable composition. More preferably, the amount is 0.01 to 3 parts by mass.
  • the photocurable composition of the present invention can contain a development accelerator.
  • a development accelerator any compound having a development acceleration effect can be used, and the development accelerator may be a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group.
  • a compound having a carboxyl group or a phenolic hydroxyl group is more preferable, and a compound having a phenolic hydroxyl group is most preferable.
  • 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 photocurable composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photocurable composition, from the viewpoint of sensitivity and residual film ratio. More preferably, it is 1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass.
  • the photocurable composition of the present invention may contain a plasticizer.
  • the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
  • the content of the plasticizer in the photocurable composition of the present invention is preferably 0.1 to 30 parts by mass and preferably 1 to 10 parts by mass with respect to 100 parts by mass of the solid content excluding Component B. Is more 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.
  • crosslinking system (component M) alkali-soluble resin
  • component M alkali-soluble resin
  • component X curable component
  • Component M is not particularly limited, but is preferably a phenolic resin.
  • the phenolic resin is a resin obtained using phenol or a substituted phenol as a raw material. Specifically, (Component M-1) polyhydroxystyrenes, (Component M-2) novolak resin, and (Component M-3) are used. ) Partially alkyl etherified polyvinylphenol and partially alkyl etherified hydrogenated polyvinylphenol. Each will be described below.
  • Component M-1 Polyhydroxystyrenes
  • Polyhydroxystyrenes are hydroxystyrene homopolymers or copolymers with other monomers, and are alkali-soluble resins having a hydroxystyrene unit content of 30 mol% or more.
  • Component M-1 is an alkali-soluble resin having a hydroxystyrene unit content of 30 to 100 mol%, and the hydroxystyrene unit content is preferably 50 to 100 mol%, preferably 70 to 100 mol%. More preferably, it is more preferably 90 to 100 mol%.
  • the solubility in an alkali developer is good, and the developability and resolution are excellent.
  • hydroxystyrene in Component M-1 examples include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, and these hydroxystyrenes can be used alone or in admixture of two or more. Further, if necessary, hydroxystyrene and other unsaturated monomers may be copolymerized.
  • Examples of the other unsaturated monomers include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, and vinylxylene; (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, Unsaturated carboxylic acids such as benzyl (meth) acrylate, phenyl (meth) acrylate, methyl crotonate, methyl cinnamate, dimethyl maleate and dimethyl fumarate and esters thereof; (meth) acrylonitrile; vinylidene cyanide, ⁇ -chloro Examples are vinyl cyanide compounds such as acrylonitrile.
  • styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate are preferable, and styrene, methyl (meth) acrylate, n-Butyl (meth) acrylate and t-butyl (meth) acrylate are more preferable, and styrene and methyl (meth) acrylate are more preferable.
  • Other unsaturated monomers can be used alone or in admixture of two or more.
  • component M-1 examples include poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene), p-hydroxystyrene / o-hydroxystyrene copolymer, p-hydroxy.
  • hydroxystyrenes such as styrene / m-hydroxystyrene copolymers, o-hydroxystyrene / styrene copolymers, o-hydroxystyrene / ⁇ -methylstyrene copolymers, m-hydroxystyrene / Styrene copolymer, m-hydroxystyrene / ⁇ -methylstyrene copolymer, p-hydroxystyrene / styrene copolymer, p-hydroxystyrene / ⁇ -methylstyrene copolymer, p-hydroxystyrene / methyl (meta ) Acrylate copolymer, p-hydroxystyrene / ethyl (meth) acryl Copolymer, p-hydroxystyrene / n-propyl (meth) acryl
  • modified polyhydroxystyrenes obtained by modifying a part of the hydroxyl group derived from hydroxystyrene may be used. More specifically, those obtained by reacting the hydroxystyrenes with a benzenesulfonyl chloride derivative, a naphthalenesulfonyl chloride derivative, a benzenecarbonyl chloride derivative, a naphthalenecarbonyl chloride derivative or the like in a basic catalyst are exemplified.
  • the sulfonyl chloride derivative or the carbonyl chloride derivative is preferably used in an amount of 10 to 30 parts by mass, more preferably 15 to 25 parts by mass with respect to 100 parts by mass of the polyhydroxystyrenes.
  • Specific examples of the above sulfonyl chloride derivatives and carbonyl chloride derivatives include p-acetaminobenzenesulfonyl chloride, benzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, naphthylbenzenesulfonyl chloride, p-acetaminobenzenecarbonyl chloride, benzenecarbonyl.
  • Examples include chloride, p-chlorobenzenecarbonyl chloride, naphthylbenzenecarbonyl chloride, and the like.
  • Component M-1 a part of the benzene ring of the monomer unit derived from hydroxystyrene or the monomer unit modified from this may be hydrogenated.
  • component M-1 poly (p-hydroxystyrene), p-hydroxystyrene / styrene copolymer, p-hydroxystyrene / methyl methacrylate copolymer, p-hydroxystyrene / n-butyl acrylate A copolymer, a p-hydroxystyrene / t-butyl methacrylate copolymer, and the like are particularly preferable, and poly (p-hydroxystyrene) is most preferable.
  • Component M-1 can be used alone or in admixture of two or more.
  • the production method of component M-1 includes, for example, (i) a monomer in which the hydroxyl group of hydroxystyrene is protected, such as butoxycarbonyloxystyrene, butoxystyrene, acetoxystyrene, tetrahydropyranyloxystyrene, and other unsaturated monomers depending on the case.
  • an acid catalyst or an alkali catalyst is allowed to act to hydrolyze the protective group to obtain a (co) polymer of hydroxystyrene.
  • the method of addition polymerization can be mentioned with the unsaturated monomer, the method (i) is preferred.
  • the above addition polymerization can be carried out by an appropriate method such as radical polymerization, anionic polymerization, cationic polymerization, thermal polymerization, etc., but the method based on anionic polymerization or cationic polymerization can reduce the degree of dispersion of the resulting resin.
  • the acid catalyst include inorganic acids such as hydrochloric acid and sulfuric acid.
  • the alkali catalyst include sodium hydroxide and potassium hydroxide.
  • Component M-2 Novolak Resin
  • Component M-2 novolac resin
  • the novolak resin is obtained by condensing a phenolic compound and an aldehyde in the presence of an acid catalyst or an alkali catalyst.
  • the phenolic compound used for the production of the novolak resin is an aromatic compound having a phenolic hydroxyl group, for example, phenol, o-, m- or p-cresol, 2,3-, 2,5-, 3,4 -Or 3,5-xylenol, 2,3,5-trimethylphenol, 2-, 3- or 4-tert-butylphenol, 2-tert-butyl-4- or -5-methylphenol, 2-, 4- or 5-methylresorcinol, 2-, 3- or 4-methoxyphenol, 2,3-, 2,5- or 3,5-dimethoxyphenol, 2-methoxyresorcinol, 4-tert-butylcatechol, 2-, 3- Or 4-ethylphenol, 2,5- or 3,5-diethylphenol, 2,3,5-triethylphenol, 2-naphthol, 1,3-, 1 , 5- or 1,7-dihydroxynaphthalene, polyhydroxytriphenylmethane compounds obtained by condensation of xylenol and hydroxy
  • the aldehyde used for producing the novolak resin is a compound having at least one aldehyde group in the molecule or a compound that easily generates an aldehyde group in the reaction system.
  • formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde Aliphatic aldehydes such as isobutyraldehyde, pivalaldehyde, hexylaldehyde, acrolein and crotonaldehyde, cycloaliphatic aldehydes such as cyclohexanealdehyde, cyclopentanealdehyde, furfural and furylacrolein, benzaldehyde, o-, m- or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4- or 3,5-dimethylbenzaldehyde, o-,
  • Examples of acid catalysts used for the condensation of phenolic compounds with aldehydes include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid and phosphoric acid, formic acid, acetic acid, oxalic acid, malonic acid, trichloroacetic acid and p-toluenesulfone Examples thereof include organic acids such as acids, divalent metal salts such as zinc acetate, zinc chloride and magnesium acetate.
  • Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia, tetramethylammonium hydroxide, triethylamine, morpholine, pyridine and the like.
  • an acid catalyst it is preferable to use an acid catalyst, and it is preferable to use an organic acid such as acetic acid, oxalic acid, malonic acid, and p-toluenesulfonic acid.
  • the acid catalyst or alkali catalyst can be used alone or in combination of two or more.
  • the condensation reaction can be carried out according to a conventional method, for example, at a temperature in the range of 60 to 120 ° C. for about 2 to 30 hours.
  • Reaction solvents used for polycondensation include alcohols such as methanol, ethanol, isopropanol, and t-butyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl hexyl ketone, methyl heptyl ketone, and cyclohexyl ketone; propyl acetate, Esters such as butyl acetate, isobutyl acetate, methyl propionate, methyl lactate, and propylene glycol acetate; ethers such as dibutyl ether, tetrahydrofuran, tetrahydropyran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; dichloromethane, Halogenated hydrocarbons such as chloroform, carbon tetrachloride, and bromoform; hydrocarbons such as hexane, hept
  • reaction solvent water may coexist in the reaction system, and in the case of a solvent that does not dissolve in water, a reaction solvent separated into two layers may be used. Water may be removed by distillation dehydration or the like. Among these, ketones, esters, and aromatic hydrocarbons are preferably used as the reaction solvent.
  • Component M It is preferable to contain a novolak resin having a weight average molecular weight of 900 or less as part of the alkali-soluble resin in order to improve the resolution.
  • a low molecular weight novolak resin oligomer can also be produced by condensing a phenolic compound and an aldehyde as described above in the presence of an acid catalyst according to a conventional method, in which case a low molecular weight product is produced.
  • the reaction conditions for example, the acid catalyst may be used as little as about 0.001 to 0.01 mole times the starting phenolic compound, and the reaction time may be shortened to about 1 to 5 hours.
  • the remaining alkali-soluble resin having a higher weight average molecular weight for example, a weight average molecular weight of 2,000 or more is suitable.
  • a novolak resin mainly composed of a high molecular weight component in order to improve the resolution.
  • the pattern area having a molecular weight of 1,000 or less is 25% or less, further 20% with respect to the total pattern area excluding the unreacted raw material phenol compound. The following is preferable.
  • the pattern area means that measured using a 254 nm UV detector.
  • Such a novolak resin mainly composed of high molecular weight can be produced, for example, by subjecting the novolak resin obtained by the condensation reaction to an operation such as fractionation.
  • novolak resin is mixed with a good solvent, for example, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, methyl isobutyl ketone, glycol ethers such as ethyl cellosolve, and ethyl cellosolve acetate.
  • a method of separating the lower layer mainly composed of high molecular weight can be employed.
  • the novolak resin mainly composed of a high molecular weight those having a weight average molecular weight of 5,000 or more, particularly 6,000 or more are advantageous.
  • Component M-3-3 Partially alkyletherified polyvinylphenol and Partially alkyletherified hydrogenated polyvinylphenol
  • Component M-3-1 partially alkylether Polyvinyl alcohol (hereinafter also referred to as component M-3-1) and partially alkyl etherified hydrogenated polyvinyl phenol
  • component M-3-1 partially alkyl etherification rate of 10 to 30 mol%, more preferably 15 to 22 mol%.
  • Component M-3-2 preferably has an alkyl etherification rate of 5 to 30 mol%, more preferably 8 to 20 mol%.
  • Component M-3-1 and Component M-3-2 may be used in combination, and the mixing ratio may be appropriately selected and is not particularly limited.
  • alkyl ether examples include linear or branched alkyl ethers, preferably having 1 to 4 carbon atoms, and more preferably methyl ether or ethyl ether.
  • Polyvinylphenol can be produced, for example, by hydrolyzing poly (t-butoxystyrene) obtained by polymerization of t-butoxystyrene.
  • Component M-3-1 includes polyvinylphenol and alkyl halides such as G.I. N. Vyas et al., Org. Syntheses Coll. Vol. IV, 836 (1963) and the like.
  • Component M-3-2 includes, for example, hydrogenated polyvinylphenol and an alkyl halide, as described in G. N. It can be produced by the method of Vyas et al. Hydrogenated polyvinylphenol can be produced by hydrogenating polyvinylphenol according to a conventional method.
  • alkali-soluble resins and water-soluble resins may be used together with the components M-1 to M-3.
  • an alkali-soluble resin and a water-soluble resin it is preferable to use a linear organic polymer, and a known one can be arbitrarily used.
  • a water-soluble organic polymer when used, water development becomes possible.
  • examples of such a linear organic polymer include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. No.
  • the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxyl styrene.
  • Examples of the monomer having an acid anhydride group include maleic anhydride. Can be mentioned. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful. Further, vinylphenol resin, isopropenylphenol resin, a copolymer of isopropenylphenol and styrene (the proportion of isopropenylphenol in the copolymer is preferably 50 mol% or more), partially t-butoxycarbonyloxylation Polyvinylphenol, hydrogenated polyvinylphenol, and the like.
  • the total amount of Component M-1 to Component M-3 is preferably 50% by mass or more, more preferably 65% by mass or more of the entire component M. Preferably, it is 80 mass% or more.
  • the photocurable composition of the present invention may contain a cardo resin as (Component M) alkali-soluble resin, together with Component M-1 to Component M-3, or alone.
  • a cardo resin is preferable because a film having a high refractive index can be obtained.
  • the cardo resin is a resin having a cardo structure, that is, a skeletal structure in which two cyclic structures are bonded to quaternary carbon atoms constituting the cyclic structure.
  • a common cardo structure is a fluorene ring bonded with a benzene ring.
  • the skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and an acrylic group. And a fluorene skeleton having the same.
  • the cardo resin is formed by polymerizing a skeleton having the cardo structure by a reaction between functional groups bonded thereto.
  • the cardo resin has a structure in which a main chain and bulky side chains are connected by one element (cardo structure), and has a ring structure in a direction substantially perpendicular to the main chain.
  • Monomers having a cardo structure include, for example, bis (glycidyloxyphenyl) fluorene type epoxy resin; condensate of bisphenolfluorene type epoxy resin and acrylic acid; 9,9-bis (4-hydroxyphenyl) fluorene, Cardio structure-containing bisphenols such as 9-bis (4-hydroxy-3-methylphenyl) fluorene; 9,9-bis (cyanoalkyl) fluorenes such as 9,9-bis (cyanomethyl) fluorene; -9,9-bis (aminoalkyl) fluorenes such as bis (3-aminopropyl) fluorene;
  • the cardo resin is a polymer obtained by polymerizing a monomer having a cardo structure, but may be a copolymer with other copolymerizable monomers.
  • the polymerization method of the monomer may be according to a conventional method, and for example, a ring-opening polymerization method or an addition polymerization method is employed.
  • a cardo resin from a compound represented by the following formula (Z-1), a compound represented by the following formula (Z-2), pyromellitic anhydride, terephthalic acid and its acid chloride Mention may also be made of polyester-based cardo resins obtained by copolymerizing at least one selected from the above, and compounds represented by the following formula (Z-3).
  • R 10 represents oxygen, a carbonyl group, a tetrafluoroethylene group, or a single bond.
  • the weight average molecular weight of Component M-1 is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 5,000 to 30,000.
  • the weight average molecular weight of Component M-2 is preferably 200 to 20,000, more preferably 300 to 10,000, and still more preferably 500 to 10,000.
  • the weight average molecular weight of Component M-3 is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 5,000 to 30,000.
  • the weight average molecular weight is determined in terms of polystyrene having a known molecular weight by the GPC method.
  • the content of Component M in the photocurable composition of the present invention is preferably 10 to 99.9% by mass with respect to the total solid content of the photocurable composition excluding Component B, preferably 25 to 98. More preferably, it is more preferably 35% to 95% by mass. When the content is within this range, the pattern formability during development is good, and a cured product having a higher refractive index can be obtained.
  • the solid content of the photocurable composition represents an amount excluding volatile components such as a solvent.
  • the total content of the polymer (resin) component including the component M in the photocurable composition of the present invention is 20 to 99.9% by mass with respect to the total solid content of the photocurable composition. It is preferably 50 to 98% by mass, more preferably 70 to 95% by mass. When it is in the above range, the pattern formability at the time of development becomes good, and a cured product having a higher refractive index can be obtained.
  • (Component N) Crosslinking agent When the photocurable composition of the present invention is a crosslinking system, it is preferable to contain (Component N) a crosslinking agent as the (Component X) curable component.
  • the crosslinking agent preferably contains (Component N-1) a compound having a group represented by the following formula (L).
  • Component N-1 functions as a crosslinking agent and crosslinks components M together.
  • the component A does not have group represented by a formula (L).
  • X 1 and X 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an acyl group, and Y represents a hydrogen atom or a monovalent substituent.
  • * Represents a connecting position, and is connected to a carbon atom constituting an aromatic ring, a nitrogen atom or a carbon atom constituting a heterocyclic ring, or a secondary or tertiary nitrogen atom.
  • X 1 and X 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an acyl group, and the alkyl group has 1 to 12 carbon atoms.
  • An alkyl group is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group or ethyl group is still more preferred.
  • the cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, and more preferably a cycloalkyl group having 5 to 10 carbon atoms.
  • the alkenyl group and alkynyl group preferably have 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably a phenyl group.
  • the acyl group preferably has 1 to 6 carbon atoms, more preferably 1 carbon (formyl group), 2 carbon atoms (acetyl group), or 3 carbon atoms (propionyl group).
  • X 1 and X 2 are preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.
  • Y represents a hydrogen atom or a monovalent substituent, and the monovalent substituent includes an alkyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably a methyl group). Or an ethyl group, particularly preferably a methyl group, an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms), an alkynyl group (preferably having 2 to 2 carbon atoms).
  • a cycloalkyl group (preferably 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms), an aryl group (preferably a carbon number) 6 to 20, more preferably 6 to 10), a haloalkyl group (preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 or 2 carbon atoms), an acyl group (preferably 1 carbon atom) ⁇ 6, better Or an alkylsulfonyl group (preferably 1 to 6, more preferably 1 to 4, more preferably 1 or 2), an arylsulfonyl group.
  • Y is preferably a hydrogen atom, an alkyl group, or an acyl group, and more preferably a hydrogen atom or an alkyl group.
  • the group represented by the formula (L) is a hydroxymethyl group which may have a substituent, an alkoxymethyl group which may have a substituent, or an acyloxymethyl group which may have a substituent.
  • an acetoxymethyl group is preferable.
  • As the alkoxymethyl group a methoxymethyl group is particularly preferable. It is more preferably a hydroxymethyl group or an alkoxymethyl group, and a hydroxymethyl group (—CH 2 OH), a methoxymethyl group (—CH 2 —O—CH 3 ), or an ethoxymethyl group (—CH 2 —O—CH 2).
  • CH 3 is more preferable, hydroxymethyl group or methoxymethyl group is particularly preferable, and methoxymethyl group is most preferable.
  • the group represented by the formula (L) is linked to a carbon atom constituting an aromatic ring, a nitrogen atom or a carbon atom constituting a heterocyclic ring, or a secondary or tertiary nitrogen atom. It is preferable to link to a carbon atom constituting an aromatic ring, a nitrogen atom or carbon atom constituting a heterocyclic ring, or a nitrogen atom bonded to the heterocyclic ring. That is, the group represented by the formula (L) is preferably bonded to an aromatic ring or a heterocyclic ring directly or via a linking group, and in the case of being connected to a linking group, When bonded and directly bonded, it is preferably bonded to a carbon atom or a nitrogen atom.
  • Component N-1 has at least one group represented by the formula (L), preferably two or more, more preferably 3 to 6.
  • the heterocycle may be a heteroaromatic ring or a non-aromatic heterocycle.
  • the aromatic ring and the heterocyclic ring may be monocyclic or polycyclic and are not particularly limited.
  • the polycyclic structure may be a condensed ring, a bridged ring, or a spiro ring. Further, two or more single rings may be connected by a single bond.
  • component N-1 is a urea compound in which the group represented by the formula (L) is bonded to the nitrogen atom constituting the ureylene group, and the group represented by the formula (L) is nitrogen on the ring of glycol lauryl.
  • a glycol lauryl compound linked to an atom, a triazine compound linked to a nitrogen atom in which a group represented by formula (L) is bound to a triazine ring, or a group represented by formula (L) is substituted on an aromatic ring Preference is given to phenolic compounds.
  • component N-1 is preferably a glycol lauryl compound or a triazine compound, and more preferably a triazine compound.
  • component N-1 is particularly preferably a melamine compound. That is, component N-1 is particularly preferably a melamine compound in which a group represented by the formula (L) is bonded to a nitrogen atom constituting an amino group bonded to a triazine ring.
  • the triazine compound is preferably a compound represented by the following formula (I) or (II), and particularly preferably a melamine compound represented by formula (II).
  • R 1 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group
  • L represents a group represented by the formula (L).
  • R 2 and R 3 each independently represent a hydrogen atom or a group represented by Formula (L), and L represents a group represented by Formula (L).
  • the alkyl group and alkoxy group as R 1 preferably have 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 or 2.
  • the aryl group or aryloxy group as R 1 preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, still more preferably 6 or 10, and 6 (phenyl group or phenoxy group). Is particularly preferred.
  • the alkyl group, aryl group, heteroaromatic group, alkoxy group, and aryloxy group may have a substituent, and examples of the substituent include an alkyl group, a hydroxyl group, and an aryl group. Among these, in formula (I), R 1 is preferably an aryl group, and a phenyl group is particularly preferable.
  • L represents a group represented by formula (L), and a preferred range is as described above.
  • component N-1 which is a triazine compound
  • component N-1 which is a triazine compound
  • component N-1 which is a triazine compound
  • component N-1 which is a triazine compound
  • component N-1 which is a triazine compound
  • component N-1 which is a triazine compound
  • component N-1 which is a triazine compound
  • component N-1 which is a triazine compound
  • component N-1 which is a triazine compound
  • component N-1 which is a triazine compound
  • component N-1 which is a triazine compound
  • Tetramethoxymethylbenzoguanamine trimethoxymethylbenzoguanamine, and tetraethoxymethylbenzoguanamine.
  • the following compounds are also preferably exemplified.
  • B-16 dimethylol trimethylene urea or (b-17) its dimethyl ether form,
  • a commercially available product may be used.
  • Nicarak MW-30HM, Nicarak MW-390, Nicarac MW-100LM, Nicarax MX-750LM, Nicarac MX-270, Nicarac MX- 280, Nicalak MX-290 manufactured by Sanwa Chemical Co., Ltd.
  • Component N is preferably a low molecular compound, and the molecular weight (in the case of having a molecular weight distribution, the weight average molecular weight) is preferably 1,000 or less. It is more preferably 100 to 800, and further preferably 200 to 500. When the weight average molecular weight is within the above range, the curability is excellent.
  • component N may be used individually by 1 type, and can also use 2 or more types together.
  • the content of component N in the photocurable composition of the present invention is preferably 0.1 to 20% by mass, and preferably 0.5 to 15%, based on the total solid content of the photocurable composition of the present invention. More preferably, it is more preferably 0.5 to 10% by mass. Within the above range, the curability is excellent and the resolution is excellent.
  • the photocurable composition of the present invention is a crosslinking system, it is preferable to contain (Component O) an acid generator as the (Component X) curable component.
  • the (Component O) acid generator is preferably a photoacid generator, preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, more preferably a wavelength of 300 to 450 nm, and generates an acid.
  • the chemical structure is not limited.
  • an acid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be combined with a sensitizer as long as 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 the sensitizer.
  • the acid generator used in the present invention is preferably an acid generator that generates an acid having a pKa of 4 or less, more preferably an acid generator that generates an acid having a pKa of 3 or less, and an acid having a pKa of 2 or less.
  • the acid generator that is generated is most preferred.
  • pKa is preferably ⁇ 15 or more.
  • Examples of the photoacid generator 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 and sensitivity.
  • These acid 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 (C1).
  • 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 (C1) is also preferably an oxime sulfonate compound represented by the following formula (C2).
  • 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 (C1) is also preferably an oxime sulfonate compound represented by the following formula (C3).
  • R 43 has the same meaning as R 42 in formula (C2), and X 1 represents 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.
  • 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 (C3) 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. It can also be used in combination with other types of (component O) acid generators.
  • the compound containing an oxime sulfonate structure represented by the above formula (C1) 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 (C1) 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 (C1) is particularly preferably an oxime sulfonate compound represented by any one 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 acid generator is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (resin) component containing Component M in the photocurable composition. It is preferable to use 0.5 to 10 parts by mass.
  • Component O is preferably 0.1 to 10% by mass, and preferably 0.5 to 10% by mass, based on the solid content of the photocurable composition (excluding metal oxide particles). More preferred.
  • the component O may be used individually by 1 type, and can also use 2 or more types together.
  • the photocurable composition of the present invention may contain (Component P) an antioxidant in the case of a crosslinking system.
  • an antioxidant a well-known antioxidant can be contained.
  • 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 photocurable 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.
  • various ultraviolet absorbers described in “New Development of Polymer Additives” (Nikkan Kogyo Shimbun Co., Ltd.), metal deactivators, etc. are photocured according to the present invention. May be added to the composition.
  • the photocurable composition of the present invention may contain (Component Q) a basic compound in the case of a crosslinking system.
  • 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 photocurable 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 photocurable composition. More preferred is 1 part by mass.
  • the photocurable composition of the present invention can use (Component R) 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.
  • 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 multiplication agent in the photocurable composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the acid generator, from the viewpoint of dissolution contrast between the exposed part and the unexposed part.
  • the amount is preferably 20 to 500 parts by mass.
  • a sensitizer, a co-sensitizer, and an adhesion improver can be preferably added to the photocurable composition of the present invention, if necessary, in addition to the above components.
  • known UV absorbers, surfactants, development accelerators, plasticizers, metal deactivators, thermal radical generators, thermal acid generators, thickeners, and organic or inorganic precipitation inhibitors Additives can be added.
  • sensitizers, co-sensitizers, adhesion improvers, ultraviolet absorbers, surfactants, development accelerators, and plasticizers can be the same as those described in the polymerization system. .
  • the haze when the photocurable composition of the present invention is formed to a film thickness of 1 ⁇ m is preferably 2% or less. When the haze is 2% or less, the transparency is excellent.
  • forming into a film thickness of 1 micrometer means that the film thickness after forming the layer of a photocurable composition, heating this, removing a solvent, and carrying out exposure hardening after that is 1 micrometer.
  • the film thickness after the baking process is 1 ⁇ m.
  • the haze is more preferably 1% or less, and further preferably 0.5% or less.
  • the lower limit of the haze is not particularly limited and may be 0% or more, and is preferably 0.01% or more and more preferably 0.05% or more from the viewpoint of achievability.
  • the photocurable composition of the present invention preferably has a refractive index of 1.65 or more at a wavelength of 589 nm.
  • the refractive index means the refractive index of a layer formed by forming a photocurable composition layer, heating it to remove the solvent, and then exposing and curing. Further, when there is a baking process, it means the refractive index after the baking process.
  • the refractive index is more preferably 1.70 or more, still more preferably 1.75 or more.
  • the upper limit of the refractive index is not particularly limited, but is preferably 2.50 or less, more preferably 2.30 or less, and even more preferably 2.10 or less.
  • the method for producing a cured film of the present invention preferably includes the following steps (1) to (4).
  • a coating process for coating the photocurable composition of the present invention on a substrate (2) a solvent removal step of removing the solvent from the applied composition; (3) An exposure step of exposing the composition from which the solvent has been removed to a pattern with actinic rays; (4) A developing step in which the composition in the unexposed area is removed with an aqueous developer and developed.
  • a heat treatment step of heat-treating the developed composition Each step will be described below in order.
  • the coating step (1) it is preferable to apply the photocurable composition of the present invention on a substrate to form a wet film containing a solvent.
  • substrate cleaning such as alkali cleaning or plasma cleaning
  • the method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed 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.
  • the coating method on the substrate is not particularly limited, and for example, a method such as an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method 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 acid generator is decomposed to generate an acid.
  • radicals are generated from the polymerization initiator.
  • 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 heat treatment
  • PEB post-exposure Bake
  • the temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
  • a negative image can be formed by exposure without necessarily performing PEB.
  • the developer used in the development step (4) preferably contains a basic compound.
  • basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and diethyldimethylammonium hydroxide; Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamine
  • 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.
  • a water-soluble organic solvent such as methanol or ethanol or a surfactant
  • sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
  • An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
  • the pH of the developer is preferably 10.0 to 14.0.
  • the development time is preferably 30 to 500 seconds, and the development method may be 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.
  • Both the crosslinking system and the polymerization system preferably have the heat treatment step (post bake) of (5).
  • the cross-linking system by heating the negative image obtained in the heat treatment step (post-bake) of (5), an acid group, for example, a carboxyl group or a phenolic hydroxyl group is generated, and a crosslinkable group, a crosslinking agent, etc. By crosslinking, a stronger cured film can be formed.
  • the polymerizable compound remaining without reacting at the time of exposure causes a polymerization reaction by heat, thereby forming a stronger cured film. This heating is performed using a heating device such as a hot plate or oven at a predetermined temperature, for example, 180 ° C.
  • the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step).
  • middle baking and post baking can be heated in three or more stages.
  • the taper angle of the pattern can be adjusted by devising such middle baking and post baking.
  • These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
  • the entire surface of the patterned substrate is re-exposed with actinic rays (post-exposure) and post-baked to generate acid from the acid generator present in the exposed area, further accelerating the crosslinking process. It can function as a catalyst that promotes the film curing reaction.
  • 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 photocurable composition of the present invention can also be used as a dry etching resist.
  • dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
  • the cured film of the present invention is a cured film obtained by curing the photocurable 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 a high temperature can be obtained.
  • the interlayer insulating film formed using the photocurable composition of the present invention has high transparency and excellent cured film properties, and thus is useful for applications of organic EL display devices and liquid crystal display devices.
  • cured material of this invention is a hardened
  • 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.
  • Process (a) and process (b) are synonymous with the said application
  • Step (c) is the same step as the above exposure step, and the preferred embodiment is also the same.
  • 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 flattening film or an interlayer insulating film formed using the photocurable 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 photocurable composition of this invention and the cured film of this invention are not limited to the said use, but 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 photocurable 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.
  • 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 photocurable 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) described 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. 4 (a) of JP2009-128577A, and described in FIG. 3 of JP2010-182638A. It can also be used to form a planarization film (12), a pixel isolation insulating film (14), and the like.
  • imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.
  • the photocurable composition of the present invention is excellent in transparency and refractive index, it is suitably used as a member for microlenses and prisms and a member for extracting light.
  • a member for microlenses and prisms and a member for extracting light can be used as a prism member or a member for joining a prism and a light guide plate used in a backlight unit of a flat panel for display.
  • it can be used as a member for improving the light extraction efficiency of an organic EL display.
  • the touch panel display device of the present invention includes a capacitive input device having the cured film of the present invention. Moreover, the capacitance-type input device of the present invention has the cured 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, and the following (4) is the cured 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.
  • 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 which will be described later, are a photocurable transfer material having a photocurable composition using the conductive fibers. It 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 provided so as to cover all of the components, but the transparent protective layer 37 may be configured to cover only a part of the components. .
  • the insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.
  • the capacitive input device obtained by the manufacturing method of the present invention and the touch panel display device including the capacitive input device as a constituent element are “latest touch panel technology” (issued July 6, 2009). 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 transfer material of the present invention is preferably formed using the transfer material described in JP-A-5-72724, that is, an integral film.
  • the structure of the integral film include a structure in which a support (temporary support) / thermoplastic resin layer / intermediate layer / curable resin layer / protective film is laminated in this order, but is not limited thereto.
  • At least one layer of the photocurable composition of the present invention is formed on the support. That is, it is essential for the transfer material of the present invention to provide a photocurable layer by using the above-described photocurable composition of the present invention. In addition, it can form into a film by providing the layer which consists of a photocurable composition, and removing a solvent as needed.
  • the temporary support is required to be flexible and not to cause significant deformation, shrinkage or elongation even under pressure or pressure and heating.
  • a support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.
  • the component used in the thermoplastic resin layer is preferably an organic polymer substance described in JP-A-5-72724, and is a polymer softening point according to the Viker Vicat method (specifically, American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferred that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof.
  • Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer United nylon, copolymer nylon, - alkoxymethyl nylon, and organic polymers of the polyamide resin such as N- dimethylamino nylon.
  • the dry thickness of the thermoplastic resin layer is preferably 2 to 30 ⁇ m, more preferably 5 to 20 ⁇ m, and even more preferably 7 to 16 ⁇ m.
  • an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application.
  • an oxygen-blocking film having an oxygen-blocking function which is described as “separation layer” in JP-A-5-72724. Time load is reduced and productivity is improved.
  • the oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Of these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.
  • the dry thickness of the intermediate layer is preferably 0.2 to 5 ⁇ m, more preferably 0.5 to 3 ⁇ m, and even more preferably 1 to 2.5 ⁇ m.
  • ⁇ Protective film> It is preferable to provide a thin protective film on the curable resin layer in order to protect it from contamination and damage during storage.
  • the protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the curable resin layer.
  • silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.
  • the thickness of the protective film is preferably 4 to 40 ⁇ m, more preferably 5 to 30 ⁇ m, and still more preferably 10 to 25 ⁇ m.
  • the transfer material of the present invention is provided with a thermoplastic resin layer by applying a coating solution (a coating solution for a thermoplastic resin layer) in which a thermoplastic resin layer additive is dissolved on a temporary support, followed by drying.
  • a coating solution a coating solution for a thermoplastic resin layer
  • An intermediate layer material solution made of a solvent that does not dissolve the thermoplastic resin layer is applied on the plastic resin layer, dried, and then the curable resin layer is applied by applying a solvent that does not dissolve the intermediate layer and then dried. be able to.
  • a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the curable resin layer on the protective film are prepared, and the intermediate layer and the curable resin layer are in contact with each other.
  • thermoplastic resin layer on the temporary support a sheet provided with a curable resin layer and an intermediate layer on a protective film are prepared, and a thermoplastic resin layer is prepared. It can also be produced by sticking them together so that the intermediate layer is in contact with it. Note that the coating in the above production method can be performed by a known coating apparatus or the like.
  • Compound 2 PGMEA 30% solution of a compound having the following structure (weight average molecular weight 3,000)
  • Cross-linking agent (K-1): Nicalak MW-100LM (the following structure, manufactured by Sanwa Chemical Co., Ltd.)
  • (Acid generator) B-1 Photoacid generator represented by the following structure
  • polymer Polymer
  • Polymer Polymer
  • P-1 PGMEA 30 wt% solution of the following polymer (weight average molecular weight 30,000) (The following polymerization ratio means molar ratio.)
  • Polymer (P-3) polymer synthesized by the following method (weight average molecular weight 17,500, PGMEA 31 wt% solution) ⁇ Synthesis method>
  • a flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of propylene glycol monomethyl ether acetate, followed by 25 parts by mass of methacrylic acid, dicyclo 35 parts by mass of pentanyl methacrylate, 40 parts by mass of ⁇ -methylglycidyl methacrylate, and 1.5 parts by mass of ⁇ -methylstyrene dimer were charged, and gently stirring was started while replacing with nitrogen. Thereafter, the temperature of the reaction solution was raised to 70 ° C., and polymerization was carried out at this temperature for 5 hours to obtain a polymer solution containing a copolymer and having a solid content concentration of 31.2% by mass.
  • Polymer (P-4): PGMEA 40 wt% solution of Marcalinker M (polyhydroxystyrene, weight average molecular weight 18,000, manufactured by Maruzen Chemical Co., Ltd.) Polymer (P-5): PR54046 (novolak resin, m-cresol / p -Cresol 60/40, manufactured by Sumitomo Durres Co., Ltd.) PGMEA 40 wt% solution
  • dispersion D1 A dispersion having the following composition was prepared, mixed with 17,000 parts of zirconia beads (0.3 mm ⁇ ), and dispersed for 12 hours using a paint shaker. Zirconia beads (0.3 mm ⁇ ) were filtered off to obtain dispersion D1.
  • ⁇ Titanium dioxide made by Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C), average primary particle size: 10-30 nm
  • Dispersant DISPERBYK-111: manufactured by Big Chemie Japan
  • PGMEA solution 2,200 parts
  • Solvent (PGMEA) 3,425 parts
  • Dispersions D2 to D10 were prepared in the same manner as the dispersion D1, except that the titanium dioxide particles and the dispersant were changed to the compounds shown in Table 1 below.
  • Example 1 ⁇ Preparation of photocurable composition> Each component was mixed so that it might become the following composition using the titanium dioxide dispersion liquid obtained above, and the photocurable composition of Example 1 was obtained.
  • Propylene glycol monomethyl ether acetate 362.3 parts
  • Examples 2 to 22, 25 to 26, Comparative Examples 1 to 4 A photocurable composition was obtained in the same manner as in Example 1 except that the dispersion, the heterocyclic compound, and the polymer were changed to those shown in Table 2 below.
  • Example 23 Each component was mixed so that it might become the following compositions, and the photocurable composition of Example 23 was obtained.
  • Propylene glycol monomethyl ether acetate 362.3 parts
  • Example 24 Each component was mixed so that it might become the following compositions, and the photocurable composition of Example 24 was obtained.
  • Propylene glycol monomethyl ether acetate 362.3 parts
  • Heterocyclic compound F-5 5.00 parts
  • the haze of the cured film thus obtained is NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd., with the film surface facing upward, in accordance with the plastic product test method (JIS K7136, JIS K7361, ASTM D1003), The haze (haze value) was measured.
  • 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. 1: Haze value of less than 0.5% 2: Haze value of 0.5% or more and less than 0.7% 3: Haze value of 0.7% or more and less than 1.0% 4: Haze value of 1.0% or more and 2.0% Less than 5: Haze value 2.0% or more
  • ⁇ Development residue evaluation> The obtained photocurable 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 on a hot plate at 90 ° C. 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 30 seconds by immersion, and further rinsed with ultrapure water for 10 seconds. The glass substrate was observed with an optical microscope, and the presence or absence of a development residue (residue) of the film was evaluated. The evaluation criteria are as shown below. 1: No residue 2: Slightly residue 3: Residue
  • the obtained photocurable 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 at 200 mJ / cm 2 (measured by i-line) using an ultrahigh pressure mercury lamp. Then, it heated at 220 degreeC minutes for 45 minutes in oven.
  • 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.
  • the resulting photocurable 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 to 3 is a practical range, and 1 or 2 is preferable. 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.
  • ITO pattern visibility An ITO pattern is formed in advance on a 100 mm ⁇ 100 mm glass substrate (trade name: XG, manufactured by Corning), and the obtained photocurable 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. Then, it heated at 220 degreeC for 45 minutes, and provided the dry film
  • the obtained substrate was observed with the naked eye in a bright room while tilting, and the visibility was evaluated as compared with the case where the photocurable composition was not provided on the ITO pattern. Note that 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.
  • Example 27 Each component was mixed so that it might become the following compositions, and the photocurable composition of Example 27 was obtained.
  • Propylene glycol monomethyl ether acetate 321.4 parts
  • Polymer (P-4) 162.1 parts
  • Example 28 A photocurable composition of Example 28 was obtained in the same manner as in Example 27 except that the polymer (P-4) was changed to the polymer (P-5).
  • Comparative Example 5 A photocurable composition of Comparative Example 5 was obtained in the same manner as in Example 27 except that the heterocyclic compound F-5 was not added as Component A.
  • the resulting photocurable 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 . Thereafter, heat treatment was performed at 110 ° C. for 90 seconds.
  • 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. 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.
  • Example 29 In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3312003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 29 was obtained. That is, as a pretreatment for improving the wettability between the substrate and the interlayer insulating film 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the light of Example 4 was used.
  • HMDS hexamethyldisilazane
  • the curable composition was spin-coated on a substrate, pre-baked on a hot plate (90 ° C./120 seconds) to evaporate the solvent, and a 3 ⁇ m-thick photocurable composition layer was formed.
  • the obtained photocurable composition layer was subjected to 40 mJ / cm 2 (energy intensity: 20 mW / mm) through a mask for forming a 10 ⁇ m ⁇ hole pattern using an MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. cm 2 , i-line).
  • the photocurable composition layer after the exposure was subjected to paddle development at 23 ° C./60 seconds with an alkaline developer (0.4% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained. The applicability when applying the photocurable composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and baking.
  • Example 30 A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the exposure apparatus was changed from MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The performance of the obtained liquid crystal display device was as good as in Example 29.
  • MPA 5500CF high pressure mercury lamp
  • FX-803M gh-Line stepper
  • Example 31 A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the exposure apparatus was changed from Canon's MPA 5500CF (high pressure mercury lamp) to “AEGIS” manufactured by Buoy Technology Co., Ltd., to a wavelength of 355 nm and a pulse width of 6 nsec. The performance of the obtained liquid crystal display device was as good as in Example 29.
  • Example 32 A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the photocurable composition of Example 1 was applied without the hexamethyldisilazane (HMDS) treatment, which was a pretreatment of the substrate. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. This is presumably because the composition of the present invention has excellent adhesion to the substrate. From the viewpoint of improving productivity, it is also preferable to omit the substrate pretreatment step.
  • HMDS hexamethyldisilazane
  • Example 33 A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, a vacuum drying step (VCD) was introduced after pre-baking. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. It is also preferable to introduce a reduced-pressure drying step from the viewpoint of suppressing coating unevenness according to the solid content concentration and the film thickness of the composition.
  • VCD vacuum drying step
  • Example 34 The photocurable composition to be used was changed to the photocurable composition of Example 27, or the same process as in Example 29 was changed to obtain a similar liquid crystal display device. That is, a PEB process (post-exposure heat treatment process, 90 ° C., 1 minute) was introduced between the mask exposure and the development process. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. From the viewpoint of improving dimensional stability, it is also preferable to introduce a PEB process.
  • PEB process post-exposure heat treatment process, 90 ° C., 1 minute
  • Example 35 A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 2.38% tetramethylammonium hydroxide aqueous solution. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • Example 36 A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the alkali development method was changed from paddle development to shower development. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • Example 37 A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
  • 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 38 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 planarizing film 4 is formed on the insulating film 3 by spin-coating the photocurable composition of Example 27 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, heat treatment is performed at 110 ° C. for 90 seconds on a hot plate, and the pattern is developed with an aqueous alkali solution.
  • 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 photocurable composition of Example 13 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus.
  • a second electrode made of Al was formed on the entire surface above the substrate.
  • substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
  • a touch panel display device was prepared by using the high refractive index curable resin material of the present invention by the method described below.
  • etching resist was applied onto ITO and dried to form an etching resist layer.
  • Development was performed, and a post-bake treatment at 130 ° C. for 30 minutes was further performed 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 photocurable composition of Example 1 was applied and dried (film thickness: 1 ⁇ m, 90 ° C., 120 seconds) to form a photocurable composition layer.
  • the distance between the exposure mask (quartz exposure mask having an insulating layer pattern) surface and the photocurable 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 In the same manner as in the formation of the first transparent electrode pattern, a commercially available etching resist is used, the first transparent electrode pattern, the insulating layer pattern formed using the photocurable composition of Example 1, and the transparent electrode A front plate on which a layer and an etching resist pattern were formed was obtained (post-bake treatment; 130 ° C. for 30 minutes). Further, the mask layer, the first transparent electrode pattern, and the photocurable composition of Example 1 were used by etching and removing the etching resist layer in the same manner as the formation of the first transparent electrode pattern. A front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was obtained.
  • the photocurable composition of Example 1 was applied and dried (film thickness: 1 ⁇ m) on the front plate formed up to the conductive element different from the first and second transparent electrode patterns. , 90 ° C. for 120 seconds) to obtain a photocurable 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
  • the electrode pattern, the insulating layer pattern formed using the photocurable composition of Example 1, the second transparent electrode pattern, and all the conductive elements different from the first and second transparent electrode patterns are covered.
  • stacked the insulating layer (transparent protective layer) formed using the photocurable composition of Example 1 was obtained.
  • Example 40 Provide of transfer material- On a 75 ⁇ m thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, the photocurable composition of Example 4 was applied and dried, and a thermoplastic resin layer with a dry film thickness of 14.6 ⁇ m, an intermediate layer with a dry film thickness of 1.6 ⁇ m, A curable resin layer having a thickness of 1 ⁇ m was provided, and a protective film (12 ⁇ m thick polypropylene film) was pressure-bonded. Thus, a transfer material T1 in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the curable resin layer were integrated was produced.
  • a non-alkali glass substrate is washed with a rotating brush having nylon bristles while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering.
  • silane coupling solution N- ⁇ (aminoethyl) A 0.3% aqueous solution of ⁇ -aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM603 0.3% aqueous solution of ⁇ -aminopropyltrimethoxysilane
  • This transfer sample was exposed through a 1% to 60% gradation mask with a line-and-space ratio of 1: 1 with an energy intensity of 20 mW / cm 2 and 200 mJ / cm 2 using a ghi-line high-pressure mercury lamp exposure machine. Thereafter, heat treatment was performed at 110 ° C. for 90 seconds. Next, 30 ° C. in a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, FUJIFILM Corporation) shower development was carried out for 50 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier film.
  • a triethanolamine developer containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, FUJIFILM Corporation
  • the curable resin layer was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds and rinsed with ultrapure water for 10 seconds. A line and space pattern corresponding to the pattern was obtained. The resolution of the obtained pattern was equivalent to that of Example 1 evaluated as a liquid material, and it was confirmed that this material was also effective as a transfer material.
  • 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

The purpose of the present invention is to provide a photocurable composition which is capable of forming a pattern that has high refractive index and high transmittance, while achieving high resolution. A photocurable composition of the present invention is characterized by containing (component A) a heterocyclic compound having two or more nitrogen atoms, (component B) metal oxide particles, (component C) a solvent and (component X) a curable component, and is also characterized in that the component A is a compound represented by formula (1). (In formula (1), each of R1 and R2 independently represents a hydrogen atom, a halogen atom or a monovalent organic group; R1 and R2 may combine together to form a divalent organic group; each of R3 and R4 independently represents a hydrogen atom or a monovalent organic group; L1 represents a divalent linking group that forms a five-membered ring or a six-membered ring; and L1 and R3 or R4 may combine together to form a ring.)

Description

光硬化性組成物、転写材料、硬化物及びその製造方法、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Photocurable composition, transfer material, cured product and method for producing the same, resin pattern production method, cured film, liquid crystal display device, organic EL display device, and touch panel display device
　本発明は、光硬化性組成物（以下、単に、「本発明の組成物」ということがある。）に関する。また、上記光硬化性組成物の層を有する転写材料、上記光硬化性組成物を硬化してなる硬化物及びその製造方法、上記光硬化性組成物を用いた樹脂パターン製造方法、上記光硬化性組成物を硬化してなる硬化膜、並びに、上記硬化膜を用いた各種画像表示装置に関する。
　更に詳しくは、液晶表示装置、有機ＥＬ表示装置、タッチパネル表示装置、集積回路素子、固体撮像素子などの電子部品の平坦化膜、保護膜や層間絶縁膜の形成に好適な、光硬化性組成物及びそれを用いた硬化膜の製造方法に関する。 The present invention relates to a photocurable composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, the transfer material which has the layer of the said photocurable composition, the hardened | cured material formed by hardening | curing the said photocurable composition, its manufacturing method, the resin pattern manufacturing method using the said photocurable composition, the said photocuring The present invention relates to a cured film obtained by curing an adhesive composition, and various image display devices using the cured film.
More specifically, a photocurable composition suitable for forming a planarizing film, a protective film or an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, a touch panel display device, an integrated circuit element, and a solid-state imaging device. And a method for producing a cured film using the same.
　固体撮像素子や液晶表示装置の発達により、有機素材（樹脂）によりマイクロレンズ、光導波路、反射防止膜などの光学部材を作製することが広く行われるようになっている。
　これら光学部材は、高屈折率にするために、酸化チタンなどの粒子を添加することが検討されている（特許文献１参照）。
　また、従来のネガ型光硬化性組成物としては、特許文献２及び３に記載の光硬化性組成物が知られている。 With the development of solid-state imaging devices and liquid crystal display devices, it has become widely practiced to produce optical members such as microlenses, optical waveguides, and antireflection films using organic materials (resins).
In order to make these optical members have a high refractive index, it has been studied to add particles such as titanium oxide (see Patent Document 1).
Moreover, as a conventional negative photocurable composition, the photocurable composition of patent document 2 and 3 is known.
特開２００６－９８９８５号公報JP 2006-98985 A 特開２０１１－１２７０９６号公報JP 2011-127096 A 特開２００９－１７９６７８号公報JP 2009-179678 A
　本発明は、高い解像性が得られ、高屈折率かつ透過率が高いパターンを形成可能な光硬化性組成物を提供することを目的とする。 An object of the present invention is to provide a photocurable composition that can form a pattern with high resolution and high refractive index and high transmittance.
　本発明の上記課題は、以下の＜１＞、＜２０＞～＜２４＞、＜２６＞～＜２８＞に記載の手段により解決された。好ましい実施態様である＜２＞～＜１９＞及び＜２５＞と共に以下に記載する。
　＜１＞　（成分Ａ）２つ以上の窒素原子を有する複素環化合物、（成分Ｂ）金属酸化物粒子、（成分Ｃ）溶剤、及び、（成分Ｘ）硬化性成分を含有することを特徴とする光硬化性組成物、
　＜２＞　成分Ａが、１，３位に窒素原子を少なくとも有する複素環構造を有する化合物である、＜１＞に記載の光硬化性組成物、
　＜３＞　成分Ａが、１，３位に窒素原子を少なくとも有する５員又は６員複素環構造を有する化合物である、＜１＞又は＜２＞に記載の光硬化性組成物、
　＜４＞　成分Ａの複素環の環員が、炭素原子及び窒素原子よりなる、＜１＞～＜３＞のいずれか１つに記載の光硬化性組成物、
　＜５＞　成分Ａが、下記式（１）で表される化合物である、＜１＞～＜４＞のいずれか１つに記載の光硬化性組成物、 The above-described problems of the present invention have been solved by means described in the following <1>, <20> to <24>, <26> to <28>. It is described below together with <2> to <19> and <25>, which are preferred embodiments.
<1> (Component A) containing a heterocyclic compound having two or more nitrogen atoms, (Component B) metal oxide particles, (Component C) solvent, and (Component X) a curable component A photocurable composition,
<2> The photocurable composition according to <1>, wherein component A is a compound having a heterocyclic structure having at least a nitrogen atom at the 1,3-position.
<3> The photocurable composition according to <1> or <2>, wherein the component A is a compound having a 5-membered or 6-membered heterocyclic structure having at least a nitrogen atom at the 1,3-position.
<4> The photocurable composition according to any one of <1> to <3>, wherein the ring member of the heterocyclic ring of component A is composed of a carbon atom and a nitrogen atom,
<5> The photocurable composition according to any one of <1> to <4>, wherein component A is a compound represented by the following formula (1):
Figure JPOXMLDOC01-appb-C000003
 （式（１）中、Ｒ1及びＲ2はそれぞれ独立に、水素原子、ハロゲン原子又は一価の有機基を表し、Ｒ1とＲ2とが結合して二価の有機基であってもよく、Ｒ3及びＲ4はそれぞれ独立に、水素原子又は一価の有機基を表し、Ｌ1は５員環又は６員環を形成する二価の連結基を表し、Ｒ3又はＲ4とＬ1とが結合して環を形成していてもよく、また、点線の結合は、点線で記載した含窒素二重結合が存在する場合は、Ｒ2及びＲ4が存在しないことを表し、点線で記載した含窒素二重結合が存在しない場合は、Ｒ2及びＲ4が存在することを表す。）
Figure JPOXMLDOC01-appb-C000003
 (In formula (1), R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and even if R 1 and R 2 are bonded to form a divalent organic group, Well, R 3 and R 4 each independently represents a hydrogen atom or a monovalent organic group, L 1 represents a divalent linking group forming a 5-membered ring or a 6-membered ring, and R 3 or R 4 and L 1 may be bonded to form a ring, and the dotted bond indicates that when the nitrogen-containing double bond described by the dotted line is present, R 2 and R 4 are not present; (If the nitrogen-containing double bond indicated by the dotted line is not present, it represents that R 2 and R 4 are present.)
　＜６＞　式（１）中、Ｒ1及びＲ2が表す一価の有機基が、アルキル基（好ましくは炭素数１～２０、より好ましくは炭素数１～８、更に好ましくは炭素数１～６）、アルケニル基（好ましくは炭素数２～２０、より好ましくは炭素数２～１２、更に好ましくは炭素数２～６）、アリール基（好ましくは炭素数２～２０、より好ましくは炭素数６～１６、更に好ましくは炭素数６～１０）、又は、メルカプト基であり、Ｒ1とＲ2とが結合した二価の有機基が、オキソ基、チオキソ基、又は、アルキリデン基であり、Ｒ3及びＲ4が表す一価の有機基がアルキル基（好ましくは炭素数１～２０、より好ましくは炭素数１～８、更に好ましくは炭素数１～４）、アルケニル基（好ましくは炭素数２～２０、より好ましくは炭素数２～１２、更に好ましくは炭素数２～６）、アルキニル基（好ましくは炭素数２～２０、より好ましくは炭素数２～１２、更に好ましくは炭素数２～６）、アリール基（好ましくは炭素数２～２０、より好ましくは炭素数６～１６、更に好ましくは炭素数６～１０）、又は、ヘテロ環基である、＜５＞に記載の光硬化性組成物、 <6> In the formula (1), the monovalent organic group represented by R 1 and R 2 is an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 1 to 8 carbon atoms). 6), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an aryl group (preferably having 2 to 20 carbon atoms, more preferably 6 carbon atoms). -16, more preferably 6-10 carbon atoms, or a mercapto group, and the divalent organic group in which R 1 and R 2 are bonded is an oxo group, a thioxo group, or an alkylidene group, The monovalent organic groups represented by 3 and R 4 are alkyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 4 carbon atoms), alkenyl groups (preferably having 2 carbon atoms). ~ 20, more preferably 2 to 12 carbon atoms, even more preferred Or 2 to 6 carbon atoms), an alkynyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an aryl group (preferably 2 to 20 carbon atoms, More preferably, the photocurable composition according to <5>, which has 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms, or a heterocyclic group,
　＜７＞　式（１）中、Ｒ1及びＲ2がそれぞれ独立に水素原子若しくはメルカプト基を表すか、又は、Ｒ1とＲ2とが結合してチオキソ基を表す、＜５＞又は＜６＞に記載の光硬化性組成物、
　＜８＞　式（１）中、Ｒ3及びＲ4がそれぞれ独立に水素原子、アルキル基、又はアリール基である、＜５＞～＜７＞のいずれか１つに記載の光硬化性組成物、
　＜９＞　式（１）中、Ｒ3及びＲ4がそれぞれ独立に、水素原子、モルフォリノメチル基、又は、フェニル基を表す、＜５＞～＜８＞のいずれか１つに記載の光硬化性組成物、 <7> In the formula (1), R 1 and R 2 each independently represent a hydrogen atom or a mercapto group, or R 1 and R 2 are bonded to each other to represent a thioxo group, <5> or <6 > The photocurable composition as described in>
<8> The photocurable composition according to any one of <5> to <7>, wherein in formula (1), R 3 and R 4 are each independently a hydrogen atom, an alkyl group, or an aryl group. ,
<9> The light according to any one of <5> to <8>, wherein in formula (1), R 3 and R 4 each independently represents a hydrogen atom, a morpholinomethyl group, or a phenyl group. Curable composition,
　＜１０＞　成分Ａが、メルカプト基又はチオキソ基を有する、＜１＞～＜９＞のいずれか１つに記載の光硬化性組成物、
　＜１１＞　成分Ａが、下記式（１－１）又は式（１－２）で表される化合物である、＜１＞～＜１０＞のいずれか１つに記載の光硬化性組成物、 <10> The photocurable composition according to any one of <1> to <9>, wherein Component A has a mercapto group or a thioxo group,
<11> The photocurable composition according to any one of <1> to <10>, wherein component A is a compound represented by the following formula (1-1) or formula (1-2):
Figure JPOXMLDOC01-appb-C000004
 （式（１－１）及び式（１－２）中、Ｒ6～Ｒ8はそれぞれ独立に、水素原子又は一価の有機基を表し、Ｌ2及びＬ3はそれぞれ独立に、５員環又は６員環を形成する二価の連結基を表し、Ｒ6とＬ2とが結合して環を形成していてもよく、Ｒ7又はＲ8とＬ3とが結合して環を形成していてもよい。）
Figure JPOXMLDOC01-appb-C000004
 (In Formula (1-1) and Formula (1-2), R 6 to R 8 each independently represents a hydrogen atom or a monovalent organic group, and L 2 and L 3 each independently represents a 5-membered ring. Or a divalent linking group forming a 6-membered ring, wherein R 6 and L 2 may be combined to form a ring, and R 7 or R 8 and L 3 are combined to form a ring. You may do it.)
　＜１２＞　式（１－１）及び式（１－２）中、Ｒ6～Ｒ8が表す一価の有機基がアルキル基（好ましくは炭素数１～２０、より好ましくは炭素数１～８、更に好ましくは炭素数１～４）、アルケニル基（好ましくは炭素数２～２０、より好ましくは炭素数２～１２、更に好ましくは炭素数２～６）、アルキニル基（好ましくは炭素数２～２０、より好ましくは炭素数２～１２、更に好ましくは炭素数２～６）、アリール基（好ましくは炭素数２～２０、より好ましくは炭素数６～１６、更に好ましくは炭素数６～１０）、又は、ヘテロ環基である、＜１１＞に記載の光硬化性組成物、
　＜１３＞　式（１－１）及び式（１－２）中、Ｒ6～Ｒ8がそれぞれ独立に水素原子、アルキル基、又はアリール基である、＜１１＞又は＜１２＞に記載の光硬化性組成物、
　＜１４＞　式（１－１）及び式（１－２）中、Ｒ6～Ｒ8がそれぞれ独立に、水素原子、モルフォリノメチル基、又は、フェニル基を表す、＜１１＞～＜１３＞のいずれか１つに記載の光硬化性組成物、 <12> In the formulas (1-1) and (1-2), the monovalent organic group represented by R 6 to R 8 is an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms). More preferably 1 to 4 carbon atoms), an alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an alkynyl group (preferably 2 to 2 carbon atoms). 20, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an aryl group (preferably 2 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 10 carbon atoms) Or a photocurable composition according to <11>, which is a heterocyclic group,
<13> The light according to <11> or <12>, wherein in formulas (1-1) and (1-2), R 6 to R 8 are each independently a hydrogen atom, an alkyl group, or an aryl group. Curable composition,
<14> In the formulas (1-1) and (1-2), R 6 to R 8 each independently represents a hydrogen atom, a morpholinomethyl group, or a phenyl group, <11> to <13> The photocurable composition according to any one of
　＜１５＞　成分Ａの分子量が、１，０００以下である、＜１＞～＜１４＞のいずれか１つに記載の光硬化性組成物、
　＜１６＞　成分Ａの含有量が、組成物の全固形分に対し、３０質量％以上である、＜１＞～＜１５＞のいずれか１つに記載の光硬化性組成物、
　＜１７＞　（成分Ｄ）分散剤を更に含む、＜１＞～＜１６＞のいずれか１つに記載の光硬化性組成物、
　＜１８＞　成分Ｘとして、（成分Ｅ）重合性化合物、及び、（成分Ｆ）重合開始剤を含む、＜１＞～＜１７＞のいずれか１つに記載の光硬化性組成物、
　＜１９＞　成分Ｘとして、（成分Ｍ）アルカリ可溶性樹脂、（成分Ｎ）架橋剤、及び、（成分Ｏ）酸発生剤を含む、＜１＞～＜１７＞のいずれか１つに記載の光硬化性組成物、
　＜２０＞　支持体上に、＜１＞～＜１９＞のいずれか１つに記載の光硬化性組成物を少なくとも１層製膜させてなる、転写材料、
　＜２１＞　少なくとも工程（ａ）～（ｃ）をこの順に含む硬化物の製造方法、
　（ａ）＜１＞～＜１９＞のいずれか１つに記載の光硬化性組成物を基板上に塗布する塗布工程
　（ｂ）塗布された組成物から溶剤を除去する溶剤除去工程
　（ｃ）溶剤が除去された組成物に活性光線を照射する露光工程
　＜２２＞　少なくとも工程（１）～（４）をこの順に含む樹脂パターン製造方法、
　（１）＜１＞～＜１９＞のいずれか１つに記載の光硬化性組成物を基板上に塗布する塗布工程
　（２）塗布された組成物から溶剤を除去する溶剤除去工程
　（３）溶剤が除去された組成物を活性光線によりパターン状に露光する露光工程
　（４）未露光部の組成物を水性現像液により除去して現像する現像工程
　＜２３＞　＜２１＞に記載の硬化物の製造方法、又は、＜２２＞に記載の樹脂パターン製造方法により得られた硬化物、
　＜２４＞　＜１＞～＜１９＞のいずれか１つに記載の光硬化性組成物を硬化してなる硬化膜、
　＜２５＞　層間絶縁膜である、＜２４＞に記載の硬化膜、
　＜２６＞　＜２４＞又は＜２５＞に記載の硬化膜を有する液晶表示装置、
　＜２７＞　＜２４＞又は＜２５＞に記載の硬化膜を有する有機ＥＬ表示装置、
　＜２８＞　＜２４＞又は＜２５＞に記載の硬化膜を有するタッチパネル表示装置。 <15> The photocurable composition according to any one of <1> to <14>, wherein the molecular weight of component A is 1,000 or less,
<16> The photocurable composition according to any one of <1> to <15>, wherein the content of component A is 30% by mass or more based on the total solid content of the composition,
<17> The photocurable composition according to any one of <1> to <16>, further comprising (Component D) a dispersant,
<18> The photocurable composition according to any one of <1> to <17>, which comprises (Component E) a polymerizable compound and (Component F) a polymerization initiator as Component X.
<19> The light according to any one of <1> to <17>, comprising (Component M) an alkali-soluble resin, (Component N) a crosslinking agent, and (Component O) an acid generator as Component X Curable composition,
<20> A transfer material obtained by forming at least one layer of the photocurable composition according to any one of <1> to <19> on a support,
<21> A method for producing a cured product comprising at least steps (a) to (c) in this order,
(A) Application step of applying the photocurable composition according to any one of <1> to <19> on a substrate (b) Solvent removal step of removing the solvent from the applied composition (c) An exposure step of irradiating the composition from which the solvent has been removed with an actinic ray <22> a resin pattern manufacturing method comprising at least steps (1) to (4) in this order;
(1) Application step of applying the photocurable composition according to any one of <1> to <19> on a substrate (2) Solvent removal step of removing the solvent from the applied composition (3) The exposure process which exposes the composition from which the solvent was removed to the pattern shape with actinic rays (4) The development process which removes and develops the composition of an unexposed part with an aqueous developing solution <23> Cured material as described in <21> Or a cured product obtained by the resin pattern production method according to <22>,
<24> A cured film obtained by curing the photocurable composition according to any one of <1> to <19>,
<25> The cured film according to <24>, which is an interlayer insulating film,
<26> A liquid crystal display device having the cured film according to <24> or <25>,
<27> An organic EL display device having the cured film according to <24> or <25>,
<28> A touch panel display device having the cured film according to <24> or <25>.
　本発明によれば、高い解像性が得られ、高屈折率かつ透過率が高いパターンを形成可能な光硬化性組成物を提供することができた。 According to the present invention, it was possible to provide a photocurable composition capable of forming a pattern with high resolution and high refractive index and high transmittance.
液晶表示装置の一例の構成概念図を示す。液晶表示装置におけるアクティブマトリックス基板の模式的断面図を示し、層間絶縁膜である硬化膜１７を有している。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. 有機ＥＬ表示装置の一例の構成概念図を示す。ボトムエミッション型の有機ＥＬ表示装置における基板の模式的断面図を示し、平坦化膜４を有している。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. 静電容量型入力装置の構成を示す断面図である。It is sectional drawing which shows the structure of an electrostatic capacitance type input device. 前面板の一例を示す説明図である。It is explanatory drawing which shows an example of a front plate. 第一の透明電極パターン及び第二の透明電極パターンの一例を示す説明図である。It is explanatory drawing which shows an example of a 1st transparent electrode pattern and a 2nd transparent electrode pattern.
　以下において、本発明の内容について詳細に説明する。以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
　なお、本発明において、数値範囲を表す「下限～上限」の記載は、「下限以上、上限以下」を表し、「上限～下限」の記載は、「上限以下、下限以上」を表す。すなわち、上限及び下限を含む数値範囲を表す。
　また、本発明において、「（成分Ａ）２つ以上の窒素原子を有する複素環化合物」等を、単に「成分Ａ」等ともいう。
　更に、本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　また、本発明において、「質量％」と「重量％」とは同義であり、「質量部」と「重量部」とは同義である。 Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present invention, the description of “lower limit to upper limit” representing the numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit.
In the present invention, “(Component A) a heterocyclic compound having two or more nitrogen atoms” or the like is also simply referred to as “Component A” or the like.
Furthermore, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
（光硬化性組成物）
　本発明の光硬化性組成物は、（成分Ａ）２つ以上の窒素原子を有する複素環化合物、（成分Ｂ）金属酸化物粒子、（成分Ｃ）溶剤、及び、（成分Ｘ）硬化性成分を含有することを特徴とする。
　本発明の光硬化性組成物は、ネガ型レジスト組成物として好適に用いることができる。本発明の光硬化性組成物は、光で硬化する性質を有する組成物である。
　更に、本発明の光硬化性組成物は、マイクロレンズ、光導波路、反射防止膜、ＬＥＤ用封止材及びＬＥＤ用チップコート材等の光学部材用組成物、又は、タッチパネルに使用される配線電極の視認性低減用組成物であることが好ましい。なお、タッチパネルに使用される配線電極の視認性低減用組成物とは、タッチパネルに使用される配線電極の視認性を低減する、すなわち、配線電極を見えにくくする部材用組成物であり、例えば、ＩＴＯ（酸化インジウムスズ）電極間の層間絶縁膜などが挙げられ、本発明の光硬化性組成物は、当該用途に好適に使用することができる。 (Photocurable composition)
The photocurable composition of the present invention comprises (Component A) a heterocyclic compound having two or more nitrogen atoms, (Component B) metal oxide particles, (Component C) a solvent, and (Component X) a curable component. It is characterized by containing.
The photocurable composition of the present invention can be suitably used as a negative resist composition. The photocurable composition of the present invention is a composition having a property of being cured by light.
Furthermore, the photocurable composition of the present invention is a composition for an optical member such as a microlens, an optical waveguide, an antireflection film, an LED sealing material, and an LED chip coating material, or a wiring electrode used for a touch panel. It is preferable that the composition is for reducing visibility. In addition, 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 include an interlayer insulating film between ITO (indium tin oxide) electrodes, and the photocurable composition of the present invention can be suitably used for the application.
　タッチパネル分野では、ブリッジ型のＩＴＯ配線における絶縁層（フォトインシュレーター、ＰＩ）見えや酸化インジウムスズ（ＩＴＯ）に起因する配線見えが問題であった。
　これらは、ＩＴＯと絶縁層との屈折率の差、又は、ＩＴＯとその周囲のガラス基板やオーバーコート層などとの屈折率の差により、光の反射率に差が生じ、透明なＩＴＯ及び／又は絶縁層が視認できてしまう現象である。例えば、ＩＴＯの屈折率は約１．９程度と大きく、ガラス基板の屈折率は１．５程度であるため、屈折率の差が生じ、視認できてしまうと推定される。
　高屈折率の材料として金属酸化物粒子を用いることが知られているが、屈折率を上げるために金属酸化物粒子を絶縁膜などの組成物に充填、特には、４０質量％以上の高充填にして塗布すると、金属酸化物粒子が多く、粒子の凝集を分散剤だけでは防ぐことができない、いわゆる塗布時の金属酸化物粒子の凝集が生じることを本発明者等は見出した。これは、分散剤を増量することで多少の良化はするが、上記絶縁層の膜厚におけるヘイズの値として、１％以下のヘイズを目的にする用途には達成できていない。
　本発明者等は詳細な検討の結果、成分Ａ～成分Ｃ及び成分Ｘを含有する光硬化性組成物とすることにより、（成分Ｂ）金属酸化物粒子の分散性を改良し、透明性に優れ、高屈折率であり、解像性に優れた光硬化性組成物が得られることを見いだした。
　以下、本発明の光硬化性組成物について詳細に説明する。 In the touch panel field, the appearance of the insulating layer (photo insulator, PI) in the bridge-type ITO wiring and the wiring appearance due to indium tin oxide (ITO) have been problems.
The difference in refractive index between the ITO and the insulating layer, or the refractive index difference between the ITO and the surrounding glass substrate, overcoat layer, etc. causes a difference in the reflectance of the light. Or it is a phenomenon in which the insulating layer is visible. For example, the refractive index of ITO is as large as about 1.9, and the refractive index of the glass substrate is about 1.5. Therefore, it is estimated that a difference in refractive index occurs and the glass substrate can be visually recognized.
It is known that metal oxide particles are used as a material having a high refractive index, but in order to increase the refractive index, the metal oxide particles are filled into a composition such as an insulating film, in particular, a high filling of 40 mass% or more The present inventors have found that, when applied in such a manner, there are many metal oxide particles, and aggregation of the particles cannot be prevented only by the dispersant, so-called aggregation of the metal oxide particles during application occurs. This is somewhat improved by increasing the amount of the dispersant, but it has not been achieved for the purpose of haze of 1% or less as the haze value in the film thickness of the insulating layer.
As a result of detailed studies, the present inventors have improved the dispersibility of (Component B) metal oxide particles by making a photocurable composition containing Component A to Component C and Component X, thereby improving transparency. It has been found that a photocurable composition having an excellent, high refractive index and excellent resolution can be obtained.
Hereinafter, the photocurable composition of the present invention will be described in detail.
（成分Ａ）２つ以上の窒素原子を有する複素環化合物
　本発明の光硬化性組成物は、（成分Ａ）２つ以上の窒素原子を有する複素環化合物を含有する。成分Ａが金属酸化物粒子の表面に吸着することで、金属酸化物粒子同士の静電反発や立体的な反発を引き起こし、特に組成物を塗布・乾燥した際の金属酸化物の凝集を防ぐため、ヘイズが小さくなると推定される。
　成分Ａとしては、２つ以上の窒素原子を有する以外は特に制限はないが、複素環の環員として２つ以上の窒素原子を有する複素環化合物であることが好ましく、１，３位に窒素原子を少なくとも有する複素環構造を有する化合物であることがより好ましく、１，３位に窒素原子を少なくとも有する５員又は６員複素環構造を有する化合物であることが更に好ましく、１，３位に窒素原子を少なくとも有する５員複素環構造を有する化合物であることが特に好ましい。上記態様であると、金属酸化物粒子の分散性により優れ、ヘイズがより小さい硬化物が得られる。
　なお、「１，３位に窒素原子を少なくとも有する複素環構造」とは、複素環中に炭素原子の両側に窒素原子が結合した構造であればよく、正式な命名法における複素環上の１位及び３位でなくともよい。
　成分Ａにおける複素環の環員は、炭素原子及び窒素原子から少なくとも構成されていることが好ましく、更に酸素原子や硫黄原子を環員として含んでいてもよいが、炭素原子及び窒素原子よりなることが特に好ましい。
　成分Ａが有する窒素原子の数は、２つ以上であり、２～６つであることが好ましく、２～４つであることがより好ましい。また、成分Ａは、複素環の環員として、窒素原子を２～４つ有していることが好ましく、２つ又は３つ有していることがより好ましく、２つ有していることが更に好ましい。
　成分Ａにおける複素環は、飽和複素環であっても、不飽和複素環であってもよく、芳香族複素環であってもよい。
　また、成分Ａにおける複素環は、更に他の環と縮合していてもよい。また、上記他の環としては、複素環だけでなく、脂肪族環であっても、芳香環であってもよい。
　成分Ａは、複素環の環員以外の窒素原子を有していてもよいが、複素環の環員以外の窒素原子の数は、０～３つであることが好ましく、０～２つであることが好ましく、０又は１つであることが更に好ましく、複素環の環員以外の窒素原子を有していないことが特に好ましい。 (Component A) Heterocyclic Compound Having Two or More Nitrogen Atoms The photocurable composition of the present invention contains (Component A) a heterocyclic compound having two or more nitrogen atoms. Component A adsorbs on the surface of the metal oxide particles to cause electrostatic repulsion and steric repulsion between the metal oxide particles, and in particular to prevent aggregation of the metal oxide when the composition is applied and dried. It is estimated that haze is reduced.
Component A is not particularly limited except that it has two or more nitrogen atoms, but is preferably a heterocyclic compound having two or more nitrogen atoms as a ring member of the heterocyclic ring, and nitrogen at the 1,3-position. More preferably, it is a compound having a heterocyclic structure having at least atoms, more preferably a compound having a 5-membered or 6-membered heterocyclic structure having at least a nitrogen atom at the 1,3-positions, and at 1,3-positions. A compound having a 5-membered heterocyclic structure having at least a nitrogen atom is particularly preferable. If it is the said aspect, the hardened | cured material which is excellent by the dispersibility of a metal oxide particle, and has a smaller haze is obtained.
The “heterocyclic structure having at least a nitrogen atom at positions 1 and 3” may be a structure in which nitrogen atoms are bonded to both sides of a carbon atom in the heterocyclic ring. It does not have to be in the third or third place.
The ring member of the heterocyclic ring in component A is preferably composed of at least a carbon atom and a nitrogen atom, and may further contain an oxygen atom or a sulfur atom as a ring member, but consists of a carbon atom and a nitrogen atom. Is particularly preferred.
Component A has 2 or more nitrogen atoms, preferably 2 to 6, and more preferably 2 to 4. Component A preferably has 2 to 4 nitrogen atoms as ring members of the heterocyclic ring, more preferably has 2 or 3 nitrogen atoms, and preferably has 2 nitrogen atoms. Further preferred.
The heterocyclic ring in component A may be a saturated heterocyclic ring, an unsaturated heterocyclic ring, or an aromatic heterocyclic ring.
Moreover, the heterocyclic ring in Component A may be further condensed with other rings. Moreover, as said other ring, not only a heterocyclic ring but an aliphatic ring or an aromatic ring may be sufficient.
Component A may have a nitrogen atom other than the ring member of the heterocyclic ring, but the number of nitrogen atoms other than the ring member of the heterocyclic ring is preferably 0 to 3, preferably 0 to 2. It is preferably 0, more preferably 0, and particularly preferably no nitrogen atoms other than the ring members of the heterocyclic ring.
　成分Ａが有する複素環構造の具体例としては、イミダゾール構造、ベンゾイミダゾール構造、１，２，４－トリアゾール構造、４，５－ジヒドロ－１，２，４－トリアゾール構造、テトラゾール構造、２－イミダゾリン構造、４－イミダゾリン構造（２，３－ジヒドロイミダゾール構造）、イミダゾリジン構造、ピリミジン構造、キノキサリン構造、プリン構造、プテリジン構造、及び、ペリミジン構造よりなる群から選ばれた環構造が好ましく挙げられ、イミダゾール構造、ベンゾイミダゾール構造、１，２，４－トリアゾール構造、４，５－ジヒドロ－１，２，４－トリアゾール構造、テトラゾール構造、２－イミダゾリン構造、４－イミダゾリン構造、イミダゾリジン構造、及び、ピリミジン構造よりなる群から選ばれた環構造がより好ましく挙げられ、ベンゾイミダゾール構造又はイミダゾリジン構造が特に好ましく挙げられる。上記態様であると、金属酸化物粒子の分散性により優れ、ヘイズがより小さい硬化物が得られる。 Specific examples of the heterocyclic structure of component A include imidazole structure, benzimidazole structure, 1,2,4-triazole structure, 4,5-dihydro-1,2,4-triazole structure, tetrazole structure, 2-imidazoline Preferred examples thereof include a ring structure selected from the group consisting of a structure, 4-imidazoline structure (2,3-dihydroimidazole structure), imidazolidine structure, pyrimidine structure, quinoxaline structure, purine structure, pteridine structure, and perimidine structure, Imidazole structure, benzimidazole structure, 1,2,4-triazole structure, 4,5-dihydro-1,2,4-triazole structure, tetrazole structure, 2-imidazoline structure, 4-imidazoline structure, imidazolidine structure, and A ring structure selected from the group consisting of pyrimidine structures Mentioned Preferably, benzimidazole structure or imidazolidine structure are exemplified particularly preferred. If it is the said aspect, the hardened | cured material which is excellent by the dispersibility of a metal oxide particle, and has a smaller haze is obtained.
　成分Ａは、メルカプト基（－ＳＨ）又はチオキソ基（＝Ｓ）を有することが好ましい。上記態様であると、金属酸化物粒子の分散性により優れ、ヘイズがより小さい硬化物が得られる。
　また、成分Ａとしては、下記式（１）で表される化合物であることが好ましい。 Component A preferably has a mercapto group (—SH) or a thioxo group (═S). If it is the said aspect, the hardened | cured material which is excellent by the dispersibility of a metal oxide particle, and has a smaller haze is obtained.
Component A is preferably a compound represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000005
 （式（１）中、Ｒ1及びＲ2はそれぞれ独立に、水素原子、ハロゲン原子又は一価の有機基を表し、Ｒ1とＲ2とが結合して二価の有機基であってもよく、Ｒ3及びＲ4はそれぞれ独立に、水素原子又は一価の有機基を表し、Ｌ1は５員環又は６員環を形成する二価の連結基を表し、Ｒ3又はＲ4とＬ1とが結合して環を形成していてもよく、また、点線の結合は、点線で記載した含窒素二重結合が存在する場合は、Ｒ2及びＲ4が存在しないことを表し、点線で記載した含窒素二重結合が存在しない場合は、Ｒ2及びＲ4が存在することを表す。）
Figure JPOXMLDOC01-appb-C000005
 (In formula (1), R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and even if R 1 and R 2 are bonded to form a divalent organic group, Well, R 3 and R 4 each independently represents a hydrogen atom or a monovalent organic group, L 1 represents a divalent linking group forming a 5-membered ring or a 6-membered ring, and R 3 or R 4 and L 1 may be bonded to form a ring, and the dotted bond indicates that when the nitrogen-containing double bond described by the dotted line is present, R 2 and R 4 are not present; (If the nitrogen-containing double bond indicated by the dotted line is not present, it represents that R 2 and R 4 are present.)
　Ｒ1～Ｒ4における一価の有機基としては、アルキル基（シクロアルキル基、ビシクロアルキル基、トリシクロアルキル基を含む）、アルケニル基（シクロアルケニル基、ビシクロアルケニル基を含む）、アルキニル基、アリール基、複素環基（ヘテロ環基と言ってもよい）、シアノ基、ヒドロキシル基、ニトロ基、カルボキシル基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基（アルキルアミノ基、アリールアミノ基、ヘテロ環アミノ基を含む）、アンモニオ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキル及びアリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、アルキルジチオ基、アリールジチオ基、ヘテロ環ジチオ基、スルファモイル基、スルホ基、アルキル及びアリールスルフィニル基、アルキル及びアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリール及びヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、ホスホノ基、シリル基、ヒドラジノ基、ウレイド基、チオウレイド基、ボロン酸基（－Ｂ（ＯＨ）2）、ホスファト基（－ＯＰＯ（ＯＨ）2）、スルファト基（－ＯＳＯ3Ｈ）、その他の公知の置換基が例として挙げられる。また、上記基は、更に置換基により置換されていてもよい。 Examples of the monovalent organic group in R 1 to R 4 include an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, Aryl group, heterocyclic group (also called heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group , Alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonyl Amino group, sulf Moylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, alkyldithio group, aryldithio group, heterocyclic dithio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl And arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group , Silyl group, hydrazino group, ureido group, thioureido group, boronic acid group (—B (OH) 2 ), phosphato group (—OPO (OH) 2 ), sulfato group (—OSO 3 H), and other known substitutions Examples are the groups. Moreover, the said group may be further substituted by the substituent.
　Ｒ1及びＲ2はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アリール基、又は、メルカプト基であることが好ましく、水素原子、ハロゲン原子、アルキル基（好ましくは炭素数炭１～２０、より好ましくは炭素数１～８、更に好ましくは炭素数１～４）、アルケニル基（好ましくは炭素数２～２０、より好ましくは炭素数２～８、更に好ましくは炭素数２～４）、アリール基（好ましくは炭素数６～２０、より好ましくは炭素数６～１６、更に好ましくは炭素数６～１０）、又は、メルカプト基であることがより好ましい。また、上記アルキル基、アルケニル基及びアリール基は、更に置換基により置換されていてもよく、例えばアルキル基がアリール基により置換された、アラルキル基であってもよい。
　Ｒ3及びＲ4はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、又は、ヘテロ環基であることが好ましく、水素原子、アルキル基（好ましくは炭素数炭１～２０、より好ましくは炭素数１～８、より好ましくは炭素数１～４）、アルケニル基（好ましくは炭素数２～２０、より好ましくは炭素数２～１２、更に好ましくは炭素数２～６）、アルキニル基（好ましくは炭素数２～２０、より好ましくは炭素数２～１２、更に好ましくは炭素数２～６）アリール基（好ましくは炭素数６～２０、より好ましくは炭素数６～１６、更に好ましくは炭素数６～１０）、又は、ヘテロ環基であることがより好ましい。また、上記アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基は、更に置換基により置換されていてもよく、例えばアルキル基がアリール基により置換された、アラルキル基であってもよい。 R 1 and R 2 are each independently preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, or a mercapto group, and preferably a hydrogen atom, a halogen atom, or an alkyl group (preferably having a carbon number of 1 To 20, more preferably 1 to 8, more preferably 1 to 4, and an alkenyl group (preferably 2 to 20, more preferably 2 to 8, more preferably 2 to 4 carbon atoms). ), An aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and still more preferably 6 to 10 carbon atoms), or a mercapto group. The alkyl group, alkenyl group and aryl group may be further substituted with a substituent, for example, an aralkyl group in which the alkyl group is substituted with an aryl group.
R 3 and R 4 are each independently preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, preferably a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20 More preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms), an alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), Alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and further It is preferably a carbon number of 6 to 10) or a heterocyclic group. The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group may be further substituted with a substituent, for example, an aralkyl group in which the alkyl group is substituted with an aryl group.
　Ｒ1及びＲ2における一価の有機基としては、これらの中でも、メルカプト基が特に好ましい。
　また、Ｒ1及びＲ2における一価の有機基の炭素数は、０～２０であることが好ましく、０～８であることがより好ましく、０であることが特に好ましい。
　また、Ｒ1とＲ2とが結合して形成する二価の有機基としては、オキソ基、チオキソ基、アルキリデン基等が例として挙げられる。これらの中でも、チオキソ基が特に好ましい。
　Ｒ1及びＲ2はそれぞれ独立に、水素原子又はメルカプト基であることが特に好ましく、また、Ｒ1とＲ2とが結合して二価の有機基を形成する場合は、チオキソ基であることが特に好ましい。 Among these, a mercapto group is particularly preferable as the monovalent organic group for R 1 and R 2 .
Further, the carbon number of the monovalent organic group in R 1 and R 2 is preferably 0 to 20, more preferably 0 to 8, and particularly preferably 0.
Examples of the divalent organic group formed by combining R 1 and R 2 include an oxo group, a thioxo group, and an alkylidene group. Of these, a thioxo group is particularly preferable.
R 1 and R 2 are each independently preferably a hydrogen atom or a mercapto group, and when R 1 and R 2 are combined to form a divalent organic group, they are thioxo groups. Is particularly preferred.
　Ｒ3及びＲ4における一価の有機基としては、アルキル基又はアリール基が好ましく、モルフォリノメチル基又はフェニル基がより好ましい。また、上記アルキル基又はアリール基は、置換基により置換されていてもよい。
　Ｒ3及びＲ4における一価の有機基の炭素数は、０～２０であることが好ましく、１～１０であることがより好ましく、４～８であることが更に好ましい。
　Ｒ3及びＲ4はそれぞれ独立に、水素原子、アルキル基又はアリール基であることが好ましく、水素原子、モルフォリノメチル基又はフェニル基であることがより好ましく、水素原子又はフェニル基であることが更に好ましい。 The monovalent organic group in R 3 and R 4 is preferably an alkyl group or an aryl group, and more preferably a morpholinomethyl group or a phenyl group. The alkyl group or aryl group may be substituted with a substituent.
The carbon number of the monovalent organic group in R 3 and R 4 is preferably 0 to 20, more preferably 1 to 10, and still more preferably 4 to 8.
R 3 and R 4 are each independently preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, a morpholinomethyl group or a phenyl group, and a hydrogen atom or a phenyl group. Further preferred.
　Ｌ1は５員環又は６員環を形成する二価の連結基を表し、式（１）中の炭素原子と２つの窒素原子と共に複素環を形成する。
　二価の連結基としては、式（１）中の炭素原子と２つの窒素原子と共に５員複素環又は６員複素環を形成する基であれば、特に制限はないが、その環員が、炭素原子及び／又は窒素原子から形成される基であることが好ましく、前述した複素環構造の具体例を形成する基であることがより好ましい。中でも、ベンゾイミダゾール構造を形成する基、すなわち、１，２－フェニレン基、又は、イミダゾリジン構造を形成する基、すなわち、１，２－エチレン基であることが特に好ましい。 L 1 represents a divalent linking group forming a 5-membered ring or a 6-membered ring, and forms a heterocyclic ring together with the carbon atom and the two nitrogen atoms in the formula (1).
The divalent linking group is not particularly limited as long as it is a group that forms a 5-membered heterocyclic ring or a 6-membered heterocyclic ring with the carbon atom and the two nitrogen atoms in the formula (1). A group formed from a carbon atom and / or a nitrogen atom is preferable, and a group forming a specific example of the heterocyclic structure described above is more preferable. Among them, a group that forms a benzimidazole structure, that is, a 1,2-phenylene group, or a group that forms an imidazolidine structure, that is, a 1,2-ethylene group is particularly preferable.
　更に、成分Ａとしては、下記式（１－１）又は式（１－２）で表される化合物であることがより好ましい。 Furthermore, component A is more preferably a compound represented by the following formula (1-1) or formula (1-2).
Figure JPOXMLDOC01-appb-C000006
 （式（１－１）及び式（１－２）中、Ｒ6～Ｒ8はそれぞれ独立に、水素原子又は一価の有機基を表し、Ｌ2及びＬ3はそれぞれ独立に、５員環又は６員環を形成する二価の連結基を表し、Ｒ6とＬ2とが結合して環を形成していてもよく、Ｒ7又はＲ8とＬ3とが結合して環を形成していてもよい。）
Figure JPOXMLDOC01-appb-C000006
 (In Formula (1-1) and Formula (1-2), R 6 to R 8 each independently represents a hydrogen atom or a monovalent organic group, and L 2 and L 3 each independently represents a 5-membered ring. Or a divalent linking group forming a 6-membered ring, wherein R 6 and L 2 may be combined to form a ring, and R 7 or R 8 and L 3 are combined to form a ring. You may do it.)
　式（１－１）又は式（１－２）におけるＲ6～Ｒ8は、上記式（１）におけるＲ3及びＲ4と同義であり、好ましい態様も同様である。
　また、式（１－１）又は式（１－２）におけるＬ2及びＬ3は、上記式（１）におけるＬ1と同義であり、好ましい態様も同様である。
　成分Ａの好ましい具体例（Ｆ－１～Ｆ－１４）を以下に示す。ただし、本発明においては、これらに制限されるものではない。 R 6 to R 8 in formula (1-1) or formula (1-2) have the same meanings as R 3 and R 4 in formula (1), and the preferred embodiments are also the same.
In addition, L 2 and L 3 in formula (1-1) or formula (1-2) have the same meaning as L 1 in formula (1), and the preferred embodiments are also the same.
Preferred specific examples (F-1 to F-14) of component A are shown below. However, the present invention is not limited to these.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　これらの中でも、Ｆ－３～Ｆ－１１が好ましく、Ｆ－３、Ｆ－５、Ｆ－６又はＦ－９がより好ましく、Ｆ－５又はＦ－９が特に好ましい。
　成分Ａの分子量は、好ましくは６８～２，０００、より好ましくは６８～１，０００、更に好ましくは１００～８００、特に好ましくは１００～５００の範囲である。上記の数値の範囲内であると、諸特性が良好である。 Among these, F-3 to F-11 are preferable, F-3, F-5, F-6 or F-9 is more preferable, and F-5 or F-9 is particularly preferable.
The molecular weight of component A is preferably in the range of 68 to 2,000, more preferably 68 to 1,000, still more preferably 100 to 800, and particularly preferably 100 to 500. Various characteristics are favorable in the range of said numerical value.
　また、成分Ａは、１種単独で使用してもよいし、２種以上を併用することもできる。
　本発明の光硬化性組成物における成分Ａの含有量は、本発明の光硬化性組成物の全固形分に対して、０．１～２０質量％であることが好ましく、０．５～１５質量％であることがより好ましく、０．５～１０質量％であることが更に好ましい。上記範囲であると、金属酸化物粒子の分散性により優れ、ヘイズがより小さい硬化物が得られる。ここで、光硬化性組成物の全固形分とは、光硬化性組成物から溶剤等の揮発性成分を除いた成分を意味する。 Moreover, the component A may be used individually by 1 type, and can also use 2 or more types together.
The content of Component A in the photocurable composition of the present invention is preferably 0.1 to 20% by mass, based on the total solid content of the photocurable composition of the present invention, preferably 0.5 to 15 More preferably, it is more preferably 0.5 to 10% by mass. When it is in the above range, a cured product having excellent dispersibility of the metal oxide particles and smaller haze can be obtained. Here, the total solid content of the photocurable composition means a component obtained by removing volatile components such as a solvent from the photocurable composition.
（成分Ｂ）金属酸化物粒子
　本発明の光硬化性組成物は、屈折率や光透過性を調節することを目的として、金属酸化物粒子を含有する。金属酸化物粒子は、透明性が高く、光透過性を有するため、高屈折率で、透明性に優れたネガ型光硬化性組成物が得られる。
　成分Ｂは、当該粒子を除いた材料からなる光硬化性組成物の屈折率より屈折率が高いものであることが好ましく、具体的には、４００～７５０ｎｍの波長を有する光における屈折率が１．５０以上の粒子がより好ましく、屈折率が１．７０以上の粒子が更に好ましく、１．９０以上の粒子が特に好ましい。屈折率の上限は特に限定されないが、入手容易性の観点から、４．０以下であることが好ましく、３．５以下であることがより好ましく、３．０以下であることが更に好ましい。
　ここで、４００～７５０ｎｍの波長を有する光における屈折率が１．５０以上であるとは、上記範囲の波長を有する光における平均屈折率が１．５０以上であることを意味し、上記範囲の波長を有する全ての光における屈折率が１．５０以上であることを要しない。また、平均屈折率は、上記範囲の波長を有する各光に対する屈折率の測定値の総和を、測定点の数で割った値である。 (Component B) Metal Oxide Particles The photocurable 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 negative photocurable composition having a high refractive index and excellent transparency can be obtained.
Component B preferably has a refractive index higher than the refractive index of a photocurable composition made of a material excluding the particles, and specifically has a refractive index of 1 for light having a wavelength of 400 to 750 nm. More preferably, the particles have a refractive index of 1.70 or more, more preferably 1.90 or more. The upper limit of the refractive index is not particularly limited, but is preferably 4.0 or less, more preferably 3.5 or less, and still more preferably 3.0 or less from the viewpoint of availability.
Here, 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.
　なお、本発明における金属酸化物粒子の金属には、Ｂ、Ｓｉ、Ｇｅ、Ａｓ、Ｓｂ、Ｔｅ等の半金属も含まれるものとする。
　光透過性で屈折率の高い金属酸化物粒子としては、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｇｄ、Ｔｂ、Ｄｙ、Ｙｂ、Ｌｕ、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｍｏ、Ｗ、Ｚｎ、Ｂ、Ａｌ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ、Ｔｅ等の原子を含む酸化物粒子が好ましく、酸化チタン、チタン複合酸化物、酸化亜鉛、酸化ジルコニウム、インジウム／スズ酸化物、アンチモン／スズ酸化物がより好ましく、酸化チタン、チタン複合酸化物、酸化ジルコニウムが更に好ましく、酸化チタン、酸化ジルコニウムが特に好ましく、二酸化チタンが最も好ましい。二酸化チタンとしては、特に屈折率の高いルチル型が好ましい。これら金属酸化物粒子は、分散安定性付与のために表面を有機材料で処理することもできる。 Note that 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.
　金属酸化物粒子の平均一次粒子径は、１～２００ｎｍであることが好ましく、１～１００ｎｍであることがより好ましく、１～８０ｎｍであることが更に好ましく、１～５０ｎｍであることが特に好ましい。上記範囲であると、粒子の分散性に優れ、また、高屈折率であり、かつ透明性により優れる硬化物が得られる。
　金属酸化物粒子の平均一次粒子径は、分散した金属酸化物粒子を透過型電子顕微鏡により観察し、得られた写真から求めることができる。具体的には金属酸化物粒子の投影面積を求め、それに対応する円相当径を金属酸化物粒子の平均一次粒子径とする。なお、本発明における平均一次粒子径は、３００個の金属酸化物粒子について求めた円相当径の算術平均値とする。
　また、本発明においては、平均一次粒子径の指標として数平均粒子径を用いることもできる。本発明における金属酸化物粒子の数平均粒子径は、金属酸化物粒子を含む混合液又は分散液を、プロピレングリコールモノメチルエーテルアセテートで８０倍に希釈し、得られた希釈液について動的光散乱法を用いて測定することにより得られた値のことを言う。この測定は、日機装（株）製マイクロトラックＵＰＡ－ＥＸ１５０を用いて行って得られた数平均粒子径であることが好ましい。 The average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, more preferably 1 to 100 nm, still more preferably 1 to 80 nm, and particularly preferably 1 to 50 nm. Within the above range, a cured product having excellent particle dispersibility, a high refractive index, and excellent transparency can be obtained.
The average primary particle diameter of the metal oxide particles can be obtained from a photograph obtained by observing the dispersed metal oxide particles with a transmission electron microscope. Specifically, the projected area of the metal oxide particles is obtained, and the corresponding equivalent circle diameter is defined as the average primary particle diameter of the metal oxide particles. In addition, let the average primary particle diameter in this invention be the arithmetic mean value of the equivalent circle diameter calculated | required about 300 metal oxide particles.
In the present invention, the number average particle diameter can also be used as an index of the average primary particle diameter. The number average particle diameter of the metal oxide particles in the present invention is obtained by diluting a mixed solution or dispersion containing the metal oxide particles 80 times with propylene glycol monomethyl ether acetate, and using the obtained diluted solution, a dynamic light scattering method. It means the value obtained by measuring using. This measurement is preferably the number average particle diameter obtained by using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd.
　金属酸化物粒子の屈折率としては、特に制限はないが、高屈折率を得る観点から、１．７０～２．７０であることが好ましく、１．９０～２．７０であることが更に好ましい。
　また、金属酸化物粒子の比表面積は、１０～４００ｍ2／ｇであることが好ましく、２０～２００ｍ2／ｇであることが更に好ましく、３０～１５０ｍ2／ｇであることが最も好ましい。
　金属酸化物粒子の形状には、特に制限はない。例えば、米粒状、球形状、立方体状、紡錘形状又は不定形状であることができる。 The refractive index of the metal oxide particles is not particularly limited, but is preferably 1.70 to 2.70, more preferably 1.90 to 2.70 from the viewpoint of obtaining a high refractive index. .
The specific surface area of the metal oxide particles is preferably 10 ~ 400m 2 / g, more preferably from 20 ~ 200m 2 / g, and most preferably 30 ~ 150m 2 / g.
There is no restriction | limiting in particular in the shape of a metal oxide particle. For example, it can be a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape.
　金属酸化物粒子は、有機化合物により表面処理されたものであってもよい。表面処理に用いる有機化合物の例には、ポリオール、アルカノールアミン、ステアリン酸、シランカップリング剤及びチタネートカップリング剤が含まれる。中でも、ステアリン酸が好ましい。
　表面処理は、１種単独の表面処理剤でも、２種類以上の表面処理剤を組み合わせて実施してもよい。
　また、金属酸化物粒子の表面が、アルミニウム、ケイ素、ジルコニアなどの酸化物により覆われていることも好ましい。これにより、より耐候性が向上する。 The metal oxide particles may have been surface-treated with an organic compound. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, stearic acid is preferred.
The surface treatment may be carried out by using a single surface treatment agent or a combination of two or more surface treatment agents.
It is also preferable that the surface of the metal oxide particles is covered with an oxide such as aluminum, silicon, or zirconia. Thereby, a weather resistance improves more.
　本発明における金属酸化物粒子としては、市販されているものを好ましく用いることができる。具体的には、例えば、酸化チタン粒子として石原産業（株）製ＴＴＯシリーズ（ＴＴＯ－５１（Ａ）、ＴＴＯ－５１（Ｃ）など）、ＴＴＯ－Ｓ、Ｖシリーズ（ＴＴＯ－Ｓ－１、ＴＴＯ－Ｓ－２、ＴＴＯ－Ｖ－３など）、テイカ（株）製ＭＴシリーズ（ＭＴ－０１、ＭＴ－０５など）、酸化スズ－酸化チタン複合粒子としてオプトレイクＴＲ－５０２、オプトレイクＴＲ－５０４、酸化ケイ素－酸化チタン複合粒子としてオプトレイクＴＲ－５０３、オプトレイクＴＲ－５１３、オプトレイクＴＲ－５２０、オプトレイクＴＲ－５２１、オプトレイクＴＲ－５２７、酸化ジルコニウム粒子（（株）高純度化学研究所製）、酸化スズ－酸化ジルコニウム複合粒子（日揮触媒化成工業（株）製）、酸化ニオブ粒子としてバイラールＮｂ－Ｘ１０（多木化学（株）製）などが挙げられる。 As the metal oxide particles in the present invention, commercially available particles can be preferably used. Specifically, for example, TTO series (TTO-51 (A), TTO-51 (C), etc.), TTO-S, V series (TTO-S-1, TTO) manufactured by Ishihara Sangyo Co., Ltd. are used as titanium oxide particles. -S-2, TTO-V-3, etc.), MT series (MT-01, MT-05, etc.) manufactured by Teika Co., Ltd., OPTRAIK TR-502, OPTRAIK TR-504 as tin oxide-titanium oxide composite particles , Op-tlake TR-503, Op-tray TR-513, Op-tlake TR-520, Op-tlake TR-521, Op-tlake TR-527, Zirconium oxide particles (Co) ), Tin oxide-zirconium oxide composite particles (manufactured by JGC Catalysts & Chemicals Co., Ltd.), and niobium oxide particles such as viral Nb-X10 Chemical Co., Ltd.), and the like.
　また、成分Ｂは、１種単独で使用してもよいし、２種以上を併用することもできる。
　本発明の光硬化性組成物における金属酸化物粒子の含有量は、光硬化性組成物により得られる光学部材に要求される屈折率や、光透過性等を考慮して、適宜決定すればよいが、本発明の光硬化性組成物の全固形分に対して、１０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることが更に好ましい。また、８０質量％以下であることが好ましく、７０質量％以下であることがより好ましい。 Moreover, the component B 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 photocurable composition of the present invention may be appropriately determined in consideration of the refractive index required for the optical member obtained from the photocurable composition, light transmittance, and the like. However, it is preferable that it is 10 mass% or more with respect to the total solid of the photocurable composition of this invention, It is more preferable that it is 30 mass% or more, It is still more preferable that it is 40 mass% or more. Moreover, it is preferable that it is 80 mass% or less, and it is more preferable that it is 70 mass% or less.
　本発明において、粒子は、適当な分散剤及び溶媒中でボールミル、ロッドミル等の混合装置を用いて混合・分散することにより調製された分散液として使用に供することもできる。分散剤については、後述する。
　上記分散液の調製に使用される溶媒としては、例えば、後述する（成分Ｃ）溶剤のほか、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、２－メチル－２－プロパノール、１－ペンタノール、２－ペンタノール、３－ペンタノール、３－メチル－１－ブタノール、２－メチル－２－ブタノール、ネオペンタノール、シクロペンタノール、１－ヘキサノール、シクロヘキサノール等のアルコール類等を挙げることができる。
　これらの溶媒は、１種単独又は２種以上を混合して使用することができる。 In the present invention, the particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill. The dispersant will be described later.
Examples of the solvent used in the preparation of the dispersion include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, in addition to the (Component C) solvent described below. -Alcohols such as pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol, etc. Can be mentioned.
These solvent can be used individually by 1 type or in mixture of 2 or more types.
（成分Ｃ）溶剤
　本発明の光硬化性組成物は、（成分Ｃ）溶剤を含有する。本発明の光硬化性組成物は、本発明の必須成分と、更に後述の任意の成分を（成分Ｃ）溶剤に溶解した溶液として調製されることが好ましい。
　本発明の光硬化性組成物に使用される溶剤としては、公知の溶剤を用いることができ、エチレングリコールモノアルキルエーテル類、エチレングリコールジアルキルエーテル類、エチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールジアルキルエーテル類、プロピレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジアルキルエーテル類、ジエチレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、ジプロピレングリコールモノアルキルエーテルアセテート類、エステル類、ケトン類、アミド類、ラクトン類等が例示できる。また、本発明の光硬化性組成物に使用される溶剤の具体例としては特開２０１１－２２１４９４号公報の段落０１７４～０１７８に記載の溶剤も挙げられる。 (Component C) Solvent The photocurable composition of the present invention contains (Component C) a solvent. The photocurable composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in the (component C) solvent.
As the solvent used in the photocurable 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. Further, specific examples of the solvent used in the photocurable composition of the present invention include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A.
　また、これらの溶剤に更に必要に応じて、ベンジルエチルエーテル、ジヘキシルエーテル、エチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、イソホロン、カプロン酸、カプリル酸、１－オクタノール、１－ノナール、ベンジルアルコール、アニソール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、炭酸エチレン、炭酸プロピレン等の溶剤を添加することもできる。
　これら溶剤は、１種単独で又は２種以上を混合して使用することができる。本発明に用いることができる溶剤は、１種単独、又は、２種を併用することが好ましい。 In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added.
These solvents can be used alone or in combination of two or more. It is preferable that the solvent which can be used for this invention is single 1 type, or uses 2 types together.
　また、成分Ｃとしては、沸点１３０℃以上１６０℃未満の溶剤、沸点１６０℃以上の溶剤、又は、これらの混合物であることが好ましい。
　沸点１３０℃以上１６０℃未満の溶剤としては、プロピレングリコールモノメチルエーテルアセテート（沸点１４６℃）、プロピレングリコールモノエチルエーテルアセテート（沸点１５８℃）、プロピレングリコールメチル－ｎ－ブチルエーテル（沸点１５５℃）、プロピレングリコールメチル－ｎ－プロピルエーテル（沸点１３１℃）が例示できる。
　沸点１６０℃以上の溶剤としては、３－エトキシプロピオン酸エチル（沸点１７０℃）、ジエチレングリコールメチルエチルエーテル（沸点１７６℃）、プロピレングリコールモノメチルエーテルプロピオネート（沸点１６０℃）、ジプロピレングリコールメチルエーテルアセテート（沸点２１３℃）、３－メトキシブチルエーテルアセテート（沸点１７１℃）、ジエチレングリコールジエチエルエーテル（沸点１８９℃）、ジエチレングリコールジメチルエーテル（沸点１６２℃）、プロピレングリコールジアセテート（沸点１９０℃）、ジエチレングリコールモノエチルエーテルアセテート（沸点２２０℃）、ジプロピレングリコールジメチルエーテル（沸点１７５℃）、１，３－ブチレングリコールジアセテート（沸点２３２℃）が例示できる。
　これらの中でも、溶剤としては、プロピレングリコールモノアルキルエーテルアセテート類が好ましく、プロピレングリコールモノメチルエーテルアセテートが特に好ましい。 Component C is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.
Among these, as the solvent, propylene glycol monoalkyl ether acetates are preferable, and propylene glycol monomethyl ether acetate is particularly preferable.
　本発明の光硬化性組成物における（成分Ｃ）溶剤の含有量は、光硬化性組成物中の固形分１００質量部当たり、５０～９５質量部であることが好ましく、６０～９０質量部であることが更に好ましい。 The content of the (component C) solvent in the photocurable composition of the present invention is preferably 50 to 95 parts by mass, preferably 60 to 90 parts by mass, per 100 parts by mass of the solid content in the photocurable composition. More preferably it is.
（成分Ｄ）分散剤
　本発明の光硬化性組成物は、（成分Ｄ）分散剤を含有することが好ましい。分散剤を含有することにより、成分Ｂの組成物中での分散性をより向上させることができる。
　（成分Ｄ）分散剤としては、例えば、公知の顔料分散剤を適宜選択して用いることができるが、後述する（成分Ｓ）式（Ｓ）で表され、少なくとも１種の酸基を有する分散剤が特に好ましい。
　（成分Ｄ）分散剤としては、高分子分散剤を好ましく用いることができる。なお、高分子分散剤とは、分子量（重量平均分子量）が１，０００以上の分散剤である。 (Component D) Dispersant The photocurable composition of the present invention preferably contains (Component D) a dispersant. By containing a dispersing agent, the dispersibility in the composition of the component B can be improved more.
As the (Component D) dispersant, for example, a known pigment dispersant can be appropriately selected and used. (Component S) A dispersion represented by the formula (S) described later and having at least one acid group Agents are particularly preferred.
As (Component D) dispersant, a polymer dispersant can be preferably used. The polymer dispersant is a dispersant having a molecular weight (weight average molecular weight) of 1,000 or more.
　（成分Ｄ）分散剤としては、多くの種類の化合物を使用可能であり、具体的には、例えば、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系（共）重合体ポリフローＮｏ．７５、Ｎｏ．９０、Ｎｏ．９５（共栄社化学（株）製）、Ｗ００１（裕商（株）製）等のカチオン系界面活性剤；ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル等のノニオン系界面活性剤；Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株）製）等のアニオン系界面活性剤；ＥＦＫＡ－４６、ＥＦＫＡ－４７、ＥＦＫＡ－４７ＥＡ、ＥＦＫＡポリマー１００、ＥＦＫＡポリマー４００、ＥＦＫＡポリマー４０１、ＥＦＫＡポリマー４５０（いずれもチバ・スペシャルティ・ケミカルズ社製）、ディスパースエイド６、ディスパースエイド８、ディスパースエイド１５、ディスパースエイド９１００（いずれもサンノプコ（株）製）等の高分子分散剤；ソルスパース３０００、５０００、９０００、１２０００、１３２４０、１３９４０、１７０００、２４０００、２６０００、２８０００、４１０００などの各種ソルスパース分散剤（Ｌｕｂｒｉｚｏｌ社製）；アデカプルロニックＬ３１，Ｆ３８，Ｌ４２，Ｌ４４，Ｌ６１，Ｌ６４，Ｆ６８，Ｌ７２，Ｐ９５，Ｆ７７，Ｐ８４，Ｆ８７、Ｐ９４，Ｌ１０１，Ｐ１０３，Ｆ１０８、Ｌ１２１、Ｐ－１２３（ＡＤＥＫＡ（株）製）及びイソネットＳ－２０（三洋化成工業（株）製）、ＤＩＳＰＥＲＢＹＫ　１０１，１０３，１０６，１０８，１０９，１１１，１１２，１１６，１３０，１４０，１４２，１６２，１６３，１６４，１６６，１６７，１７０，１７１，１７４，１７６，１８０，１８２，２０００，２００１，２０５０，２１５０（ビックケミー社製）が挙げられる。その他、アクリル系共重合体など、分子末端又は側鎖に極性基を有するオリゴマー又はポリマーが挙げられる。 (Component D) As the dispersant, many types of compounds can be used. Specifically, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) Polymer Polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl Nonionic surfactants such as ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), DE Polymer dispersing agents such as Sparse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000 , 26000, 28000, 41000, and the like (manufactured by Lubrizol); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by ADEKA) and ISONET S-20 (manufactured by Sanyo Chemical Industries), DISPERBYK 101, 103, 106, 108, 109, 111, 112, 116, 130, 1 0,142,162,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (manufactured by BYK-Chemie GmbH) and the like. In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.
　本発明の光硬化性組成物は、（成分Ｄ）分散剤として、（成分Ｓ）下記式（Ｓ）で表され、少なくとも１種の酸基を有する分散剤を含有することが好ましい。本発明の光硬化性組成物は、成分Ｓを含有することにより、金属酸化物粒子の分散時において粗大粒子が少なく、分散液と重合体成分とを混合したときの凝集もないので、高屈折率で、透明性に優れた硬化物を形成することができる。 The photocurable composition of the present invention preferably contains (Component S) a dispersant represented by the following formula (S) and having at least one acid group as (Component D) a dispersant. Since the photocurable 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 at a high rate.
Figure JPOXMLDOC01-appb-C000008
 （式（Ｓ）中、Ｒ3は（ｍ＋ｎ）価の連結基を表し、Ｒ4及びＲ5はそれぞれ独立に、単結合又は二価の連結基を表し、Ａ2は有機色素構造、複素環構造、酸基、塩基性窒素原子を有する基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基及び水酸基よりなる群から選択された部分構造を少なくとも１種含む一価の有機基を表し、ｎ個のＡ2、Ｒ4は、同一であっても、異なっていてもよく、ｍは０～８を表し、ｎは２～９を表し、ｍ＋ｎは３～１０であり、Ｐ2は高分子骨格を表し、ｍ個のＰ2、Ｒ5は、同一であっても、異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000008
 (In the formula (S), 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, and 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, hydrocarbon group having 4 or more carbon atoms, alkoxysilyl group, epoxy group, isocyanate group and hydroxyl group Represents a monovalent organic group containing at least one partial structure selected from the group, n A 2 and R 4 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, and m P 2 and R 5 may be the same or different.)
　成分Ｓは、少なくとも１種の酸基を有する分散剤である。酸基を有することにより、金属酸化物粒子に対し吸着基として作用すると推定され、金属酸化物粒子の分散性に優れる。
　酸基としては、カルボン酸基（カルボキシ基）、スルホン酸基、リン酸基、フェノール性水酸基などが挙げられ、金属酸化物粒子への吸着力と分散性との観点から、カルボン酸基、スルホン酸基及びリン酸基よりなる群から選ばれた少なくとも１種であることが好ましく、カルボン酸基が特に好ましい。上記分散剤における酸基は、これらを１種単独で、又は、２種以上を組み合わせて有していてもよい。
　成分Ｓにおける酸基は、式（Ｓ）のいずれの構造が有していてもよい。具体的には例えば、酸基は、上記式（Ｓ）におけるＡ2に含まれてもよく、また、Ｐ2で示される高分子骨格中に含まれてもよく、Ａ2及びＰ2の両方に含まれてもよいが、効果の観点からは、Ａ2に含まれることが好ましい。 Component S is a dispersant having at least one 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.
Examples of 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.
　上記式（Ｓ）において、Ａ2は、有機色素構造、複素環構造、酸基、塩基性窒素原子を有する基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基、及び、水酸基よりなる群から選択された部分構造を少なくとも１種含む一価の有機基を表す。また、式（Ｓ）中にｎ個存在するＡ2はそれぞれ、同一であっても、異なっていてもよい。 In the above formula (S), 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, or a group having 4 or more carbon atoms. A monovalent organic group containing at least one partial structure selected from the group consisting of a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. Further, n A 2 present in the formula (S) may be the same or different.
　つまり、上記Ａ2は、有機色素構造、複素環構造のような金属酸化物粒子に対する吸着能を有する構造や、酸基、塩基性窒素原子を有する基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基、及び、水酸基のように、金属酸化物粒子に対する吸着能を有する官能基を少なくとも１種含む一価の有機基を表す。
　なお、以下、この金属酸化物粒子に対する吸着能を有する部分構造（上記構造及び官能基）を、適宜、「吸着部位」と総称して、説明する。 That is, 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. A monovalent containing at least one functional group capable of adsorbing to metal oxide particles, such as a group having an atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. Represents an organic group.
Hereinafter, 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.
　上記吸着部位は、１つのＡ2の中に、少なくとも１種含まれていればよく、２種以上を含んでいてもよい。
　また、本発明において、「吸着部位を少なくとも１種含む一価の有機基」は、前述の吸着部位と、１個～２００個の炭素原子、０個～２０個の窒素原子、０個～１００個の酸素原子、１個～４００個の水素原子、及び、０個～４０個の硫黄原子から成り立つ連結基と、が結合してなる一価の有機基である。なお、吸着部位自体が一価の有機基を構成しうる場合には、吸着部位そのものがＡ2で表される一価の有機基であってもよい。
　まず、上記Ａ2を構成する吸着部位について以下に説明する。 The adsorption sites are in one A 2, it may be contained at least one, may contain two or more kinds.
Further, in the present invention, 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. It is a monovalent organic group formed by bonding together oxygen atoms, 1 to 400 hydrogen atoms, and a linking group consisting of 0 to 40 sulfur atoms. In the case where adsorption sites themselves may constitute a monovalent organic group, the adsorption sites itself may be a monovalent organic group represented by A 2.
First, the adsorption site constituting A 2 will be described below.
　上記「有機色素構造」としては、例えば、フタロシアニン系、不溶性アゾ系、アゾレーキ系、アントラキノン系、キナクリドン系、ジオキサジン系、ジケトピロロピロール系、アントラピリジン系、アンサンスロン系、インダンスロン系、フラバンスロン系、ペリノン系、ペリレン系、チオインジゴ系の色素構造が好ましい例として挙げられ、フタロシアニン系、アゾレーキ系、アントラキノン系、ジオキサジン系、ジケトピロロピロール系の色素構造がより好ましく、フタロシアニン系、アントラキノン系、ジケトピロロピロール系の色素構造が特に好ましい。 Examples of the “organic dye structure” include, for example, phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavan. Examples of 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.
　また、上記「複素環構造」としては、複素環を少なくとも１以上有する基であればよい。上記「複素環構造」におけるヘテロ原子としては、Ｏ（酸素原子）、Ｎ（窒素原子）、又は、Ｓ（硫黄原子）の少なくとも１つを含むことが好ましく、窒素原子を少なくとも１つ含むことがより好ましい。上記「複素環構造」における複素環としては、例えば、チオフェン、フラン、キサンテン、ピロール、ピロリン、ピロリジン、ジオキソラン、ピラゾール、ピラゾリン、ピラゾリジン、イミダゾール、オキサゾール、チアゾール、オキサジアゾール、トリアゾール、チアジアゾール、ピラン、ピリジン、ピペリジン、ジオキサン、モルホリン、ピリダジン、ピリミジン、ピペラジン、トリアジン、トリチアン、イソインドリン、イソインドリノン、ベンズイミダゾロン、ベンゾチアゾール、コハクイミド、フタルイミド、ナフタルイミド、ヒダントイン、インドール、キノリン、カルバゾール、アクリジン、アクリドン、及び、アントラキノンよりなる群から選ばれた複素環が好ましい例として挙げられ、ピロリン、ピロリジン、ピラゾール、ピラゾリン、ピラゾリジン、イミダゾール、トリアゾール、ピリジン、ピペリジン、モルホリン、ピリダジン、ピリミジン、ピペラジン、トリアジン、イソインドリン、イソインドリノン、ベンズイミダゾロン、ベンゾチアゾール、コハクイミド、フタルイミド、ナフタルイミド、ヒダントイン、カルバゾール、アクリジン、アクリドン、及び、アントラキノンよりなる群から選ばれた複素環がより好ましい。 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 contains at least one nitrogen atom. More preferred. Examples of the heterocyclic ring in the “heterocyclic structure” 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, acridone And a heterocyclic ring selected from the group consisting of anthraquinone is a preferred example, pyrroline, pyrrolidine, pyrazole Pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carbazole, acridine, acridone And a heterocyclic ring selected from the group consisting of anthraquinone is more preferable.
　なお、上記「有機色素構造」又は「複素環構造」は、更に置換基を有していてもよく、置換基としては、例えば、メチル基、エチル基等の炭素数１～２０のアルキル基、フェニル基、ナフチル基等の炭素数６～１６のアリール基、水酸基、アミノ基、カルボキシ基、スルホンアミド基、Ｎ－スルホニルアミド基、アセトキシ基等の炭素数１～６のアシルオキシ基、メトキシ基、エトキシ基等の炭素数１～２０のアルコキシ基、塩素原子、臭素原子等のハロゲン原子、メトキシカルボニル基、エトキシカルボニル基、シクロヘキシルオキシカルボニル基等の炭素数２～７のアルコキシカルボニル基、シアノ基、ｔ－ブチルカーボネート基等の炭酸エステル基、等が挙げられる。ここで、これらの置換基は、下記の構造単位又は該構造単位が組み合わさって構成される連結基を介して有機色素構造又は複素環構造と結合していてもよい。 The “organic dye structure” or “heterocyclic structure” may further have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, An aryl group having 6 to 16 carbon atoms such as phenyl group and naphthyl group, an acyloxy group having 1 to 6 carbon atoms such as hydroxyl group, amino group, carboxy group, sulfonamide group, N-sulfonylamide group and acetoxy group, methoxy group, An alkoxy group having 1 to 20 carbon atoms such as an ethoxy group, a halogen atom such as a chlorine atom and a bromine atom, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a cyclohexyloxycarbonyl group, a cyano group, and carbonic acid ester groups such as t-butyl carbonate group. Here, 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.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　上記「酸基」としては、例えば、カルボン酸基、スルホン酸基、モノ硫酸エステル基、リン酸基、モノリン酸エステル基、ホウ酸基が好ましい例として挙げられ、カルボン酸基、スルホン酸基、モノ硫酸エステル基、リン酸基、モノリン酸エステル基がより好ましく、カルボン酸基、スルホン酸基、リン酸基が更に好ましく、カルボン酸基が特に好ましい。 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.
　また、上記「塩基性窒素原子を有する基」としては、例えば、アミノ基（－ＮＨ2）、置換イミノ基（－ＮＨＲ8、－ＮＲ9Ｒ10、ここで、Ｒ8、Ｒ9及びＲ10はそれぞれ独立に、炭素数１～２０のアルキル基、炭素数６以上のアリール基、炭素数７以上のアラルキル基を表し、炭素数１～２０のアルキル基、炭素数６～２０のアリール基、炭素数７～２０のアラルキル基であることが好ましい。）、下記式（ａ１）で表されるグアニジル基、下記式（ａ２）で表されるアミジニル基などが好ましい例として挙げられる。 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, an aryl group having 6 to 20 carbon atoms, Preferred examples include aralkyl groups having 7 to 20 carbon atoms.), Guanidyl groups represented by the following formula (a1), amidinyl groups represented by the following formula (a2), and the like.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式（ａ１）中、Ｒ11及びＲ12はそれぞれ独立に、炭素数１～２０のアルキル基、炭素数６以上のアリール基、炭素数７以上のアラルキル基を表し、炭素数１～２０のアルキル基、炭素数６～２０のアリール基、他素数７～２０のアラルキル基が好ましい。
　式（ａ２）中、Ｒ13及びＲ14はそれぞれ独立に、炭素数１～２０のアルキル基、炭素数６以上のアリール基、炭素数７以上のアラルキル基を表し、炭素数１～２０のアルキル基、炭素数６～２０のアリール基、炭素数７～２０のアラルキル基が好ましい。 In the formula (a1), R 11 and R 12 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, and an alkyl having 1 to 20 carbon atoms Group, aryl group having 6 to 20 carbon atoms, and other aralkyl groups having 7 to 20 carbon atoms are preferable.
In the formula (a2), 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, and an alkyl having 1 to 20 carbon atoms Group, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms are preferable.
　これらの中でも、アミノ基（－ＮＨ2）、置換イミノ基（－ＮＨＲ8、－ＮＲ9Ｒ10、ここで、Ｒ8、Ｒ9及びＲ10はそれぞれ独立に、炭素数１～１０のアルキル基、フェニル基、ベンジル基を表す。）、上記式（ａ１）で表されるグアニジル基（式（ａ１）中、Ｒ11及びＲ12はそれぞれ独立に、炭素数１～１０のアルキル基、フェニル基、ベンジル基を表す。）、上記式（ａ２）で表されるアミジニル基（式（ａ２）中、Ｒ13及びＲ14はそれぞれ独立に、炭素数１～１０のアルキル基、フェニル基、ベンジル基を表す。）などがより好ましい。
　特に、アミノ基（－ＮＨ2）、置換イミノ基（－ＮＨＲ8、－ＮＲ9Ｒ10、ここで、Ｒ8、Ｒ9及びＲ10はそれぞれ独立に、炭素数１～５のアルキル基、フェニル基、ベンジル基を表す。）、上記式（ａ１）で表されるグアニジル基（式（ａ１）中、Ｒ11及びＲ12はそれぞれ独立に、炭素数１～５のアルキル基、フェニル基、ベンジル基を表す。）、上記式（ａ２）で表されるアミジニル基（式（ａ２）中、Ｒ13及びＲ14は各々独立に、炭素数１～５のアルキル基、フェニル基、ベンジル基を表す。）などが好ましく用いられる。 Among these, 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 group having 1 to 10 carbon atoms. , A phenyl group and a benzyl group), and a guanidyl group represented by the above formula (a1) (in the formula (a1), R 11 and R 12 are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group. Amidinyl group represented by the above formula (a2) (in the formula (a2), R 13 and R 14 are each independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, a benzyl group). And the like are more preferable.
In particular, 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 group having 1 to 5 carbon atoms, phenyl A benzyl group), a guanidyl group represented by the above formula (a1) (in the formula (a1), R 11 and R 12 are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group, benzyl Amidinyl group represented by the above formula (a2) (in the formula (a2), R 13 and R 14 each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group). Etc.) are preferably used.
　上記「ウレア基」としては、例えば、－ＮＲ15ＣＯＮＲ16Ｒ17（ここで、Ｒ15、Ｒ16及びＲ17はそれぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６以上のアリール基、又は、炭素数７以上のアラルキル基を表し、炭素数１～２０のアルキル基、炭素数６～２０のアリール基、又は、炭素数７～２０のアラルキル基が好ましい。）が好ましい例として挙げられ、－ＮＲ15ＣＯＮＨＲ17（ここで、Ｒ15及びＲ17はそれぞれ独立に、水素原子、炭素数１～１０のアルキル基、炭素数６以上のアリール基、又は、炭素数７以上のアラルキル基を表し、炭素数１～１０のアルキル基、炭素数６～１０のアリール基、又は、炭素数７～１２のアラルキル基が好ましい。）がより好ましく、－ＮＨＣＯＮＨＲ17（ここで、Ｒ17は水素原子、炭素数１～１０のアルキル基、炭素数６以上のアリール基、又は、炭素数７以上のアラルキル基を表し、炭素数１～１０のアルキル基、炭素数６～１０のアリール基、又は、炭素数７～１２のアラルキル基が好ましい。）が特に好ましい。 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, 6 or more carbon atoms). Or an aryl group having 7 or more carbon atoms, 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 is preferable. -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, an aryl group having 6 or more carbon atoms, or 7 or more carbon atoms) More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms), and —NHCONHR 17 (where R 17 is hydrogen source Represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or And an aralkyl group having 7 to 12 carbon atoms is preferred).
　上記「ウレタン基」としては、例えば、－ＮＨＣＯＯＲ18、－ＮＲ19ＣＯＯＲ20、－ＯＣＯＮＨＲ21、－ＯＣＯＮＲ22Ｒ23（ここで、Ｒ18、Ｒ19、Ｒ20、Ｒ21、Ｒ22及びＲ23はそれぞれ独立に、炭素数１～２０のアルキル基、炭素数６以上のアリール基、又は、炭素数７以上のアラルキル基を表し、炭素数１～２０のアルキル基、炭素数６～２０のアリール基、炭素数７～２０のアラルキル基が好ましい。）などが好ましい例として挙げられ、－ＮＨＣＯＯＲ18、－ＯＣＯＮＨＲ21（ここで、Ｒ18及びＲ21はそれぞれ独立に、炭素数１～２０のアルキル基、炭素数６以上のアリール基、又は、炭素数７以上のアラルキル基を表し、炭素数１～２０のアルキル基、炭素数６～２０のアリール基、炭素数７～２０のアラルキル基が好ましい。）などがより好ましく、－ＮＨＣＯＯＲ18、－ＯＣＯＮＨＲ21（ここで、Ｒ18及びＲ21はそれぞれ独立に、炭素数１～１０のアルキル基、炭素数６以上のアリール基、又は、炭素数７以上のアラルキル基を表し、炭素数１～１０のアルキル基、炭素数６～１０のアリール基、炭素数７～１２のアラルキル基が好ましい。）などが特に好ましい。 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). 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, and an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Group, an aralkyl group having 7 to 20 carbon atoms is preferred) and the like. —NHCOOR 18 , —OCONHR 21 (wherein R 18 and R 21 are each independently an alkyl having 1 to 20 carbon atoms). Group, an aryl group having 6 or more carbon atoms, 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. Better .) Are more preferable,, -NHCOOR 18, -OCONHR 21 (wherein, R 18 and R 21 are each independently an alkyl group having 6 or more aryl group having a carbon number of 1 to 10 carbon atoms, or, to 7 carbon atoms The above aralkyl groups are preferred, and an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms are preferred.
　上記「配位性酸素原子を有する基」としては、例えば、アセチルアセトナト基、クラウンエーテル構造を有する基などが挙げられる。 Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a group having a crown ether structure.
　上記「炭素数４以上の炭化水素基」としては、炭素数４以上のアルキル基、炭素数６以上のアリール基、炭素数７以上のアラルキル基などが好ましい例として挙げられ、炭素数４～２０のアルキル基、炭素数６～２０のアリール基、炭素数７～２０のアラルキル基などがより好ましく、炭素数４～１５のアルキル基（例えば、オクチル基、ドデシル基など）、炭素数６～１５のアリール基（例えば、フェニル基、ナフチル基など）、炭素数７～１５のアラルキル基（例えば、ベンジル基など）などが特に好ましい。 Preferred examples of the “hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferably, an alkyl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and 6 to 15 carbon atoms. Particularly preferred are aryl groups such as phenyl group and naphthyl group, and aralkyl groups having 7 to 15 carbon atoms (such as benzyl group).
　上記「アルコキシシリル基」としては、例えば、トリメトキシシリル基、トリエトキシシリル基などが挙げられる。 Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.
　上記吸着部位と結合する連結基としては、単結合、又は、１個～１００個の炭素原子、０個～１０個の窒素原子、０個～５０個の酸素原子、１個～２００個の水素原子、及び、０個～２０個の硫黄原子から成り立つ連結基が好ましく、この連結基は、無置換であってもよいし、置換基を更に有していてもよい。この連結基の具体的な例として、下記の構造単位又は該構造単位が組み合わさって構成される基を挙げることができる。 The linking group bonded to the adsorption site is a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms. A linking group consisting of 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.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記連結基が置換基を有する場合、置換基としては、例えば、メチル基、エチル基等の炭素数１～２０のアルキル基、フェニル基、ナフチル基等の炭素数６～１６のアリール基、水酸基、アミノ基、カルボキシ基、スルホンアミド基、Ｎ－スルホニルアミド基、アセトキシ基等の炭素数１～６のアシルオキシ基、メトキシ基、エトキシ基等の炭素数１～６のアルコキシ基、塩素原子、臭素原子等のハロゲン原子、メトキシカルボニル基、エトキシカルボニル基、シクロヘキシルオキシカルボニル基等の炭素数２～７のアルコキシカルボニル基、シアノ基、ｔ－ブチルカーボネート基等の炭酸エステル基等が挙げられる。 When the linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, and a hydroxyl group. An acyloxy group having 1 to 6 carbon atoms such as amino group, carboxy group, sulfonamido group, N-sulfonylamide group and acetoxy group, alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group, chlorine atom, bromine Examples thereof include halogen atoms such as atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, and cyclohexyloxycarbonyl group, and carbonate ester groups such as cyano group and t-butyl carbonate group.
　上記の中では、上記Ａ2として、有機色素構造、複素環構造、酸基、塩基性窒素原子を有する基、ウレア基、及び、炭素数４以上（好ましくは炭素数４以上２０以下）の炭化水素基よりなる群から選択された部分構造を少なくとも１種含む一価の有機基であることが好ましく、酸基を少なくとも１種含む一価の有機基であることが特に好ましい。 In the above, as A 2 , an organic dye structure, a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, and carbonization of 4 or more carbon atoms (preferably 4 to 20 carbon atoms) A monovalent organic group containing at least one partial structure selected from the group consisting of hydrogen groups is preferred, and a monovalent organic group containing at least one acid group is particularly preferred.
　上記Ａ2としては、下記式（４）で表される一価の有機基であることがより好ましい。 As the A 2, and more preferably a monovalent organic group represented by the following formula (4).
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　上記式（４）中、Ｂ1は上記吸着部位（すなわち、有機色素構造、複素環構造、酸基、塩基性窒素原子を有する基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基、及び、水酸基よりなる群から選択された部分構造）を表し、Ｒ24は単結合又は（ａ＋１）価の連結基を表す。ａは、１～１０の整数を表し、式（４）中にａ個存在するＢ1はそれぞれ、同一であっても、異なっていてもよい。 In the above 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, and B 1 existing in the formula (4) may be the same or different.
　上記Ｂ1で表される吸着部位としては、上記式（Ｓ）のＡ2を構成する吸着部位と同様のものが挙げられ、好ましい例も同様である。
　中でも、有機色素構造、複素環構造、酸基、塩基性窒素原子を有する基、ウレア基、及び、炭素数４以上の炭化水素基よりなる群から選択された部分構造が好ましく、酸基が特に好ましい。 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.
Among these, 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, and a hydrocarbon group having 4 or more carbon atoms is preferable, and an acid group is particularly preferable preferable.
　Ｒ24は、単結合又は（ａ＋１）価の連結基を表し、ａは１～１０の整数を表し、１～７の整数であることが好ましく、１～５の整数であることがより好ましく、１～３の整数であることが特に好ましい。
　（ａ＋１）価の連結基としては、１個～１００個の炭素原子、０個～１０個の窒素原子、０個～５０個の酸素原子、１個～２００個の水素原子、及び、０個～２０個の硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。 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.
The (a + 1) -valent linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 Groups comprised of up to 20 sulfur atoms are included and may be unsubstituted or further substituted.
　上記（ａ＋１）価の連結基は、具体的な例として、下記の構造単位又は該構造単位が組み合わさって構成される基（環構造を形成していてもよい。）を挙げることができる。 Specific examples of the (a + 1) -valent linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　Ｒ24としては、単結合、又は、１個～５０個の炭素原子、０個～８個の窒素原子、０個～２５個の酸素原子、１個～１００個の水素原子、及び、０個～１０個の硫黄原子から成り立つ（ａ＋１）価の連結基が好ましく、単結合、又は、１個～３０個の炭素原子、０個～６個の窒素原子、０個～１５個の酸素原子、１個～５０個の水素原子、及び０個～７個の硫黄原子から成り立つ（ａ＋１）価の連結基がより好ましく、単結合、又は、１個～１０個の炭素原子、０個～５個の窒素原子、０個～１０個の酸素原子、１個～３０個の水素原子、及び、０個～５個の硫黄原子から成り立つ（ａ＋１）価の連結基が特に好ましい。 R 24 is 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 0 (A + 1) -valent linking groups consisting of ˜10 sulfur atoms are preferred, a single bond, or 1-30 carbon atoms, 0-6 nitrogen atoms, 0-15 oxygen atoms, (A + 1) -valent linking group consisting of 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms is more preferred, a single bond or 1 to 10 carbon atoms, 0 to 5 (A + 1) -valent linking group consisting of 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms is particularly preferred.
　上記のうち、（ａ＋１）価の連結基が置換基を有する場合、置換基としては、例えば、メチル基、エチル基等の炭素数１～２０のアルキル基、フェニル基、ナフチル基等の炭素数６～１６のアリール基、水酸基、アミノ基、カルボキシ基、スルホンアミド基、Ｎ－スルホニルアミド基、アセトキシ基等の炭素数１～６のアシルオキシ基、メトキシ基、エトキシ基等の炭素数１～６のアルコキシ基、塩素原子、臭素原子等のハロゲン原子、メトキシカルボニル基、エトキシカルボニル基、シクロヘキシルオキシカルボニル基等の炭素数２～７のアルコキシカルボニル基、シアノ基、ｔ－ブチルカーボネート基等の炭酸エステル基、等が挙げられる。 Among the above, when the (a + 1) -valent linking group has a substituent, 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 6 to 16 aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., C1-C6 acyloxy groups, methoxy groups, ethoxy groups, etc. Alkoxy groups, halogen atoms such as chlorine atoms and bromine atoms, C2-C7 alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexyloxycarbonyl groups, carbonate esters such as cyano groups and t-butyl carbonate groups Group, and the like.
　上記式（Ｓ）において、Ｒ4及びＲ5はそれぞれ独立に、単結合又は二価の連結基を表す。ｎ個存在するＲ4はそれぞれ、同一であっても、異なっていてもよい。また、ｍ個存在するＲ5はそれぞれ、同一であっても、異なっていてもよい。
　Ｒ4及びＲ5における二価の連結基としては、１個～１００個の炭素原子、０個～１０個の窒素原子、０個～５０個の酸素原子、１個～２００個の水素原子、及び、０個～２０個の硫黄原子から成り立つ基が含まれ、無置換であっても、置換基を更に有していてもよい。 In the above formula (S), 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. Further, m R 5 s may be the same or different.
Examples of the divalent linking group for R 4 and R 5 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 consisting of 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.
　上記二価の連結基は、具体的な例として、下記の構造単位又は該構造単位が組み合わさって構成される基を挙げることができる。 Specific examples of the divalent linking group include the following structural units or groups formed by combining the structural units.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　Ｒ4及びＲ5としてはそれぞれ独立に、単結合、又は、１個～５０個の炭素原子、０個～８個の窒素原子、０個～２５個の酸素原子、１個～１００個の水素原子、及び、０個～１０個の硫黄原子から成り立つ二価の連結基が好ましく、単結合、又は、１個～３０個の炭素原子、０個～６個の窒素原子、０個～１５個の酸素原子、１個～５０個の水素原子、及び０個～７個の硫黄原子から成り立つ二価の連結基がより好ましく、単結合、又は、１個～１０個の炭素原子、０個～５個の窒素原子、０個～１０個の酸素原子、１個～３０個の水素原子、及び、０個～５個の硫黄原子から成り立つ二価の連結基が特に好ましい。 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 hydrogen atoms. A divalent linking group consisting of an atom and 0 to 10 sulfur atoms is preferred, a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 And more preferably a divalent linking group comprising 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms, a single bond, or 1 to 10 carbon atoms, 0 to Particularly preferred is a divalent linking group consisting of 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms.
　上記のうち、二価の連結基が置換基を有する場合、置換基としては、例えば、メチル基、エチル基等の炭素数１～２０のアルキル基、フェニル基、ナフチル基等の炭素数６～１６のアリール基、水酸基、アミノ基、カルボキシ基、スルホンアミド基、Ｎ－スルホニルアミド基、アセトキシ基等の炭素数１～６のアシルオキシ基、メトキシ基、エトキシ基等の炭素数１～６のアルコキシ基、塩素原子、臭素原子等のハロゲン原子、メトキシカルボニル基、エトキシカルボニル基、シクロヘキシルオキシカルボニル基等の炭素数２～７のアルコキシカルボニル基、シアノ基、ｔ－ブチルカーボネート基等の炭酸エステル基、等が挙げられる。 Among the above, when the divalent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and 6 to 6 carbon atoms such as a phenyl group and a naphthyl group. 16 aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups and other C1-C6 acyloxy groups, methoxy groups, ethoxy groups and other C1-C6 alkoxy groups Groups, halogen atoms such as chlorine atom and bromine atom, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate group, Etc.
　上記式（Ｓ）において、Ｒ3は、（ｍ＋ｎ）価の連結基を表す。ｍ＋ｎは３～１０を満たす。
　上記Ｒ3で表される（ｍ＋ｎ）価の連結基としては、１個～６０個の炭素原子、０個～１０個の窒素原子、０個～５０個の酸素原子、１個～１００個の水素原子、及び、０個～２０個の硫黄原子から成り立つ基が含まれ、無置換であっても、置換基を更に有していてもよい。 In the above formula (S), R 3 represents a (m + n) -valent linking group. m + n satisfies 3 to 10.
Examples of the (m + n) -valent linking group represented by R 3 include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100 carbon atoms. A group consisting of a hydrogen atom and 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.
　上記（ｍ＋ｎ）価の連結基は、具体的な例として、下記の構造単位又は該構造単位が組み合わさって構成される基（環構造を形成していてもよい。）を挙げることができる。 Specific examples of the (m + n) -valent linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　（ｍ＋ｎ）価の連結基としては、１個～６０個の炭素原子、０個～１０個の窒素原子、０個～４０個の酸素原子、１個～１２０個の水素原子、及び、０個～１０個の硫黄原子から成り立つ基が好ましく、１個～５０個の炭素原子、０個～１０個の窒素原子、０個～３０個の酸素原子、１個～１００個の水素原子、及び、０個～７個の硫黄原子から成り立つ基がより好ましく、１個～４０個の炭素原子、０個～８個の窒素原子、０個～２０個の酸素原子、１個～８０個の水素原子、及び、０個～５個の硫黄原子から成り立つ基が特に好ましい。 The (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 0 Preferred are groups consisting of ˜10 sulfur atoms, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and More preferred are groups consisting of 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, and 1 to 80 hydrogen atoms. And groups consisting of 0 to 5 sulfur atoms are particularly preferred.
　上記のうち、（ｍ＋ｎ）価の連結基が置換基を有する場合、置換基としては、例えば、メチル基、エチル基等の炭素数１～２０のアルキル基、フェニル基、ナフチル基等の炭素数６～１６のアリール基、水酸基、アミノ基、カルボキシ基、スルホンアミド基、Ｎ－スルホニルアミド基、アセトキシ基等の炭素数１～６のアシルオキシ基、メトキシ基、エトキシ基等の炭素数１～６のアルコキシ基、塩素原子、臭素原子等のハロゲン原子、メトキシカルボニル基、エトキシカルボニル基、シクロヘキシルオキシカルボニル基等の炭素数２～７のアルコキシカルボニル基、シアノ基、ｔ－ブチルカーボネート基等の炭酸エステル基等が挙げられる。 Among the above, when the (m + n) -valent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon number such as a phenyl group and a naphthyl group. 1 to 6 carbon atoms such as 6 to 16 aryl groups, hydroxyl groups, amino groups, carboxy groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups, etc., C1-C6 acyloxy groups, methoxy groups, ethoxy groups, etc. Alkoxy groups, halogen atoms such as chlorine atoms and bromine atoms, C2-C7 alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups and cyclohexyloxycarbonyl groups, carbonate esters such as cyano groups and t-butyl carbonate groups Groups and the like.
　上記Ｒ3で表される（ｍ＋ｎ）価の連結基の具体的な例〔具体例（１）～（１７）〕を以下に示す。ただし、本発明においては、これらに制限されるものではない。 Specific examples (specific examples (1) to (17)) of the (m + n) -valent linking group represented by R 3 are shown below. However, the present invention is not limited to these.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記の具体例の中でも、原料の入手性、合成の容易さ、各種溶媒への溶解性の観点から、最も好ましい（ｍ＋ｎ）価の連結基は下記の基である。 Among the above specific examples, 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.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記式（Ｓ）中、ｍは０～８を表す。ｍとしては、０．５～５が好ましく、０．５～４がより好ましく、０．５～３が特に好ましい。
　また、上記式（Ｓ）中、ｎは２～９を表す。ｎとしては、２～８が好ましく、２～７がより好ましく、３～６が特に好ましい。 In the above formula (S), m represents 0-8. m is preferably 0.5 to 5, more preferably 0.5 to 4, and particularly preferably 0.5 to 3.
In the above formula (S), n represents 2 to 9. n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.
　また、式（Ｓ）中のＰ2は、高分子骨格を表し、公知のポリマーなどから目的等に応じて選択することができる。式（Ｓ）中にｍ個存在するＰ2はそれぞれ、同一であっても、異なっていてもよい。また、Ｐ2は、一価の高分子骨格であることが好ましい。
　高分子骨格を構成するポリマー鎖としては、ビニルモノマーの単独重合体若しくは共重合体、エステル系ポリマー、エーテル系ポリマー、ウレタン系ポリマー、アミド系ポリマー、エポキシ系ポリマー、シリコーン系ポリマー、及び、これらの変性物又は共重合体〔例えば、ポリエーテル／ポリウレタン共重合体、ポリエーテル／ビニルモノマーの重合体の共重合体など（ランダム共重合体、ブロック共重合体、グラフト共重合体のいずれであってもよく、ランダム共重合体であることが好ましい。）を含む。〕よりなる群から選択された少なくとも１種が好ましく、ビニルモノマーの重合体若しくは共重合体、エステル系ポリマー、エーテル系ポリマー、ウレタン系ポリマー、及び、これらの変性物又は共重合体よりなる群から選択された少なくとも１種がより好ましく、ビニルモノマーの重合体又は共重合体が更に好ましく、アクリル樹脂（（メタ）アクリルモノマーの重合体又は共重合体）が特に好ましい。
　更には、上記ポリマーは、有機溶媒に可溶であることが好ましい。また、成分Ｓは、有機溶媒に可溶であることが好ましい。有機溶媒との親和性が低いと、例えば、分散媒との親和性が弱まり、分散安定化に十分な、金属酸化物粒子表面において成分Ｓにより形成される吸着層を確保できなくなることがある。 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 polymer skeleton.
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. And is preferably a random copolymer. And at least one selected from the group consisting of vinyl monomers, polymers or copolymers, ester polymers, ether polymers, urethane polymers, and their modified products or copolymers. At least one selected is more preferable, a polymer or copolymer of a vinyl monomer is further preferable, and an acrylic resin (a polymer or copolymer of a (meth) acryl monomer) is particularly preferable.
Furthermore, the polymer is preferably soluble in an organic solvent. Component S is preferably soluble in an organic solvent. When the affinity with the organic solvent is low, for example, the affinity with the dispersion medium is weakened, and it may be impossible to secure an adsorption layer formed by the component S on the surface of the metal oxide particles, which is sufficient for stabilizing the dispersion.
　本発明においては、上記Ｐ2における高分子骨格は、１種以上の酸基、例えば、カルボキシ基を有していてもよい。
　上記高分子骨格を構成する酸基を有するポリマーとしては、例えば、酸基を有する、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物）、及び、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、アルカノールアミン、顔料誘導体等を挙げることができる。これらの中でも、（メタ）アクリル酸共重合体が好ましい。 In the present invention, the polymer skeleton in P 2 may have one or more acid groups, for example, a carboxy group.
Examples of 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. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like. Among these, a (meth) acrylic acid copolymer is preferable.
　高分子骨格中に酸基を導入する手段には特に制限はなく、酸基を有するビニルモノマーにより導入する手段、架橋性側鎖を利用して酸基を付加させることにより導入する手段などをとることができるが、後述するように、高分子骨格が酸基を有するビニルモノマー由来の構成単位を含んで構成されることにより酸基が導入される態様が、酸基の導入量の制御が容易である点、合成コストの点から好ましい。
　ここで、「酸基」とは、上記Ａ2の説明において「酸基」として挙げたものを同様に挙げることができ、好ましくは、カルボキシ基である。 The means for introducing an acid group into the polymer skeleton is not particularly limited. For example, 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. However, as will be described later, 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. From the viewpoint of synthesis cost.
Here, 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.
　上記ビニルモノマーとしては、特に制限されないが、例えば、（メタ）アクリル酸エステル類、クロトン酸エステル類、ビニルエステル類、マレイン酸ジエステル類、フマル酸ジエステル類、イタコン酸ジエステル類、（メタ）アクリルアミド類、スチレン類、ビニルエーテル類、ビニルケトン類、オレフィン類、マレイミド類、（メタ）アクリロニトリル、酸基を有するビニルモノマーなどが好ましい。
　以下、これらのビニルモノマーの好ましい例について説明する。 Although it does not restrict | limit especially as said 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.
Hereinafter, preferable examples of these vinyl monomers will be described.
　（メタ）アクリル酸エステル類の例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸アミル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ｔ－ブチルシクロヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ｔ－オクチル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸アセトキシエチル、（メタ）アクリル酸フェニル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸２－（２－メトキシエトキシ）エチル、（メタ）アクリル酸３－フェノキシ－２－ヒドロキシプロピル、（メタ）アクリル酸２－クロロエチル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸３，４－エポキシシクロヘキシルメチル、（メタ）アクリル酸ビニル、（メタ）アクリル酸２－フェニルビニル、（メタ）アクリル酸１－プロペニル、（メタ）アクリル酸アリル、（メタ）アクリル酸２－アリロキシエチル、（メタ）アクリル酸プロパルギル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸ジエチレングリコールモノメチルエーテル、（メタ）アクリル酸ジエチレングリコールモノエチルエーテル、（メタ）アクリル酸トリエチレングリコールモノメチルエーテル、（メタ）アクリル酸トリエチレングリコールモノエチルエーテル、（メタ）アクリル酸ポリエチレングリコールモノメチルエーテル、（メタ）アクリル酸ポリエチレングリコールモノエチルエーテル、（メタ）アクリル酸β－フェノキシエトキシエチル、（メタ）アクリル酸ノニルフェノキシポリエチレングリコール、（メタ）アクリル酸ジシクロペンテニル、（メタ）アクリル酸ジシクロペンテニルオキシエチル、（メタ）アクリル酸トリフルオロエチル、（メタ）アクリル酸オクタフルオロペンチル、（メタ）アクリル酸パーフルオロオクチルエチル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸トリブロモフェニル、（メタ）アクリル酸トリブロモフェニルオキシエチル、（メタ）アクリル酸γ－ブチロラクトン－２－イルなどが挙げられる。 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) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth ) 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) (meth) acrylate ) Ethyl, (meth) acrylic acid 3-phenoxy-2-hydroxypropyl, (meth) acrylic acid 2-chloroethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl, (meth) acrylic Vinyl acetate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, (meth) Benzyl acrylate, (meth) acrylic acid diethylene glycol monomethyl ether , (Meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene Glycol monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acryl Trifluoroethyl acid, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) Acrylic acid tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, and (meth) acrylic acid γ- butyrolactone-2-yl.
　クロトン酸エステル類の例としては、クロトン酸ブチル、及び、クロトン酸ヘキシル等が挙げられる。
　ビニルエステル類の例としては、ビニルアセテート、ビニルクロロアセテート、ビニルプロピオネート、ビニルブチレート、ビニルメトキシアセテート、及び安息香酸ビニルなどが挙げられる。
　マレイン酸ジエステル類の例としては、マレイン酸ジメチル、マレイン酸ジエチル、及び、マレイン酸ジブチルなどが挙げられる。
　フマル酸ジエステル類の例としては、フマル酸ジメチル、フマル酸ジエチル、及び、フマル酸ジブチルなどが挙げられる。
　イタコン酸ジエステル類の例としては、イタコン酸ジメチル、イタコン酸ジエチル、及び、イタコン酸ジブチルなどが挙げられる。 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.
　（メタ）アクリルアミド類としては、（メタ）アクリルアミド、Ｎ－メチル（メタ）アクリルアミド、Ｎ－エチル（メタ）アクリルアミド、Ｎ－プロピル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ｎ－ブチルアクリル（メタ）アミド、Ｎ－ｔ－ブチル（メタ）アクリルアミド、Ｎ－シクロヘキシル（メタ）アクリルアミド、Ｎ－（２－メトキシエチル）（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－フェニル（メタ）アクリルアミド、Ｎ－ニトロフェニルアクリルアミド、Ｎ－エチル－Ｎ－フェニルアクリルアミド、Ｎ－ベンジル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、ジアセトンアクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－ヒドロキシエチルアクリルアミド、ビニル（メタ）アクリルアミド、Ｎ，Ｎ－ジアリル（メタ）アクリルアミド、Ｎ－アリル（メタ）アクリルアミドなどが挙げられる。 (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- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.
　スチレン類の例としては、スチレン、メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、イソプロピルスチレン、ブチルスチレン、ヒドロキシスチレン、メトキシスチレン、ブトキシスチレン、アセトキシスチレン、クロロスチレン、ジクロロスチレン、ブロモスチレン、クロロメチルスチレン、酸性物質により脱保護可能な基（例えばｔ－ブトキシカルボニル基（ｔ－Ｂｏｃ）など）で保護されたヒドロキシスチレン、ビニル安息香酸メチル、及び、α－メチルスチレンなどが挙げられる。 Examples of styrenes 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 Examples thereof include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-butoxycarbonyl group (t-Boc), etc.), methyl vinylbenzoate, and α-methylstyrene.
　ビニルエーテル類の例としては、メチルビニルエーテル、エチルビニルエーテル、２－クロロエチルビニルエーテル、ヒドロキシエチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、ヘキシルビニルエーテル、オクチルビニルエーテル、メトキシエチルビニルエーテル及びフェニルビニルエーテルなどが挙げられる。
　ビニルケトン類の例としては、メチルビニルケトン、エチルビニルケトン、プロピルビニルケトン、フェニルビニルケトンなどが挙げられる。
　オレフィン類の例としては、エチレン、プロピレン、イソブチレン、ブタジエン、イソプレンなどが挙げられる。
　マレイミド類の例としては、マレイミド、ブチルマレイミド、シクロヘキシルマレイミド、フェニルマレイミドなどが挙げられる。 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.
　（メタ）アクリロニトリル、ビニル基が置換した複素環式基（例えば、ビニルピリジン、Ｎ－ビニルピロリドン、ビニルカルバゾールなど）、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、Ｎ－ビニルイミダゾール、ビニルカプロラクトン等も使用できる。 Also used are (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. it can.
　上記の化合物以外にも、例えば、ウレタン基、ウレア基、スルホンアミド基、フェノール基、イミド基などの官能基を有するビニルモノマーも用いることができる。このようなウレタン基又はウレア基を有する単量体としては、例えば、イソシアナート基と水酸基又はアミノ基との付加反応を利用して、適宜合成することが可能である。具体的には、イソシアナート基含有モノマーと水酸基を１個含有する化合物、若しくは、１級若しくは２級アミノ基を１個含有する化合物との付加反応、又は、水酸基含有モノマー、若しくは、１級若しくは２級アミノ基含有モノマーとモノイソシアネートとの付加反応等により適宜合成することができる。 In addition to the above compounds, for example, 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. Such 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. Specifically, 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.
　次に、高分子骨格Ｐ2に酸基を導入するために用いられる酸基を有するビニルモノマーについて説明する。
　上記酸基を有するビニルモノマーの例としては、カルボキシ基を有するビニルモノマーやスルホン酸基を有するビニルモノマーが挙げられる。
　カルボキシ基を有するビニルモノマーとして、（メタ）アクリル酸、ビニル安息香酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、イタコン酸、クロトン酸、桂皮酸、アクリル酸ダイマーなどが挙げられる。また、２－ヒドロキシエチル（メタ）アクリレートなどの水酸基を有する単量体と無水マレイン酸や無水フタル酸、シクロヘキサンジカルボン酸無水物のような環状無水物との付加反応物、ω－カルボキシポリカプロラクトンモノ（メタ）アクリレートなども利用できる。また、カルボキシ基の前駆体として無水マレイン酸、無水イタコン酸、無水シトラコン酸などの無水物含有モノマーを用いてもよい。なお、これらの中では、共重合性やコスト、溶解性などの観点から（メタ）アクリル酸が特に好ましい。 Next, a vinyl monomer having an acid group used for introducing an acid group into the polymer skeleton P 2 will be described.
Examples of the vinyl monomer having an acid group include a vinyl monomer having a carboxy group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxy group 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. Further, 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, ω-carboxypolycaprolactone mono (Meth) acrylate and the like can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
　また、スルホン酸基を有するビニルモノマーとして、２－アクリルアミド－２－メチルプロパンスルホン酸などが挙げられ、リン酸基を有するビニルモノマーとして、リン酸モノ（２－アクリロイルオキシエチルエステル）、リン酸モノ（１－メチル－２－アクリロイルオキシエチルエステル）などが挙げられる。 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.
　更に、酸基を有するビニルモノマーとして、フェノール性ヒドロキシ基を含有するビニルモノマーやスルホンアミド基を含有するビニルモノマーなども利用することができる。
　高分子骨格Ｐ2が酸基を含むビニルモノマー由来のモノマー単位を含む場合、酸基を有するビニルモノマー由来のモノマー単位の高分子骨格中の含有量は、質量換算で、高分子骨格の全体に対し、３質量％～４０質量％であることが好ましく、５質量％～２０質量％の範囲であることがより好ましい。 Furthermore, as 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.
When 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. On the other hand, 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.
　上記式（Ｓ）で表され、少なくとも１種の酸基を有する分散剤のうち、以下に示すＲ3、Ｒ4、Ｒ5、Ｐ2、ｍ及びｎを全て満たすものが最も好ましい。
Ｒ3：上記具体例（１）、（２）、（１０）、（１１）、（１６）又は（１７）
Ｒ4：単結合、又は、下記の構造単位若しくは該構造単位が組み合わさって構成される「１個～１０個の炭素原子、０個～５個の窒素原子、０個～１０個の酸素原子、１個～３０個の水素原子、及び、０個～５個の硫黄原子」から成り立つ二価の連結基（置換基を有していてもよく、置換基としては、例えば、メチル基、エチル基等の炭素数１～２０のアルキル基、フェニル基、ナフチル基等の炭素数６～１６のアリール基、水酸基、アミノ基、カルボキシ基、スルホンアミド基、Ｎ－スルホニルアミド基、アセトキシ基等の炭素数１～６のアシルオキシ基、メトキシ基、エトキシ基等の炭素数１～６のアルコキシ基、塩素原子、臭素原子等のハロゲン原子、メトキシカルボニル基、エトキシカルボニル基、シクロヘキシルオキシカルボニル基等の炭素数２～７のアルコキシカルボニル基、シアノ基、ｔ－ブチルカーボネート基等の炭酸エステル基等が挙げられる。） Of the dispersants represented by the above formula (S) and having at least one acid group, those satisfying all of R 3 , R 4 , R 5 , P 2 , m and n shown below are most preferable.
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 oxygen atoms A divalent linking group comprising 1 to 30 hydrogen atoms and 0 to 5 sulfur atoms ”(which may have a substituent, such as a methyl group, ethyl Such as an alkyl group having 1 to 20 carbon atoms such as a group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxy group, a sulfonamido group, an N-sulfonylamido group and an acetoxy group. C1-C6 acyloxy group, C1-C6 alkoxy group such as methoxy group, ethoxy group, halogen atom such as chlorine atom, bromine atom, methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl Alkoxycarbonyl group having 2 to 7 carbon atoms like, a cyano group, or the like carbonate group such as t- butyl carbonate group.)
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Ｒ5：単結合、エチレン基、プロピレン基、下記基（ａ）又は下記基（ｂ）
　なお、下記基中、Ｒ12は水素原子又はメチル基を表し、Ｌは１又は２を表す。 R 5 : single bond, ethylene group, propylene group, the following group (a) or the following group (b)
In the following groups, R 12 represents a hydrogen atom or a methyl group, and L represents 1 or 2.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Ｐ2：カルボキシ基を有するビニルモノマーと他のビニルモノマーとの共重合体；酸基を有しないビニルモノマーの重合体又は共重合体；エステル系ポリマー、エーテル系ポリマー、及び、ウレタン系ポリマー、並びに、これらの変性物よりなる群から選択され、少なくとも１種の酸基を含んでいてもよいポリマー
ｍ：０．５～３
ｎ：３～６ 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
　成分Ｓにおける酸基の含有量は、成分Ｓが有する酸価により適宜決定される。成分Ｓの酸価としては、２０～３００ｍｇＫＯＨ／ｇであることが好ましく、５０～２５０ｍｇＫＯＨ／ｇがより好ましく、５０～２１０ｍｇＫＯＨ／ｇが特に好ましい。酸価が２０ｍｇＫＯＨ／ｇ以上であると、光硬化性組成物のアルカリ現像性が十分得られ、酸価が３００ｍｇＫＯＨ／ｇ以下であると、金属酸化物粒子の分散性、及び、分散安定性に優れる。 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. When the acid value is 20 mgKOH / g or more, sufficient alkali developability of the photocurable composition is obtained, and when the acid value is 300 mgKOH / g or less, the dispersibility and dispersion stability of the metal oxide particles are improved. Excellent.
　成分Ｓの分子量としては、重量平均分子量で、２，０００～２００，０００が好ましく、２，０００～１５，０００がより好ましく、２，５００～１０，０００が特に好ましい。重量平均分子量が上記範囲内であると、ポリマーの末端に導入された複数の上記吸着部位の効果が十分に発揮され、固体表面への吸着性を発揮する。本発明の光硬化性組成物が含有する成分Ｓは、１種類のみでもよいし、２種類以上であってもよい。２種類以上の場合は、その合計が上記範囲であることが好ましい。 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. When the weight average molecular weight is within the above range, the effects of the plurality of adsorption sites introduced at the ends of the polymer are sufficiently exhibited, and the adsorptivity to the solid surface is exhibited. The component S contained in the photocurable composition of the present invention may be one type or two or more types. In the case of two or more types, the total is preferably in the above range.
　以下に、成分Ｓの例示化合物を挙げるが、本発明はこれに限定されず、式（Ｓ）に包含されるかぎりにおいて、任意の構造をとることができる。また、下記例示化合物において、Ｐ１及びＰ２はそれぞれ、任意の値をとることができる。また、下記例示化合物において、カルボン酸エステルを有するモノマー単位とカルボキシ基を有するモノマー単位とからなる高分子骨格（Ｐ2）と結合する硫黄原子は、いずれのモノマー単位と結合していてもよく、高分子骨格の硫黄原子と結合しない他末端は、下記の化学式に標記していないが、高分子骨格の末端に通常許容される原子又は基であればよい。 Although the exemplary compound of the component S is mentioned below, this invention is not limited to this, As long as it is included by Formula (S), it can take arbitrary structures. Moreover, in the following exemplary compound, P1 and P2 can take arbitrary values, respectively. In the following exemplary compounds, the sulfur atom bonded to the polymer skeleton (P 2 ) composed of a monomer unit having a carboxylic acid ester and a monomer unit having a carboxy group may be bonded to any monomer unit, The other terminal that is not bonded to the sulfur atom of the polymer skeleton is not described in the following chemical formula, but may be any atom or group that is usually allowed at the terminal of the polymer skeleton.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　上記成分Ｓの例示化合物である、（Ｓ－１－１）～（Ｓ－１－１１）中、高分子骨格におけるカルボン酸エステルを有するモノマー単位とカルボキシ基を有するモノマー単位との含有比（Ｐ１：Ｐ２）は、質量換算で、１００：０～８０：２０の範囲であることが好ましい。
　成分Ｓは、例えば、特許第５０３６２６９号公報に記載の方法を参照して合成することができる。 In (S-1-1) to (S-1-11), which are exemplary compounds of component S, the content ratio of the monomer unit having a carboxylic acid ester to the monomer unit having a carboxy group in the polymer skeleton (P1 : P2) is preferably in the range of 100: 0 to 80:20 in terms of mass.
Component S can be synthesized, for example, with reference to the method described in Japanese Patent No. 5036269.
　分散剤は、１種単独で使用しても、２種以上併用してもよい。
　本発明の光硬化性組成物における分散剤の含有量は、光硬化性組成物の全固形分に対して、５～７０質量％の範囲が好ましく、１０～５０質量％の範囲がより好ましい。 A dispersing agent may be used individually by 1 type, or may be used together 2 or more types.
The content of the dispersant in the photocurable 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 photocurable composition.
（成分Ｘ）硬化性成分
　本発明の光硬化性組成物は、（成分Ｘ）硬化性成分を含有する。
　本発明の光硬化性組成物は、上述の通り、ネガ型のレジスト組成物として好適であり、光（活性光線）の照射により、（１）重合反応、又は、（２）架橋反応を生起して硬化することが好ましい。以下、光硬化性組成物が重合反応により硬化する場合を、「重合系」と称し、架橋反応により硬化する場合を「架橋系」と称することとする。本発明の光硬化性組成物は、重合系及び架橋系のいずれでもよく、また、両者が同時に生起されるものであってもよいが、重合系の光硬化性組成物であることが好ましい。
　重合系である場合、光硬化性組成物は、（成分Ｘ）硬化性成分として、（成分Ｅ）重合性化合物、及び、（成分Ｆ）重合開始剤を含有する。また、架橋系である場合、（成分Ｘ）硬化性成分として、（成分Ｍ）アルカリ可溶性樹脂、（成分Ｎ）架橋剤、及び、（成分Ｏ）酸発生剤を含有する。
　重合系である場合、本発明の光硬化性組成物は、活性光線の照射によりラジカル又はカチオン等の重合開始種が発生し、これに生起される重合反応により硬化が生じる。一方、架橋系である場合、活性光線の照射により酸発生剤より酸が発生し、この酸の作用により、アルカリ可溶性樹脂と、架橋剤との架橋が形成されて硬化する。
　以下、重合系及び架橋系に分けて、それぞれの成分について説明する。 (Component X) Curable Component The photocurable composition of the present invention contains (Component X) a curable component.
As described above, the photocurable composition of the present invention is suitable as a negative resist composition, and (1) a polymerization reaction or (2) a crosslinking reaction occurs upon irradiation with light (active light). It is preferable to cure. Hereinafter, a case where the photocurable composition is cured by a polymerization reaction is referred to as a “polymerization system”, and a case where the photocurable composition is cured by a crosslinking reaction is referred to as a “crosslinking system”. The photocurable composition of the present invention may be either a polymerization system or a crosslinking system, and both may be generated at the same time, but is preferably a polymerization system photocurable composition.
When it is a polymerization system, the photocurable composition contains (Component E) a polymerizable compound and (Component F) a polymerization initiator as (Component X) a curable component. Moreover, when it is a crosslinking system, (Component M) an alkali-soluble resin, (Component N) a crosslinking agent, and (Component O) an acid generator are contained as the (component X) curable component.
In the case of a polymerization system, the photocurable composition of the present invention generates a polymerization initiation species such as a radical or a cation by irradiation with actinic rays, and curing occurs due to a polymerization reaction caused thereby. On the other hand, in the case of a crosslinking system, an acid is generated from the acid generator upon irradiation with actinic rays, and the action of this acid forms a bridge between the alkali-soluble resin and the crosslinking agent and cures.
Hereinafter, each component will be described separately for a polymerization system and a crosslinking system.
１．重合系
（成分Ｅ）重合性化合物
　本発明において、光硬化性組成物が重合系である場合、（成分Ｘ）硬化性成分として、（成分Ｅ）重合性化合物を含有する。重合性化合物としては、ラジカル重合性化合物、カチオン重合性化合物のいずれも使用することができるが、硬化性及び解像性の観点から、ラジカル重合性化合物であることが好ましい。
　本発明における（成分Ｅ）重合性化合物は、少なくとも１個のエチレン性不飽和二重結合を有する付加重合性化合物であることが好ましく、末端エチレン性不飽和結合を少なくとも１個、好ましくは２個以上有する化合物から選ばれることがより好ましい。このような化合物は当該技術分野において広く知られるものであり、本発明においてはこれらを特に限定なく用いることができる。 1. Polymerization (Component E) Polymerizable Compound In the present invention, when the photocurable composition is a polymerization system, (Component X) a polymerizable compound is contained as the (Component X) curable component. As the polymerizable compound, any of a radical polymerizable compound and a cationic polymerizable compound can be used. From the viewpoint of curability and resolution, a radical polymerizable compound is preferable.
The (Component E) polymerizable compound in the present invention is preferably an addition polymerizable compound having at least one ethylenically unsaturated double bond, and preferably has at least one terminal ethylenically unsaturated bond, preferably two. More preferably, it is selected from the compounds having the above. Such compounds are widely known in the technical field, and can be used without particular limitation in the present invention.
　これらは、例えばモノマー、プレポリマー、すなわち２量体、３量体及びオリゴマー、又はそれらの混合物並びにそれらの共重合体などの化学的形態をもつ。モノマー及びその共重合体の例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など）や、そのエステル類、アミド類が挙げられ、好ましくは、不飽和カルボン酸と脂肪族多価アルコール化合物とのエステル、不飽和カルボン酸と脂肪族多価アミン化合物とのアミド類が用いられる。また、ヒドロキシル基やアミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステル類あるいは不飽和カルボン酸アミド類と単官能若しくは多官能イソシアネート類あるいはエポキシ類との付加反応物、及び単官能若しくは、多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基や、エポキシ基等の親電子性置換基を有する不飽和カルボン酸エステルあるいは不飽和カルボン酸アミド類と単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物；更にハロゲン基や、トシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステルあるいは不飽和カルボン酸アミド類と単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン、ビニルエーテル等に置き換えた化合物群を使用することも可能である。 These have chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof, and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and A dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having an electrophilic substituent such as an isocyanate group or an epoxy group and a monofunctional or polyfunctional alcohol, amine, or thiol; Furthermore, a substitution reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a leaving group such as a halogen group or a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. It is. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.
　脂肪族多価アルコール化合物と不飽和カルボン酸とのエステルのモノマーの具体例としては、アクリル酸エステルとして、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、１，３－ブタンジオールジアクリレート、テトラメチレングリコールジアクリレート、プロピレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリス（アクリロイルオキシプロピル）エーテル、トリメチロールエタントリアクリレート、ヘキサンジオールジアクリレート、１，４－シクロヘキサンジオールジアクリレート、テトラエチレングリコールジアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールジアクリレート、ジペンタエリスリトールヘキサアクリレート、ソルビトールトリアクリレート、ソルビトールテトラアクリレート、ソルビトールペンタアクリレート、ソルビトールヘキサアクリレート、トリス（アクリロイルオキシエチル）イソシアヌレート、ポリエステルアクリレートオリゴマー、イソシアヌール酸ＥＯ変性トリアクリレート等がある。 Specific examples of the ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanate There are nouric acid EO-modified triacrylate and the like.
　メタクリル酸エステルとしては、テトラメチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレート、エチレングリコールジメタクリレート、１，３－ブタンジオールジメタクリレート、ヘキサンジオールジメタクリレート、ペンタエリスリトールジメタクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールジメタクリレート、ジペンタエリスリトールヘキサメタクリレート、ソルビトールトリメタクリレート、ソルビトールテトラメタクリレート、ビス〔ｐ－（３－メタクリルオキシ－２－ヒドロキシプロポキシ）フェニル〕ジメチルメタン、ビス－〔ｐ－（メタクリルオキシエトキシ）フェニル〕ジメチルメタン等がある。 Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxyp Epoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.
　イタコン酸エステルとしては、エチレングリコールジイタコネート、プロピレングリコールジイタコネート、１，３－ブタンジオールジイタコネート、１，４－ブタンジオールジイタコネート、テトラメチレングリコールジイタコネート、ペンタエリスリトールジイタコネート、ソルビトールテトライタコネート等がある。
　クロトン酸エステルとしては、エチレングリコールジクロトネート、テトラメチレングリコールジクロトネート、ペンタエリスリトールジクロトネート、ソルビトールテトラジクロトネート等がある。イソクロトン酸エステルとしては、エチレングリコールジイソクロトネート、ペンタエリスリトールジイソクロトネート、ソルビトールテトライソクロトネート等がある。
　マレイン酸エステルとしては、エチレングリコールジマレート、トリエチレングリコールジマレート、ペンタエリスリトールジマレート、ソルビトールテトラマレート等がある。 Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
　その他のエステルの例として、例えば、特公昭５１－４７３３４号公報、特開昭５７－１９６２３１号公報記載の脂肪族アルコール系エステル類や、特開昭５９－５２４０号公報、特開昭５９－５２４１号公報、特開平２－２２６１４９号公報記載の芳香族系骨格を有するもの、特開平１－１６５６１３号公報記載のアミノ基を含有するもの等も好適に用いられる。更に、前述のエステルモノマーは混合物としても使用することができる。 Examples of other esters include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are preferably used. Furthermore, the ester monomers described above can also be used as a mixture.
　また、脂肪族多価アミン化合物と不飽和カルボン酸とのアミドのモノマーの具体例としては、メチレンビス－アクリルアミド、メチレンビス－メタクリルアミド、１，６－ヘキサメチレンビス－アクリルアミド、１，６－ヘキサメチレンビス－メタクリルアミド、ジエチレントリアミントリスアクリルアミド、キシリレンビスアクリルアミド、キシリレンビスメタクリルアミド等がある。
　その他の好ましいアミド系モノマーの例としては、特公昭５４－２１７２６号公報記載のシクロへキシレン構造を有すものを挙げることができる。 Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.
　また、イソシアネートと水酸基の付加反応を用いて製造されるウレタン系付加重合性化合物も好適であり、そのような具体例としては、例えば、特公昭４８－４１７０８号公報中に記載されている１分子に２個以上のイソシアネート基を有するポリイソシアネート化合物に、下記式（Ｖ）で表され、水酸基を有するビニルモノマーを付加させた１分子中に２個以上の重合性ビニル基を含有するビニルウレタン化合物等が挙げられる。 In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer having a hydroxyl group represented by the following formula (V) to a polyisocyanate compound having two or more isocyanate groups: Etc.
Figure JPOXMLDOC01-appb-C000028
 （式（Ｖ）中、Ｒ7及びＲ8はそれぞれ独立して、水素原子又はメチル基を示す。）
Figure JPOXMLDOC01-appb-C000028
 (In formula (V), R 7 and R 8 each independently represents a hydrogen atom or a methyl group.)
　また、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。更に、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平１－１０５２３８号公報に記載される、分子内にアミノ構造やスルフィド構造を有する重合性化合物類を用いることによっては、非常に感光スピードに優れた光硬化性組成物を得ることができる。 Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Further, by using polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a photo-curable composition having an excellent photosensitive speed.
　その他の例としては、特開昭４８－６４１８３号、特公昭４９－４３１９１号、特公昭５２－３０４９０号、各公報に記載されているようなポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸を反応させて得られたエポキシアクリレート類等の多官能のアクリレートやメタクリレートを挙げることができる。また、特公昭４６－４３９４６号公報、特公平１－４０３３７号公報、特公平１－４０３３６号公報記載の特定の不飽和化合物や、特開平２－２５４９３号公報記載のビニルホスホン酸系化合物等も挙げることができる。また、ある場合には、特開昭６１－２２０４８号公報記載のペルフルオロアルキル基を含有する構造が好適に使用される。更に、日本接着協会誌ｖｏｌ．２０、Ｎｏ．７、３００～３０８ページ（１９８４年）に記載されている光硬化性モノマー及びオリゴマーも使用することができる。
　また、フルオレン骨格を有するモノマーも好適に用いられる。特に９，９－ビスフェノキシフルオレン骨格が好ましい。具体例には、例えば、ＥＡ－０２００、ＥＡ－Ｆ５００３、ＥＡ-Ｆ５５０３、ＥＡ-Ｆ５５１０、（大阪ガスケミカル（株）製）、ＮＫエステルＡ－ＢＰＥＦ、ＮＫエステルＡ－ＢＰＥＦ―４Ｅ（新中村化学工業（株）製）等が挙げられる。 Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reaction. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, photocurable monomers and oligomers described on pages 300 to 308 (1984) can also be used.
A monomer having a fluorene skeleton is also preferably used. In particular, 9,9-bisphenoxyfluorene skeleton is preferable. Specific examples include, for example, EA-0200, EA-F5003, EA-F5503, EA-F5510 (manufactured by Osaka Gas Chemical Co., Ltd.), NK ester A-BPEF, NK ester A-BPEF-4E (Shin Nakamura Chemical). Kogyo Co., Ltd.).
　これらの重合性化合物について、その構造、単独使用か併用か、添加量等の使用方法の詳細は、光硬化性組成物の最終的な性能設計にあわせて任意に設定できる。例えば、次のような観点から選択される。
　感度の点では１分子あたりの不飽和基含量が多い構造が好ましく、多くの場合、２官能以上が好ましい。また、硬化膜の強度を高くするためには、３官能以上のものがよく、更に、異なる官能数・異なる重合性基（例えばアクリル酸エステル、メタクリル酸エステル、スチレン系化合物、ビニルエーテル系化合物）のものを併用することで、感度と強度の両方を調節する方法も有効である。
　また、光硬化性組成物に含有される他の成分（例えば、重合開始剤、金属酸化物粒子等）との相溶性、分散性に対しても、重合性化合物の選択・使用法は重要な要因であり、例えば、低純度化合物の使用や、２種以上の他の成分の併用により相溶性を向上させうることがある。また、基板などの硬質表面との密着性を向上させる目的で特定の構造を選択することもありうる。 About these polymerizable compounds, the details of the usage method such as the structure, single use or combination, addition amount and the like can be arbitrarily set according to the final performance design of the photocurable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
In addition, the selection and use method of the polymerizable compound is important for the compatibility and dispersibility with other components (for example, polymerization initiator, metal oxide particles, etc.) contained in the photocurable composition. For example, compatibility may be improved by using a low-purity compound or using two or more other components in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a substrate.
　光硬化性組成物の全固形分中、（成分Ｅ）重合性化合物の含有量は、５質量％～９０質量％の範囲であることが好ましく、１０質量％～８５質量％の範囲であることがより好ましく、２０質量％～８０質量％の範囲であることが更に好ましい。
　この範囲内であると、屈折率を低下させることなく、密着感度及び現像性が共に良好で好ましい。 The content of the (Component E) polymerizable compound in the total solid content of the photocurable composition is preferably in the range of 5% by mass to 90% by mass, and in the range of 10% by mass to 85% by mass. Is more preferable, and the range of 20% by mass to 80% by mass is even more preferable.
Within this range, both adhesion sensitivity and developability are good and preferable without lowering the refractive index.
（成分Ｆ）重合開始剤
　本発明において、光硬化性組成物が重合系である場合、（成分Ｘ）硬化性成分として、（成分Ｆ）重合開始剤を含有することが好ましい。本発明に用いられる（成分Ｆ）重合開始剤は、光により分解し、（成分Ｅ）重合性化合物の重合を開始、促進する化合物であり、波長３００ｎｍ以上５００ｎｍ以下の領域に吸収を有するものであることが好ましい。また、重合開始剤は、単独で、又は２種以上を併用して用いることができる。 (Component F) Polymerization initiator In this invention, when a photocurable composition is a polymerization system, it is preferable to contain (Component F) a polymerization initiator as (Component X) curable component. The (component F) polymerization initiator used in the present invention is a compound that is decomposed by light and initiates and accelerates polymerization of the (component E) polymerizable compound, and has an absorption in a wavelength region of 300 nm to 500 nm. Preferably there is. Moreover, a polymerization initiator can be used individually or in combination of 2 or more types.
　（成分Ｆ）重合開始剤としては、例えば、有機ハロゲン化化合物、オキシジアゾール化合物、カルボニル化合物、ケタール化合物、ベンゾイン化合物、アクリジン化合物、有機過酸化化合物、アゾ化合物、クマリン化合物、アジド化合物、メタロセン化合物、ヘキサアリールビイミダゾール化合物、有機ホウ酸化合物、ジスルホン酸化合物、オキシムエステル化合物、オニウム塩化合物、アシルホスフィン（オキシド）化合物が挙げられる。
　上記の有機ハロゲン化化合物、オキシジアゾ－ル化合物、カルボニル化合物、ケタール化合物、ベンゾイン化合物、アクリジン化合物、有機過酸化化合物、アゾ化合物、クマリン化合物、アジド化合物、メタロセン化合物、ヘキサアリールビイミダゾール化合物、有機ホウ酸化合物、ジスルホン酸化合物としては、特開２０１０－１０６２６８号公報の段落０１３５～０１４９に記載の化合物が例示される。また、オニウム塩化合物、アシルホスフィン（オキシド）化合物としては、特開２０１０－１０６２６８号公報の段落０２２０～０２２４に記載の化合物が例示される。 (Component F) Examples of the polymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds. , Hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.
Organic halogenated compounds, oxydiazol compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid Examples of the compound and the disulfonic acid compound include compounds described in paragraphs 0135 to 0149 of JP 2010-106268 A. Examples of the onium salt compound and the acylphosphine (oxide) compound include compounds described in paragraphs 0220 to 0224 of JP-A-2010-106268.
　本発明に用いられる（成分Ｆ）重合開始剤としては、感度、経時安定性、後加熱時の着色の観点から、オキシム化合物が好ましい。
　オキシム化合物としては、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９）１６５３－１６６０）、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９）１５６－１６２、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５）２０２－２３２、特開２０００－６６３８５号公報記載の化合物、特開２０００－８００６８号公報、特表２００４－５３４７９７号公報記載の化合物等が挙げられる。 As the (component F) polymerization initiator used in the present invention, an oxime compound is preferable from the viewpoints of sensitivity, stability over time, and coloring during post-heating.
Examples of oxime compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.
　また、オキシム系光重合開始剤としては、下記式（１）で表される化合物（以下、「特定オキシム化合物」ともいう。）も好ましい。なお、特定オキシム化合物は、オキシムのＮ－Ｏ結合が（Ｅ）体のオキシム化合物であっても、（Ｚ）体のオキシム化合物であっても、（Ｅ）体と（Ｚ）体との混合物であってもよい。 Further, as the oxime photopolymerization initiator, a compound represented by the following formula (1) (hereinafter also referred to as “specific oxime compound”) is preferable. The specific oxime compound is a mixture of the (E) isomer and the (Z) isomer, regardless of whether the oxime N—O bond is an (E) oxime compound or a (Z) oxime compound. It may be.
Figure JPOXMLDOC01-appb-C000029
 （式（１）中、Ｒ及びＢは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表す。）
Figure JPOXMLDOC01-appb-C000029
 (In formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
　上記Ｒで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
　上記一価の非金属原子団としては、アルキル基、アリール基、アルケニル基、アルキニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、ホスフィノイル基、複素環基、アルキルチオカルボニル基、アリールチオカルボニル基、ジアルキルアミノカルボニル基、ジアルキルアミノチオカルボニル基等が挙げられる。また、これらの基は、１以上の置換基を有していてもよい。また、前述した置換基は、更に他の置換基で置換されていてもよい。
　置換基としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、メトキシ基、エトキシ基、ｔｅｒｔ－ブトキシ基等のアルコキシ基、フェノキシ基、ｐ－トリルオキシ基等のアリールオキシ基、メトキシカルボニル基、ブトキシカルボニル基、フェノキシカルボニル基等のアルコキシカルボニル基又はアリールオキシカルボニル基、アセトキシ基、プロピオニルオキシ基、ベンゾイルオキシ基等のアシルオキシ基、アセチル基、ベンゾイル基、イソブチリル基、アクリロイル基、メタクリロイル基、メトキサリル基等のアシル基、メチルスルファニル基、ｔｅｒｔ－ブチルスルファニル基等のアルキルスルファニル基、フェニルスルファニル基、ｐ－トリルスルファニル基等のアリールスルファニル基、メチルアミノ基、シクロヘキシルアミノ基等のアルキルアミノ基、ジメチルアミノ基、ジエチルアミノ基、モルホリノ基、ピペリジノ基等のジアルキルアミノ基、フェニルアミノ基、ｐ－トリルアミノ基等のアリールアミノ基、メチル基、エチル基、ｔｅｒｔ－ブチル基、ドデシル基等のアルキル基、フェニル基、ｐ－トリル基、キシリル基、クメニル基、ナフチル基、アンスリル基、フェナントリル基等のアリール基等の他、ヒドロキシ基、カルボキシ基、ホルミル基、メルカプト基、スルホ基、メシル基、ｐ－トルエンスルホニル基、アミノ基、ニトロ基、シアノ基、トリフルオロメチル基、トリクロロメチル基、トリメチルシリル基、ホスホノ基、トリメチルアンモニウム基、ジメチルスルホニウム基、トリフェニルフェナシルホスホニウム基等が挙げられる。 The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Phosphinoyl group, heterocyclic group, alkylthiocarbonyl group, arylthiocarbonyl group, dialkylaminocarbonyl group, dialkylaminothiocarbonyl group and the like. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group , Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group or aryloxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, Acyl groups such as methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group, Group, alkylamino group such as cyclohexylamino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, In addition to alkyl groups such as tert-butyl group and dodecyl group, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups , Mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphono group, trimethylammonium group, dimethylsulfonium group, triphenyl Phenacylphosphonium group And the like.
　置換基を有していてもよいアルキル基としては、炭素数１～３０のアルキル基が好ましく、具体的には、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、オクダデシル基、イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、１－エチルペンチル基、シクロペンチル基、シクロヘキシル基、トリフルオロメチル基、２－エチルヘキシル基、フェナシル基、１－ナフトイルメチル基、２－ナフトイルメチル基、４－メチルスルファニルフェナシル基、４－フェニルスルファニルフェナシル基、４－ジメチルアミノフェナシル基、４－シアノフェナシル基、４－メチルフェナシル基、２－メチルフェナシル基、３－フルオロフェナシル基、３－トリフルオロメチルフェナシル基、及び、３－ニトロフェナシル基が例示できる。 The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, Beauty, 3 Nitorofenashiru group can be exemplified.
　置換基を有していてもよいアリール基としては、炭素数６～３０のアリール基が好ましく、具体的には、フェニル基、ビフェニル基、１－ナフチル基、２－ナフチル基、９－アンスリル基、９－フェナントリル基、１－ピレニル基、５－ナフタセニル基、１－インデニル基、２－アズレニル基、９－フルオレニル基、ターフェニル基、クオーターフェニル基、ｏ－、ｍ－及びｐ－トリル基、キシリル基、ｏ－、ｍ－及びｐ－クメニル基、メシチル基、ペンタレニル基、ビナフタレニル基、ターナフタレニル基、クオーターナフタレニル基、ヘプタレニル基、ビフェニレニル基、インダセニル基、フルオランテニル基、アセナフチレニル基、アセアントリレニル基、フェナレニル基、フルオレニル基、アントリル基、ビアントラセニル基、ターアントラセニル基、クオーターアントラセニル基、アントラキノリル基、フェナントリル基、トリフェニレニル基、ピレニル基、クリセニル基、ナフタセニル基、プレイアデニル基、ピセニル基、ペリレニル基、ペンタフェニル基、ペンタセニル基、テトラフェニレニル基、ヘキサフェニル基、ヘキサセニル基、ルビセニル基、コロネニル基、トリナフチレニル基、ヘプタフェニル基、ヘプタセニル基、ピラントレニル基、並びに、オバレニル基が例示できる。 The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specifically includes a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, Anthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.
　置換基を有していてもよいアルケニル基としては、炭素数２～１０のアルケニル基が好ましく、具体的には、ビニル基、アリル基、及び、スチリル基が例示できる。 The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and specific examples include a vinyl group, an allyl group, and a styryl group.
　置換基を有していてもよいアルキニル基としては、炭素数２～１０のアルキニル基が好ましく、具体的には、エチニル基、プロピニル基、及び、プロパルギル基が例示できる。 The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and specific examples include an ethynyl group, a propynyl group, and a propargyl group.
　置換基を有していてもよいアルキルスルフィニル基としては、炭素数１～２０のアルキルスルフィニル基が好ましく、具体的には、メチルスルフィニル基、エチルスルフィニル基、プロピルスルフィニル基、イソプロピルスルフィニル基、ブチルスルフィニル基、ヘキシルスルフィニル基、シクロヘキシルスルフィニル基、オクチルスルフィニル基、２－エチルヘキシルスルフィニル基、デカノイルスルフィニル基、ドデカノイルスルフィニル基、オクタデカノイルスルフィニル基、シアノメチルスルフィニル基、及び、メトキシメチルスルフィニル基が例示できる。 The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specifically includes a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group. And hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, and methoxymethylsulfinyl group. .
　置換基を有していてもよいアリールスルフィニル基としては、炭素数６～３０のアリールスルフィニル基が好ましく、具体的には、フェニルスルフィニル基、１－ナフチルスルフィニル基、２－ナフチルスルフィニル基、２－クロロフェニルスルフィニル基、２－メチルフェニルスルフィニル基、２－メトキシフェニルスルフィニル基、２－ブトキシフェニルスルフィニル基、３－クロロフェニルスルフィニル基、３－トリフルオロメチルフェニルスルフィニル基、３－シアノフェニルスルフィニル基、３－ニトロフェニルスルフィニル基、４－フルオロフェニルスルフィニル基、４－シアノフェニルスルフィニル基、４－メトキシフェニルスルフィニル基、４－メチルスルファニルフェニルスルフィニル基、４－フェニルスルファニルフェニルスルフィニル基、及び、４－ジメチルアミノフェニルスルフィニル基が例示できる。 The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2- Chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitro Phenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanyl group Nils sulfinyl group, and a 4-dimethylaminophenyl sulfinyl group can be exemplified.
　置換基を有していてもよいアルキルスルホニル基としては、炭素数１～２０のアルキルスルホニル基が好ましく、具体的には、メチルスルホニル基、エチルスルホニル基、プロピルスルホニル基、イソプロピルスルホニル基、ブチルスルホニル基、ヘキシルスルホニル基、シクロヘキシルスルホニル基、オクチルスルホニル基、２－エチルヘキシルスルホニル基、デカノイルスルホニル基、ドデカノイルスルホニル基、オクタデカノイルスルホニル基、シアノメチルスルホニル基、メトキシメチルスルホニル基、及び、パーフルオロアルキルスルホニル基が例示できる。 The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specifically includes a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group. Group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, and perfluoro An alkylsulfonyl group can be illustrated.
　置換基を有していてもよいアリールスルホニル基としては、炭素数６～３０のアリールスルホニル基が好ましく、具体的には、フェニルスルホニル基、１－ナフチルスルホニル基、２－ナフチルスルホニル基、２－クロロフェニルスルホニル基、２－メチルフェニルスルホニル基、２－メトキシフェニルスルホニル基、２－ブトキシフェニルスルホニル基、３－クロロフェニルスルホニル基、３－トリフルオロメチルフェニルスルホニル基、３－シアノフェニルスルホニル基、３－ニトロフェニルスルホニル基、４－フルオロフェニルスルホニル基、４－シアノフェニルスルホニル基、４－メトキシフェニルスルホニル基、４－メチルスルファニルフェニルスルホニル基、４－フェニルスルファニルフェニルスルホニル基、及び、４－ジメチルアミノフェニルスルホニル基が例示できる。 The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, 2- Chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitro Phenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, and 4-dimethyl Le amino phenylsulfonyl group can be exemplified.
　置換基を有していてもよいアシル基としては、炭素数２～２０のアシル基が好ましく、具体的には、アセチル基、プロパノイル基、ブタノイル基、トリフルオロアセチル基、ペンタノイル基、ベンゾイル基、１－ナフトイル基、２－ナフトイル基、４－メチルスルファニルベンゾイル基、４－フェニルスルファニルベンゾイル基、４－ジメチルアミノベンゾイル基、４－ジエチルアミノベンゾイル基、２－クロロベンゾイル基、２－メチルベンゾイル基、２－メトキシベンゾイル基、２－ブトキシベンゾイル基、３－クロロベンゾイル基、３－トリフルオロメチルベンゾイル基、３－シアノベンゾイル基、３－ニトロベンゾイル基、４－フルオロベンゾイル基、４－シアノベンゾイル基、及び、４－メトキシベンゾイル基が例示できる。 The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.
　置換基を有していてもよいアルコキシカルボニル基としては、炭素数２～２０のアルコキシカルボニル基が好ましく、具体的には、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ブトキシカルボニル基、ヘキシルオキシカルボニル基、オクチルオキシカルボニル基、デシルオキシカルボニル基、オクタデシルオキシカルボニル基、及び、トリフルオロメチルオキシカルボニル基が例示できる。 The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specifically includes a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.
　置換基を有していてもよいアリールオキシカルボニル基として具体的には、フェノキシカルボニル基、１－ナフチルオキシカルボニル基、２－ナフチルオキシカルボニル基、４－メチルスルファニルフェニルオキシカルボニル基、４－フェニルスルファニルフェニルオキシカルボニル基、４－ジメチルアミノフェニルオキシカルボニル基、４－ジエチルアミノフェニルオキシカルボニル基、２－クロロフェニルオキシカルボニル基、２－メチルフェニルオキシカルボニル基、２－メトキシフェニルオキシカルボニル基、２－ブトキシフェニルオキシカルボニル基、３－クロロフェニルオキシカルボニル基、３－トリフルオロメチルフェニルオキシカルボニル基、３－シアノフェニルオキシカルボニル基、３－ニトロフェニルオキシカルボニル基、４－フルオロフェニルオキシカルボニル基、４－シアノフェニルオキシカルボニル基、及び、４－メトキシフェニルオキシカルボニル基が例示できる。 Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, and 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl Group, 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.
　置換基を有していてもよいホスフィノイル基としては、炭素数２～５０のホスフィノイル基が好ましく、具体的には、ジメチルホスフィノイル基、ジエチルホスフィノイル基、ジプロピルホスフィノイル基、ジフェニルホスフィノイル基、ジメトキシホスフィノイル基、ジエトキシホスフィノイル基、ジベンゾイルホスフィノイル基、及び、ビス（２，４，６－トリメチルフェニル）ホスフィノイル基が例示できる。 The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, specifically, a dimethylphosphinoyl group, a diethylphosphinoyl group, a dipropylphosphinoyl group, a diphenyl group. Examples thereof include a phosphinoyl group, a dimethoxyphosphinoyl group, a diethoxyphosphinoyl group, a dibenzoylphosphinoyl group, and a bis (2,4,6-trimethylphenyl) phosphinoyl group.
　置換基を有していてもよい複素環基としては、窒素原子、酸素原子、硫黄原子若しくはリン原子を含む、芳香族又は脂肪族の複素環が好ましい。
　具体的には、チエニル基、ベンゾ［ｂ］チエニル基、ナフト［２，３－ｂ］チエニル基、チアントレニル基、フリル基、ピラニル基、イソベンゾフラニル基、クロメニル基、キサンテニル基、フェノキサチイニル基、２Ｈ－ピロリル基、ピロリル基、イミダゾリル基、ピラゾリル基、ピリジル基、ピラジニル基、ピリミジニル基、ピリダジニル基、インドリジニル基、イソインドリル基、３Ｈ－インドリル基、インドリル基、１Ｈ－インダゾリル基、プリニル基、４Ｈ－キノリジニル基、イソキノリル基、キノリル基、フタラジニル基、ナフチリジニル基、キノキサニリル基、キナゾリニル基、シンノリニル基、プテリジニル基、４ａＨ－カルバゾリル基、カルバゾリル基、β－カルボリニル基、フェナントリジニル基、アクリジニル基、ペリミジニル基、フェナントロリニル基、フェナジニル基、フェナルサジニル基、イソチアゾリル基、フェノチアジニル基、イソキサゾリル基、フラザニル基、フェノキサジニル基、イソクロマニル基、クロマニル基、ピロリジニル基、ピロリニル基、イミダゾリジニル基、イミダゾリニル基、ピラゾリジニル基、ピラゾリニル基、ピペリジル基、ピペラジニル基、インドリニル基、イソインドリニル基、キヌクリジニル基、モルホリニル基、及び、チオキサントリル基が例示できる。 The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.
　置換基を有していてもよいアルキルチオカルボニル基として具体的には、メチルチオカルボニル基、プロピルチオカルボニル基、ブチルチオカルボニル基、ヘキシルチオカルボニル基、オクチルチオカルボニル基、デシルチオカルボニル基、オクタデシルチオカルボニル基、及び、トリフルオロメチルチオカルボニル基が例示できる。 Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.
　置換基を有していてもよいアリールチオカルボニル基として具体的には、１－ナフチルチオカルボニル基、２－ナフチルチオカルボニル基、４－メチルスルファニルフェニルチオカルボニル基、４－フェニルスルファニルフェニルチオカルボニル基、４－ジメチルアミノフェニルチオカルボニル基、４－ジエチルアミノフェニルチオカルボニル基、２－クロロフェニルチオカルボニル基、２－メチルフェニルチオカルボニル基、２－メトキシフェニルチオカルボニル基、２－ブトキシフェニルチオカルボニル基、３－クロロフェニルチオカルボニル基、３－トリフルオロメチルフェニルチオカルボニル基、３－シアノフェニルチオカルボニル基、３－ニトロフェニルチオカルボニル基、４－フルオロフェニルチオカルボニル基、４－シアノフェニルチオカルボニル基、及び、４－メトキシフェニルチオカルボニル基が挙げられる。 Specific examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyano E D thiocarbonyl group, and include 4-methoxyphenyl thio group.
　ジアルキルアミノカルボニル基として具体的には、ジメチルアミノカルボニル基、ジメエルアミノカルボニル基、ジプロピルアミノカルボニル基、及び、ジブチルアミノカルボニル基が例示できる。 Specific examples of the dialkylaminocarbonyl group include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.
　置換基を有していてもよいジアルキルアミノチオカルボニル基としては、ジメチルアミノチオカルボニル基、ジプロピルアミノチオカルボニル基、及び、ジブチルアミノチオカルボニル基が例示できる。 Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.
　中でも、高感度化の点から、Ｒとしては、アシル基がより好ましく、具体的には、アセチル基、プロパノイル基、ベンゾイル基、トルオイル基が更に好ましい。 Among these, from the viewpoint of increasing sensitivity, R is more preferably an acyl group, and specifically, an acetyl group, a propanoyl group, a benzoyl group, and a toluoyl group are more preferable.
　上記Ｂで表される一価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基を表す。また、これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。また、前述した置換基は、更に他の置換基で置換されていてもよい。
　中でも、特に好ましくは以下に示す構造である。
　下記の構造中、Ｙ、Ｘ、及び、ｎは、それぞれ、後述する式（２）におけるＹ、Ｘ、及び、ｎと同義であり、好ましい例も同様である。 The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, the structure shown below is particularly preferable.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　上記Ａで表される二価の有機基としては、炭素数１～１２のアルキレン基、シクロヘキシレン基、アルキニレン基が挙げられる。また、これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。また、前述した置換基は、更に他の置換基で置換されていてもよい。
　中でも、Ａとしては、感度を高め、加熱経時による着色を抑制する点から、無置換のアルキレン基、アルキル基（例えば、メチル基、エチル基、ｔｅｒｔ－ブチル基、ドデシル基）で置換されたアルキレン基、アルケニル基（例えば、ビニル基、アリル基）で置換されたアルキレン基、アリール基（例えば、フェニル基、ｐ－トリル基、キシリル基、クメニル基、ナフチル基、アンスリル基、フェナントリル基、スチリル基）で置換されたアルキレン基が好ましい。 Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with
　上記Ａｒで表されるアリール基としては、炭素数６～３０のアリール基が好ましく、また、置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
　具体的には、フェニル基、ビフェニル基、１－ナフチル基、２－ナフチル基、９－アンスリル基、９－フェナントリル基、１－ピレニル基、５－ナフタセニル基、１－インデニル基、２－アズレニル基、９－フルオレニル基、ターフェニル基、クオーターフェニル基、ｏ－、ｍ－及びｐ－トリル基、キシリル基、ｏ－、ｍ－及びｐ－クメニル基、メシチル基、ペンタレニル基、ビナフタレニル基、ターナフタレニル基、クオーターナフタレニル基、ヘプタレニル基、ビフェニレニル基、インダセニル基、フルオランテニル基、アセナフチレニル基、アセアントリレニル基、フェナレニル基、フルオレニル基、アントリル基、ビアントラセニル基、ターアントラセニル基、クオーターアントラセニル基、アントラキノリル基、フェナントリル基、トリフェニレニル基、ピレニル基、クリセニル基、ナフタセニル基、プレイアデニル基、ピセニル基、ペリレニル基、ペンタフェニル基、ペンタセニル基、テトラフェニレニル基、ヘキサフェニル基、ヘキサセニル基、ルビセニル基、コロネニル基、トリナフチレニル基、ヘプタフェニル基、ヘプタセニル基、ピラントレニル基、並びに、オバレニル基が例示できる。
　中でも、感度を高め、加熱経時による着色を抑制する点から、置換又は無置換のフェニル基が好ましい。 The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. Examples of the substituent include the above-described substituents.
Specifically, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group , 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group , Quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracene Nyl group, anthraquinolyl group, phenanthryl group Triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, pleiadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentaphenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group , A heptaphenyl group, a heptacenyl group, a pyrantrenyl group, and an oberenyl group.
Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.
　式（１）においては、上記Ａｒと隣接するＳとで形成される「ＳＡｒ」の構造が、以下に示す構造であることが感度の点で好ましい。なお、Ｍｅはメチル基を表し、Ｅｔはエチル基を表す。 In the formula (1), it is preferable in terms of sensitivity that the structure of “SAr” formed by the Ar and the adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　本発明における特定オキシム化合物は、下記式（２）で表される化合物であることが好ましい。 The specific oxime compound in the present invention is preferably a compound represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000032
 （式（２）中、Ｒ及びＸは各々独立に一価の置換基を表し、Ａ及びＹは各々独立に二価の有機基を表し、Ａｒはアリール基を表し、ｎは０～５の整数である。）
Figure JPOXMLDOC01-appb-C000032
 (In the formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)
　式（２）におけるＲ、Ａ、及びＡｒは、上記式（１）におけるＲ、Ａ、及びＡｒと同義であり、好ましい例も同様である。 R, A, and Ar in the formula (2) have the same meanings as R, A, and Ar in the formula (1), and preferred examples are also the same.
　上記Ｘで表される一価の置換基としては、アルキル基、アリール基、アルケニル基、アルキニル基、アルコキシ基、アリールオキシ基、アシルオキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基、カルバモイル基、スルファモイル基、アミノ基、ホスフィノイル基、複素環基、ハロゲン原子が挙げられる。また、これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。また、前述した置換基は、更に他の置換基で置換されていてもよい。 Examples of the monovalent substituent represented by X include an alkyl group, aryl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, acyloxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group. Group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, amino group, phosphinoyl group, heterocyclic group and halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
　上記Ｘにおけるアルキル基、アリール基、アルケニル基、アルキニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、ホスフィノイル基、及び、複素環基は、上記式（１）におけるＲのアルキル基、アリール基、アルケニル基、アルキニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、ホスフィノイル基、及び、複素環基と同義であり、好ましい範囲も同様である。 The alkyl group, aryl group, alkenyl group, alkynyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, phosphinoyl group, and heterocyclic ring in X above The group is an alkyl group of R in the above formula (1), an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. , Phosphinoyl group and heterocyclic group, and the preferred range is also the same.
　アルコキシ基としては、炭素数１～３０のアルコキシ基が好ましく、具体的には、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、イソブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基、ペンチルオキシ基、イソペンチルオキシ基、ヘキシルオキシキ、ヘプチルオキシ基、オクチルオキシ基、２－エチルヘキシルオキシ基、デシルオキシ基、ドデシルオキシ基、オクタデシルオキシ基、エトキシカルボニルメチル基、２－エチルヘキシルオキシカルボニルメチルオキシ基、アミノカルボニルメチルオキシ基、Ｎ，Ｎ－ジブチルアミノカルボニルメチルオキシ基、Ｎ－メチルアミノカルボニルメチルオキシ基、Ｎ－エチルアミノカルボニルメチルオキシ基、Ｎ－オクチルアミノカルボニルメチルオキシ基、Ｎ－メチル－Ｎ－ベンジルアミノカルボニルメチルオキシ基、ベンジルオキシ基、及び、シアノメチルオキシ基が例示できる。 The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, and specifically includes a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. , Pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, dodecyloxy, octadecyloxy, ethoxycarbonylmethyl, 2-ethylhexyloxycarbonylmethyl Oxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethylo group Shi group, N- methyl -N- benzylaminocarbonyl methyl group, a benzyl group, and a cyano methyl group can be exemplified.
　アリールオキシ基としては、炭素数６～３０のアリールオキシ基が好ましく、具体的には、フェニルオキシ基、１－ナフチルオキシ基、２－ナフチルオキシ基、２－クロロフェニルオキシ基、２－メチルフェニルオキシ基、２－メトキシフェニルオキシ基、２－ブトキシフェニルオキシ基、３－クロロフェニルオキシ基、３－トリフルオロメチルフェニルオキシ基、３－シアノフェニルオキシ基、３－ニトロフェニルオキシ基、４－フルオロフェニルオキシ基、４－シアノフェニルオキシ基、４－メトキシフェニルオキシ基、４－ジメチルアミノフェニルオキシ基、４－メチルスルファニルフェニルオキシ基、及び、４－フェニルスルファニルフェニルオキシ基が例示できる。 The aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms, and specifically includes a phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-chlorophenyloxy group, 2-methylphenyloxy group. Group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, 4-fluorophenyloxy Group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, and 4-phenylsulfanylphenyloxy group.
　アシルオキシ基としては、炭素数２～２０のアシルオキシ基が好ましく、具体的には、アセチルオキシ基、プロパノイルオキシ基、ブタノイルオキシ基、ペンタノイルオキシ基、トリフルオロメチルカルボニルオキシ基、ベンゾイルオキシ基、１－ナフチルカルボニルオキシ基、及び、２－ナフチルカルボニルオキシ基が例示できる。 The acyloxy group is preferably an acyloxy group having 2 to 20 carbon atoms, and specifically includes an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, a trifluoromethylcarbonyloxy group, a benzoyloxy group. , 1-naphthylcarbonyloxy group and 2-naphthylcarbonyloxy group.
　アルキルスルファニル基としては、炭素数１～２０のアルキルスルファニル基が好ましく、具体的には、メチルスルファニル基、エチルスルファニル基、プロピルスルファニル基、イソプロピルスルファニル基、ブチルスルファニル基、ヘキシルスルファニル基、シクロヘキシルスルファニル基、オクチルスルファニル基、２－エチルヘキシルスルファニル基、デカノイルスルファニル基、ドデカノイルスルファニル基、オクタデカノイルスルファニル基、シアノメチルスルファニル基、及び、メトキシメチルスルファニル基が例示できる。 The alkylsulfanyl group is preferably an alkylsulfanyl group having 1 to 20 carbon atoms, and specifically includes a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, and a cyclohexylsulfanyl group. Octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, and methoxymethylsulfanyl group.
　アリールスルファニル基としては、炭素数６～３０のアリールスルファニル基が好ましく、具体的には、フェニルスルファニル基、１－ナフチルスルファニル基、２－ナフチルスルファニル基、２－クロロフェニルスルファニル基、２－メチルフェニルスルファニル基、２－メトキシフェニルスルファニル基、２－ブトキシフェニルスルファニル基、３－クロロフェニルスルファニル基、３－トリフルオロメチルフェニルスルファニル基、３－シアノフェニルスルファニル基、３－ニトロフェニルスルファニル基、４－フルオロフェニルスルファニル基、４－シアノフェニルスルファニル基、４－メトキシフェニルスルファニル基、４－メチルスルファニルフェニルスルファニル基、４－フェニルスルファニルフェニルスルファニル基、及び、４－ジメチルアミノフェニルスルファニル基が例示できる。 The arylsulfanyl group is preferably an arylsulfanyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group. Group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group Groups, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfanyl group, and , 4-dimethylaminophenyl sulfanyl group can be exemplified.
　カルバモイル基としては、総炭素数１～３０のカルバモイル基が好ましく、具体的には、Ｎ－メチルカルバモイル基、Ｎ－エチルカルバモイル基、Ｎ－プロピルカルバモイル基、Ｎ－ブチルカルバモイル基、Ｎ－ヘキシルカルバモイル基、Ｎ－シクロヘキシルカルバモイル基、Ｎ－オクチルカルバモイル基、Ｎ－デシルカルバモイル基、Ｎ－オクタデシルカルバモイル基、Ｎ－フェニルカルバモイル基、Ｎ－２－メチルフェニルカルバモイル基、Ｎ－２－クロロフェニルカルバモイル基、Ｎ－２－イソプロポキシフェニルカルバモイル基、Ｎ－２－（２－エチルヘキシル）フェニルカルバモイル基、Ｎ－３－クロロフェニルカルバモイル基、Ｎ－３－ニトロフェニルカルバモイル基、Ｎ－３－シアノフェニルカルバモイル基、Ｎ－４－メトキシフェニルカルバモイル基、Ｎ－４－シアノフェニルカルバモイル基、Ｎ－４－メチルスルファニルフェニルカルバモイル基、Ｎ－４－フェニルスルファニルフェニルカルバモイル基、Ｎ－メチル－Ｎ－フェニルカルバモイル基、Ｎ、Ｎ－ジメチルカルバモイル基、Ｎ、Ｎ－ジブチルカルバモイル基、Ｎ、Ｎ－ジフェニルカルバモイル基が例示できる。 The carbamoyl group is preferably a carbamoyl group having 1 to 30 carbon atoms, and specifically includes an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, an N-butylcarbamoyl group, and an N-hexylcarbamoyl group. Group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2-chlorophenylcarbamoyl group, N -2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenylcarbamoyl group, N- 4-Met Siphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl Group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group.
　スルファモイル基としては、総炭素数０～３０のスルファモイル基が好ましく、具体的には、スルファモイル基、Ｎ－アルキルスルファモイル基、Ｎ－アリールスルファモイル基、Ｎ、Ｎ－ジアルキルスルファモイル基、Ｎ、Ｎ－ジアリールスルファモイル基、及び、Ｎ－アルキル－Ｎ－アリールスルファモオイル基が例示できる。より具体的には、Ｎ－メチルスルファモイル基、Ｎ－エチルスルファモイル基、Ｎ－プロピルスルファモイル基、Ｎ－ブチルスルファモイル基、Ｎ－ヘキシルスルファモイル基、Ｎ－シクロヘキシルスルファモイル基、Ｎ－オクチルスルファモイル基、Ｎ－２－エチルヘキシルスルファモイル基、Ｎ－デシルスルファモイル基、Ｎ－オクタデシルスルファモイル基、Ｎ－フェニルスルファモイル基、Ｎ－２－メチルフェニルスルファモイル基、Ｎ－２－クロロフェニルスルファモイル基、Ｎ－２－メトキシフェニルスルファモイル基、Ｎ－２－イソプロポキシフェニルスルファモイル基、Ｎ－３－クロロフェニルスルファモイル基、Ｎ－３－ニトロフェニルスルファモイル基、Ｎ－３－シアノフェニルスルファモイル基、Ｎ－４－メトキシフェニルスルファモイル基、Ｎ－４－シアノフェニルスルファモイル基、Ｎ－４－ジメチルアミノフェニルスルファモイル基、Ｎ－４－メチルスルファニルフェニルスルファモイル基、Ｎ－４－フェニルスルファニルフェニルスルファモイル基、Ｎ－メチル－Ｎ－フェニルスルファモイル基、Ｎ，Ｎ－ジメチルスルファモイル基、Ｎ，Ｎ－ジブチルスルファモイル基、及び、Ｎ，Ｎ－ジフェニルスルファモイル基が好ましく例示できる。 The sulfamoyl group is preferably a sulfamoyl group having 0 to 30 carbon atoms, specifically, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an N, N-dialkylsulfamoyl group. N, N-diarylsulfamoyl group and N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Preferred examples include N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, and N, N-diphenylsulfamoyl group.
　アミノ基としては、総炭素数０～５０のアミノ基が好ましく、具体的には、アミノ基（－ＮＨ2）、Ｎ－アルキルアミノ基、Ｎ－アリールアミノ基、Ｎ－アシルアミノ基、Ｎ－スルホニルアミノ基、Ｎ，Ｎ－ジアルキルアミノ基、Ｎ，Ｎ－ジアリールアミノ基、Ｎ－アルキル－Ｎ－アリールアミノ基、及び、Ｎ，Ｎ－ジスルホニルアミノ基が例示できる。より具体的には、Ｎ－メチルアミノ基、Ｎ－エチルアミノ基、Ｎ－プロピルアミノ基、Ｎ－イソプロピルアミノ基、Ｎ－ブチルアミノ基、Ｎ－ｔｅｒｔ－ブチルアミノ基、Ｎ－ヘキシルアミノ基、Ｎ－シクロヘキシルアミノ基、Ｎ－オクチルアミノ基、Ｎ－２－エチルヘキシルアミノ基、Ｎ－デシルアミノ基、Ｎ－オクタデシルアミノ基、Ｎ－ベンジルアミノ基、Ｎ－フェニルアミノ基、Ｎ－２－メチルフェニルアミノ基、Ｎ－２－クロロフェニルアミノ基、Ｎ－２－メトキシフェニルアミノ基、Ｎ－２－イソプロポキシフェニルアミノ基、Ｎ－２－（２－エチルヘキシル）フェニルアミノ基、Ｎ－３－クロロフェニルアミノ基、Ｎ－３－ニトロフェニルアミノ基、Ｎ－３－シアノフェニルアミノ基、Ｎ－３－トリフルオロメチルフェニルアミノ基、Ｎ－４－メトキシフェニルアミノ基、Ｎ－４－シアノフェニルアミノ基、Ｎ－４－トリフルオロメチルフェニルアミノ基、Ｎ－４－メチルスルファニルフェニルアミノ基、Ｎ－４－フェニルスルファニルフェニルアミノ基、Ｎ－４－ジメチルアミノフェニルアミノ基、Ｎ－メチル－Ｎ－フェニルアミノ基、Ｎ，Ｎ－ジメチルアミノ基、Ｎ，Ｎ－ジエチルアミノ基、Ｎ，Ｎ－ジブチルアミノ基、Ｎ，Ｎ－ジフェニルアミノ基、Ｎ，Ｎ－ジアセチルアミノ基、Ｎ，Ｎ－ジベンゾイルアミノ基、Ｎ，Ｎ－（ジブチルカルボニル）アミノ基、Ｎ，Ｎ－（ジメチルスルホニル）アミノ基、Ｎ，Ｎ－（ジエチルスルホニル）アミノ基、Ｎ，Ｎ－（ジブチルスルホニル）アミノ基、Ｎ，Ｎ－（ジフェニルスルホニル）アミノ基、モルホリノ基、及び、３，５－ジメチルモルホリノ基、カルバゾール基が好ましく例示できる。 The amino group is preferably an amino group having 0 to 50 carbon atoms, and specifically includes an amino group (—NH 2 ), an N-alkylamino group, an N-arylamino group, an N-acylamino group, an N-sulfonyl group. Examples thereof include an amino group, an N, N-dialkylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, and an N, N-disulfonylamino group. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenyla Group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino Group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenyl Amino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) An amino group, an N, N- (dibutylsulfonyl) amino group, an N, N- (diphenylsulfonyl) amino group, a morpholino group, and 3,5-dimethyl-morpholino group, a carbazole group can be preferably exemplified.
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
　これらの中でも、Ｘとしては、溶剤溶解性と長波長領域の吸収効率向上の点から、アルキル基、アリール基、アルケニル基、アルキニル基、アルコキシ基、アリールオキシ基、アルキルスルファニル基、アリールスルファニル基、アミノ基が好ましい。
　また、式（２）におけるｎは、０～５の整数を表し、０～２の整数が好ましい。 Among these, X is an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylsulfanyl group, an arylsulfanyl group, from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region, An amino group is preferred.
In the formula (2), n represents an integer of 0 to 5, and an integer of 0 to 2 is preferable.
　上記Ｙで表される二価の有機基としては、以下に示す構造が挙げられる。なお、以下に示される基において、「＊」は、上記式（２）において、Ｙと隣接する炭素原子との結合位置を示す。 Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “*” represents the bonding position between Y and the adjacent carbon atom in the above formula (2).
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　中でも、高感度化の観点から、下記に示す構造が好ましい。 Of these, the following structures are preferable from the viewpoint of increasing sensitivity.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　本発明における特定オキシム化合物は、下記式（３）で表される化合物であることが好ましい。 The specific oxime compound in the present invention is preferably a compound represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000035
 （式（３）中、Ｒ及びＸは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表し、ｎは０～５の整数である。）
Figure JPOXMLDOC01-appb-C000035
 (In formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5.)
　式（３）におけるＲ、Ｘ、Ａ、Ａｒ、及び、ｎは、上記式（２）におけるＲ、Ｘ、Ａ、Ａｒ、及び、ｎとそれぞれ同義であり、好ましい例も同様である。 R, X, A, Ar, and n in the formula (3) have the same meanings as R, X, A, Ar, and n in the formula (2), respectively, and preferred examples are also the same.
　以下、本発明における特定オキシム化合物の具体例としては特開２００９－２４４４１３の段落０１２３～０１３２に記載の（Ｋ－１）～（Ｋ－８８）が挙げられるが、本発明はこれらに限定されるものではない。 Hereinafter, specific examples of the specific oxime compound in the present invention include (K-1) to (K-88) described in paragraphs 0123 to 0132 of JP-A-2009-244413, but the present invention is limited to these. It is not a thing.
　特定オキシム化合物は、光により分解し、光重合性化合物の重合を開始、促進する光重合開始剤としての機能を有する。特に、オキシム化合物は３６５ｎｍや４０５ｎｍの光源に優れた感度を有する。 The specific oxime compound is decomposed by light and has a function as a photopolymerization initiator that initiates and accelerates the polymerization of the photopolymerizable compound. In particular, the oxime compound has excellent sensitivity to a light source of 365 nm or 405 nm.
　更に好ましくは、トリハロメチルトリアジン系化合物、α－アミノケトン化合物、アシルホスフィン系化合物、フォスフィンオキサイド系化合物、オキシム系化合物、トリアリルイミダゾールダイマー、オニウム系化合物、ベンゾフェノン系化合物、アセトフェノン系化合物であり、トリハロメチルトリアジン系化合物、α－アミノケトン化合物、オキシム系化合物、トリアリルイミダゾールダイマー、ベンゾフェノン系化合物からなる群より選ばれる少なくとも１種の化合物が最も好ましい。 More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of methyltriazine compounds, α-aminoketone compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds.
　特に、本発明の光硬化性組成物を固体撮像素子や液晶表示装置等の光学部材の作製に使用する場合には、微細なパターンをシャープな形状で形成する必要があるために、硬化性と共に未露光部に残渣がなく現像されることが重要である。このような観点からは、オキシム系化合物が特に好ましい。特に、固体撮像素子において微細なパターンを形成する場合、硬化用露光にステッパー露光を用いるが、この露光機はハロゲンにより損傷される場合があり、重合開始剤の添加量も低く抑える必要があるため、これらの点を考慮すれば、固体撮像素子の如き微細パターンを形成するには（成分Ｆ）重合開始剤としては、オキシム系化合物を用いることが最も好ましい。 In particular, when the photocurable composition of the present invention is used for the production of an optical member such as a solid-state imaging device or a liquid crystal display device, it is necessary to form a fine pattern with a sharp shape. It is important that the unexposed area is developed without residue. From such a viewpoint, an oxime compound is particularly preferable. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the addition amount of a polymerization initiator low. Considering these points, it is most preferable to use an oxime compound as the polymerization initiator (Component F) in order to form a fine pattern such as a solid-state imaging device.
　本発明の光硬化性組成物に含有される（成分Ｆ）重合開始剤の含有量は、光硬化性組成物の全固形分に対し０．１質量％以上５０質量％以下であることが好ましく、より好ましくは０．５質量％以上３０質量％以下、更に好ましくは１質量％以上２０質量％以下である。この範囲で、良好な感度とパターン形成性が得られる。 The content of (Component F) polymerization initiator contained in the photocurable composition of the present invention is preferably 0.1% by mass or more and 50% by mass or less with respect to the total solid content of the photocurable composition. More preferably, they are 0.5 mass% or more and 30 mass% or less, More preferably, they are 1 mass% or more and 20 mass% or less. Within this range, good sensitivity and pattern formability can be obtained.
（成分Ｇ）増感剤
　本発明の光硬化性組成物は、（成分Ｆ）重合開始剤のラジカル発生効率の向上、感光波長の長波長化の目的で、（成分Ｇ）増感剤を含有していてもよい。
　本発明に用いることができる増感剤としては、上記した（成分Ｆ）重合開始剤に対し、電子移動機構又はエネルギー移動機構で増感させるものが好ましい。 (Component G) Sensitizer The photocurable composition of the present invention contains (Component G) a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength. You may do it.
As the sensitizer that can be used in the present invention, those that sensitize the above-described (Component F) polymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.
　増感剤としては、以下に列挙する化合物類に属しており、かつ、３００ｎｍ～４５０ｎｍの波長領域に吸収波長を有するものが挙げられる。
　すなわち、例えば、多核芳香族類（例えば、フェナントレン、アントラセン、ピレン、ペリレン、トリフェニレン、９，１０－ジアルコキシアントラセン）、キサンテン類（例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガル）、チオキサントン類（イソプロピルチオキサントン、ジエチルチオキサントン、クロロチオキサントン）、シアニン類（例えば、チアカルボシアニン、オキサカルボシアニン）、メロシアニン類（例えば、メロシアニン、カルボメロシアニン）、フタロシアニン類、チアジン類（例えば、チオニン、メチレンブルー、トルイジンブルー）、アクリジン類（例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン）、アントラキノン類（例えば、アントラキノン）、スクアリウム類（例えば、スクアリウム）、アクリジンオレンジ、クマリン類（例えば、７－ジエチルアミノ－４－メチルクマリン）、ケトクマリン、フェノチアジン類、フェナジン類、スチリルベンゼン類、アゾ化合物、ジフェニルメタン、トリフェニルメタン、ジスチリルベンゼン類、カルバゾール類、ポルフィリン、スピロ化合物、キナクリドン、インジゴ、スチリル、ピリリウム化合物、ピロメテン化合物、ピラゾロトリアゾール化合物、ベンゾチアゾール化合物、バルビツール酸誘導体、チオバルビツール酸誘導体、アセトフェノン、ベンゾフェノン、チオキサントン、ミヒラーズケトンなどの芳香族ケトン化合物、Ｎ－アリールオキサゾリジノンなどのヘテロ環化合物などが挙げられる。 Examples of the sensitizer include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
That is, for example, polynuclear aromatics (eg, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), Thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), square Ums (eg, squalium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzene , Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, etc. Aromatic ketone compounds, and heterocyclic compounds such as N-aryloxazolidinones.
　本発明に好適に用いうる増感剤として、特開２０１１－１２７０９６号公報の段落０１８２～０２０３に記載された増感剤が挙げられる。 Examples of sensitizers that can be suitably used in the present invention include sensitizers described in paragraphs 0182 to 0203 of JP2011-127096A.
　増感剤は、１種単独で用いてもよいし、２種以上を併用してもよい。
　光硬化性組成物中における増感剤の含有量は、深部への光吸収効率と開始剤の分解効率の観点から、固形分換算で、０．１質量％以上２０質量％以下であることが好ましく、０．５質量％以上１５質量％以下がより好ましい。 A sensitizer may be used individually by 1 type and may use 2 or more types together.
The content of the sensitizer in the photocurable composition is 0.1% by mass or more and 20% by mass or less in terms of solid content from the viewpoint of light absorption efficiency in the deep part and decomposition efficiency of the initiator. Preferably, it is 0.5 mass% or more and 15 mass% or less.
（成分Ｉ）共増感剤
　本発明の光硬化性組成物は、更に（成分Ｉ）共増感剤を含有することも好ましい。
　本発明において共増感剤は、（成分Ｆ）重合開始剤や（成分Ｇ）増感剤の活性放射線に対する感度を一層向上させる、あるいは、酸素による（成分Ｅ）重合性化合物の重合阻害を抑制する等の作用を有する。 (Component I) Co-sensitizer The photocurable composition of the present invention preferably further contains (Component I) a co-sensitizer.
In the present invention, the co-sensitizer further improves the sensitivity of (component F) polymerization initiator and (component G) sensitizer to active radiation, or suppresses inhibition of polymerization of (component E) polymerizable compound by oxygen. It has an effect such as.
　このような共増感剤の例としては、アミン類、例えば、Ｍ．Ｒ．Ｓａｎｄｅｒら著「Ｊｏｕｒｎａｌ　ｏｆ　Ｐｏｌｙｍｅｒ　Ｓｏｃｉｅｔｙ」第１０巻３１７３頁（１９７２）、特公昭４４－２０１８９号公報、特開昭５１－８２１０２号公報、特開昭５２－１３４６９２号公報、特開昭５９－１３８２０５号公報、特開昭６０－８４３０５号公報、特開昭６２－１８５３７号公報、特開昭６４－３３１０４号公報、Ｒｅｓｅａｒｃｈ　Ｄｉｓｃｌｏｓｕｒｅ　３３８２５号記載の化合物等が挙げられ、具体的には、トリエタノールアミン、ｐ－ジメチルアミノ安息香酸エチルエステル、ｐ－ホルミルジメチルアニリン、ｐ－メチルチオジメチルアニリン等が挙げられる。 Examples of such co-sensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.
　また、共増感剤の別の例としては、アミノ酸化合物（例、Ｎ－フェニルグリシン等）、特公昭４８－４２９６５号公報記載の有機金属化合物（例、トリブチル錫アセテート等）、特公昭５５－３４４１４号公報記載の水素供与体、特開平６－３０８７２７号公報記載のイオウ化合物（例、トリチアン等）等が挙げられる。 Other examples of co-sensitizers include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- And a hydrogen donor described in JP 34414 and a sulfur compound (eg, trithiane) described in JP-A-6-308727.
　これら共増感剤の含有量は、重合成長速度と連鎖移動のバランスによる硬化速度の向上の観点から、光硬化性組成物の全固形分の質量に対し、０．１質量％以上３０質量％以下の範囲が好ましく、１質量％以上２５質量％以下の範囲がより好ましく、１．５質量％以上２０質量％以下の範囲が更に好ましい。 The content of these co-sensitizers is 0.1% by mass or more and 30% by mass with respect to the mass of the total solid content of the photocurable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The following ranges are preferable, the range of 1% by mass to 25% by mass is more preferable, and the range of 1.5% by mass to 20% by mass is more preferable.
（成分Ｊ）重合禁止剤
　本発明においては、光硬化性組成物の製造中あるいは保存中において重合性化合物の不要な重合を阻止するために、（成分Ｊ）重合禁止剤を添加してもよい。
　本発明に用いうる重合禁止剤としては、フェノール系水酸基含有化合物、Ｎ－オキシド化合物類、ピペリジン１－オキシルフリーラジカル化合物類、ピロリジン１－オキシルフリーラジカル化合物類、Ｎ－ニトロソフェニルヒドロキシルアミン類、ジアゾニウム化合物類、及びカチオン染料類、スルフィド基含有化合物類、ニトロ基含有化合物類、ＦｅＣｌ3、ＣｕＣｌ2等の遷移金属化合物類が挙げられる。 (Component J) Polymerization inhibitor In the present invention, (Component J) a polymerization inhibitor may be added in order to prevent unnecessary polymerization of the polymerizable compound during the production or storage of the photocurable composition. .
Polymerization inhibitors that can be used in the present invention include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium Examples include compounds, and cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, and transition metal compounds such as FeCl 3 and CuCl 2 .
　更に好ましい態様は、例えば、特開２０１０－１０６２６８号公報の段落０２６０～０２８０に記載されている。 Further preferred embodiments are described, for example, in paragraphs 0260 to 0280 of JP2010-106268A.
　重合禁止剤として好ましくは、ハイドロキノン、ｐ－メトキシフェノール、ジ－t－ブチル－ｐ－クレゾール、ピロガロール、t－ブチルカテコール、ベンゾキノン、４，４－チオビス（３－メチル－６－t－ブチルフェノール）、２，２'－メチレンビス（４－メチル－６－t－ブチルフェノール）のフェノール系水酸基含有化合物、ピペリジン１－オキシル フリーラジカル化合物類若しくは、２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－オキソ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－アセトアミド－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－マレイミド－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、及び４－ホスホノキシ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカルのピペリジン１－オキシルフリーラジカル化合物、若しくはＮ－ニトロソフェニルヒドロキシルアミン第一セリウム塩及びＮ－ニトロソフェニルヒドロキシルアミンアルミニウム塩のＮ－ニトロソフェニルヒドロキシルアミン化合物であり、より好ましくは、２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－オキソ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－アセトアミド－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、４－マレイミド－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカル、及び４－ホスホノキシ－２，２，６，６－テトラメチルピペリジン１－オキシルフリーラジカルのピペリジン１－オキシルフリーラジカル化合物、若しくはＮ－ニトロソフェニルヒドロキシルアミン第一セリウム塩及びＮ－ニトロソフェニルヒドロキシルアミンアルミニウム塩のＮ－ニトロソフェニルヒドロキシルアミン化合物であり、更に好ましくは、－ニトロソフェニルヒドロキシルアミン第一セリウム塩及びＮ－ニトロソフェニルヒドロキシルアミンアルミニウム塩のＮ－ニトロソフェニルヒドロキシルアミン化合物である。 As the polymerization inhibitor, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol) phenolic hydroxyl group-containing compound, piperidine 1-oxyl free radical compound, or 2,2,6,6-tetramethylpiperidine 1-oxyl free radical 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2 , 6,6-Tetramethylpiperidine 1-oxyl free radical, 4- Piperidine 1-oxyl free radical compound of maleimide-2,2,6,6-tetramethylpiperidine 1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, or N-nitrosophenylhydroxylamine primary cerium salt and N-nitrosophenylhydroxylamine aluminum salt N-nitrosophenylhydroxylamine compound, more preferably 2,2,6,6-tetramethylpiperidine 1-oxyl free radical 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2 , 6,6-Tetramethi Piperidine 1-oxyl free radical, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical Piperidine 1-oxyl free radical compound, or N-nitrosophenylhydroxylamine compound of N-nitrosophenylhydroxylamine primary cerium salt and N-nitrosophenylhydroxylamine aluminum salt, more preferably -nitrosophenylhydroxylamine primary N-nitrosophenylhydroxylamine compound of cerium salt and N-nitrosophenylhydroxylamine aluminum salt.
　重合禁止剤の好ましい添加量としては、（成分Ｆ）重合開始剤１００質量部に対して、０．０１質量部以上１０質量部以下であることが好ましく、０．０１質量部以上８質量部以下であることがより好ましく、０．０５質量部以上５質量部以下の範囲にあることが更に好ましい。
　上記範囲とすることで、非画像部における硬化反応抑制及び画像部における硬化反応促進が充分行われ、画像形成性及び感度が良好となる。 A preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.01 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the (Component F) polymerization initiator. It is more preferable that it is 0.05 to 5 parts by mass.
By setting it as the said range, the curing reaction suppression in a non-image part and the curing reaction acceleration in an image part are fully performed, and image forming property and a sensitivity become favorable.
（成分Ｋ）バインダーポリマー
　本発明の光硬化性組成物は、重合系である場合、解像性及び皮膜特性向上などの観点から、更に（成分Ｋ）バインダーポリマーの少なくとも１種を含むことが好ましい。
　上記（成分Ｋ）バインダーポリマーとしては線状有機ポリマーを用いることが好ましい。このような線状有機ポリマーとしては、公知のものを任意に使用できる。好ましくは水現像あるいは弱アルカリ水現像を可能とするために、水あるいは弱アルカリ水に可溶性又は膨潤性である線状有機ポリマーが選択される。線状有機ポリマーは、皮膜形成剤としてだけでなく、水、弱アルカリ水あるいは有機溶剤現像剤としての用途に応じて選択使用される。例えば、水可溶性有機ポリマーを用いると水現像が可能になる。このような線状有機ポリマーとしては、側鎖にカルボン酸基を有するラジカル重合体、例えば特開昭５９－４４６１５号公報、特公昭５４－３４３２７号公報、特公昭５８－１２５７７号公報、特公昭５４－２５９５７号公報、特開昭５４－９２７２３号公報公報、特開昭５９－５３８３６号公報、特開昭５９－７１０４８号公報に記載されているもの、すなわち、カルボキシル基を有するモノマーを単独あるいは共重合させた樹脂、酸無水物を有するモノマーを単独あるいは共重合させ酸無水物ユニットを加水分解若しくはハーフエステル化若しくはハーフアミド化させた樹脂、エポキシ樹脂を不飽和モノカルボン酸及び酸無水物で変性させたエポキシアクリレート等が挙げられる。カルボキシル基を有するモノマーとしては、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、４－カルボキシルスチレン等が挙げられ、酸無水物を有するモノマーとしては、無水マレイン酸等が挙げられる。
　また、同様に側鎖にカルボン酸基を有する酸性セルロース誘導体がある。この他に水酸基を有する重合体に環状酸無水物を付加させたものなどが有用である。 (Component K) Binder Polymer When the photocurable composition of the present invention is a polymerization system, it is preferable that it further contains (Component K) at least one binder polymer from the viewpoint of improving resolution and film properties. .
As the (component K) binder polymer, a linear organic polymer is preferably used. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such a linear organic polymer include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. No. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a monomer having a carboxyl group alone or Copolymerized resin, acid anhydride monomer alone or copolymerized, acid anhydride unit hydrolyzed, half esterified or half amidated, epoxy resin unsaturated monocarboxylic acid and acid anhydride Examples include modified epoxy acrylate. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene. Examples of the monomer having an acid anhydride include maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
　本発明において、バインダーポリマーとして、共重合体を用いる場合、共重合させる化合物として、先に挙げたモノマー以外の他のモノマーを用いることもできる。他のモノマーの例としては、下記（１）～（１２）の化合物が挙げられる。 In the present invention, when a copolymer is used as the binder polymer, a monomer other than the monomers listed above can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).
　（１）２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、３－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルアクリレート、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルメタクリレート、３－ヒドロキシプロピルメタクリレート、４－ヒドロキシブチルメタクリレート等の脂肪族水酸基を有するアクリル酸エステル類、及びメタクリル酸エステル類。
　（２）アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸アミル、アクリル酸ヘキシル、アクリル酸２－エチルヘキシル、アクリル酸オクチル、アクリル酸ベンジル、アクリル酸－２－クロロエチル、グリシジルアクリレート、３，４－エポキシシクロヘキシルメチルアクリレート、ビニルアクリレート、２－フェニルビニルアクリレート、１－プロペニルアクリレート、アリルアクリレート、２－アリロキシエチルアクリレート、プロパルギルアクリレート等のアルキルアクリレート。 (1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;
　（３）メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸イソブチル、メタクリル酸アミル、メタクリル酸ヘキシル、メタクリル酸２－エチルヘキシル、メタクリル酸シクロヘキシル、メタクリル酸ベンジル、メタクリル酸－２－クロロエチル、グリシジルメタクリレート、３，４－エポキシシクロヘキシルメチルメタクリレート、ビニルメタクリレート、２－フェニルビニルメタクリレート、１－プロペニルメタクリレート、アリルメタクリレート、２－アリロキシエチルメタクリレート、プロパルギルメタクリレート等のアルキルメタクリレート。
　（４）アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－エチルアクリルアミド、Ｎ－ヘキシルメタクリルアミド、Ｎ－シクロヘキシルアクリルアミド、Ｎ－ヒドロキシエチルアクリルアミド、Ｎ－フェニルアクリルアミド、Ｎ－ニトロフェニルアクリルアミド、Ｎ－エチル－Ｎ－フェニルアクリルアミド、ビニルアクリルアミド、ビニルメタクリルアミド、Ｎ，Ｎ－ジアリルアクリルアミド、Ｎ，Ｎ－ジアリルメタクリルアミド、アリルアクリルアミド、アリルメタクリルアミド等のアクリルアミド若しくはメタクリルアミド。 (3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate;
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.
　（５）エチルビニルエーテル、２－クロロエチルビニルエーテル、ヒドロキシエチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、オクチルビニルエーテル、フェニルビニルエーテル等のビニルエーテル類。
　（６）ビニルアセテート、ビニルクロロアセテート、ビニルブチレート、安息香酸ビニル等のビニルエステル類。
　（７）スチレン、α－メチルスチレン、メチルスチレン、クロロメチルスチレン、ｐ－アセトキシスチレン等のスチレン類。
　（８）メチルビニルケトン、エチルビニルケトン、プロピルビニルケトン、フェニルビニルケトン等のビニルケトン類。
　（９）エチレン、プロピレン、イソブチレン、ブタジエン、イソプレン等のオレフィン類。 (5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.
　（１０）Ｎ－ビニルピロリドン、アクリロニトリル、メタクリロニトリル等。
　（１１）マレイミド、Ｎ－アクリロイルアクリルアミド、Ｎ－アセチルメタクリルアミド、Ｎ－プロピオニルメタクリルアミド、Ｎ－（ｐ－クロロベンゾイル）メタクリルアミド等の不飽和イミド。
　（１２）α位にヘテロ原子が結合したメタクリル酸系モノマー。例えば、特開２００２－３０９０５７号、特開２００２－３１１５６９号等の各公報に記載の化合物を挙げることができる。 (10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in JP-A-2002-309057 and JP-A-2002-311569 can be mentioned.
　これらの中で、側鎖にアリル基やビニルエステル基とカルボキシル基を有する（メタ）アクリル樹脂及び特開２０００－１８７３２２号公報、特開２００２－６２６９８号公報に記載されている側鎖に二重結合を有するアルカリ可溶性樹脂や、特開２００１－２４２６１２号公報に記載されている側鎖にアミド基を有するアルカリ可溶性樹脂が膜強度、感度、現像性のバランスに優れており、好適である。 Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain, and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.
　また、特公平７－１２００４号公報、特公平７－１２００４１号公報、特公平７－１２００４２号公報、特公平８－１２４２４号公報、特開昭６３－２８７９４４号公報、特開昭６３－２８７９４７号公報、特開平１－２７１７４１号公報等に記載される酸基を含有するウレタン系バインダーポリマーや、特開２００２－１０７９１８号公報に記載される酸基と二重結合を側鎖に有するウレタン系バインダーポリマーは、非常に強度に優れるので、膜強度・低露光適性の点で有利である。
　また、欧州特許第９９３９６６号、欧州特許第１２０４０００号、特開２００１－３１８４６３号公報等に記載の酸基を有するアセタール変性ポリビニルアルコール系バインダーポリマーは、膜強度、現像性のバランスに優れており、好適である。
　更にこの他に水溶性線状有機ポリマーとして、ポリビニルピロリドンやポリエチレンオキサイド等が有用である。また、硬化皮膜の強度を上げるためにアルコール可溶性ナイロンや２，２－ビス－（４－ヒドロキシフェニル）－プロパンとエピクロロヒドリンのポリエーテル等も有用である。 Also, Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication No. 63-287947. Urethane binder polymers containing acid groups as described in JP-A-1-271741 and the like, and urethane binders having acid groups and double bonds in side chains as described in JP-A-2002-107918 Since the polymer is excellent in strength, it is advantageous in terms of film strength and suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 has an excellent balance of film strength and developability. Is preferred.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin are also useful.
　本発明の光硬化性組成物で使用しうるバインダーポリマーの重量平均分子量としては、好ましくは５，０００以上であり、更に好ましくは１万以上３０万以下の範囲であり、数平均分子量については好ましくは１，０００以上であり、更に好ましくは２，０００以上２５万以下の範囲である。多分散度（重量平均分子量／数平均分子量）は１以上が好ましく、更に好ましくは１．１以上１０以下の範囲である。
　これらのバインダーポリマーは、ランダムポリマー、ブロックポリマー、グラフトポリマー等いずれでもよい。 The weight average molecular weight of the binder polymer that can be used in the photocurable composition of the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably Is 1,000 or more, and more preferably 2,000 or more and 250,000 or less. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.
　本発明で用いうるバインダーポリマーは、従来公知の方法により合成できる。合成する際に用いられる溶媒としては、例えば、テトラヒドロフラン、エチレンジクロリド、シクロヘキサノン、メチルエチルケトン、アセトン、メタノール、エタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、２－メトキシエチルアセテート、ジエチレングリコールジメチルエーテル、１－メトキシ－２－プロパノール、１－メトキシ－２－プロピルアセテート、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、トルエン、酢酸エチル、乳酸メチル、乳酸エチル、ジメチルスルホキシド、水等が挙げられる。これらの溶媒は単独で又は２種以上混合して用いられる。
　本発明の光硬化性組成物において用いうるバインダーポリマーを合成する際に用いられるラジカル重合開始剤としては、アゾ系開始剤、過酸化物開始剤等公知の化合物が挙げられる。 The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include -2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing the binder polymer that can be used in the photocurable composition of the present invention include known compounds such as an azo initiator and a peroxide initiator.
　光硬化性組成物の全固形分中、バインダーポリマーの含有量は、１質量％以上４０質量％以下であることが好ましく、３質量％以上３０質量％以下であることがより好ましく、４質量％以上２０質量％以下であることが更に好ましい。 In the total solid content of the photocurable composition, the content of the binder polymer is preferably 1% by mass or more and 40% by mass or less, more preferably 3% by mass or more and 30% by mass or less, and more preferably 4% by mass. More preferably, it is 20 mass% or less.
（成分Ｌ）密着改良剤
　本発明の光硬化性組成物においては、基板などの硬質表面との密着性を向上させるために、（成分Ｌ）密着改良剤を添加することができる。密着改良剤としては、シラン系カップリング剤、チタンカップリング剤等が挙げられる。 (Component L) Adhesion Improving Agent In the photocurable composition of the present invention, (Component L) an adhesion improving agent can be added in order to improve the adhesion to a hard surface such as a substrate. Examples of the adhesion improving agent include a silane coupling agent and a titanium coupling agent.
　シラン系カップリング剤としては、例えば、γ－（２－アミノエチル）アミノプロピルトリメトキシシラン、γ－（２－アミノエチル）アミノプロピルジメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、γ－メタクリロキシプロピルトリエトキシシラン、γ－アクリロキシプロピルトリメトキシシラン、γ－アクリロキシプロピルトリエトキシシラン、γ－イソシアネートプロピルトリメトキシシラン、γ－イソシアネートプロピルトリエトキシシラン、Ｎ－β－（Ｎ－ビニルベンジルアミノエチル）－γ－アミノプロピルトリメトキシシラン・塩酸塩、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、アミノシラン、γ－メルカプトプロピルトリメトキシシラン、γ－メルカプトプロピルトリエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリアセトキシシラン、γ－クロロプロピルトリメトキシシラン、ヘキサメチルジシラザン、γ－アニリノプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β－メトキシエトキシ）シラン、オクタデシルジメチル［３－（トリメトキシシリル）プロピル］アンモニウムクロライド、γ－クロロプロピルメチルジメトキシシラン、γ－メルカプトプロピルメチルジメトキシシラン、メチルトリクロロシラン、ジメチルジクロロシラン、トリメチルクロロシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、ビスアリルトリメトキシシラン、テトラエトキシシラン、ビス（トリメトキシシリル）ヘキサン、フェニルトリメトキシシラン、Ｎ－（３－アクリロキシ－２－ヒドロキシプロピル）－３－アミノプロピルトリエトキシシラン、Ｎ－（３－メタクリロキシ－２－ヒドロキシプロピル）－３－アミノプロピルトリエトキシシラン、（メタクリロキシメチル）メチルジエトキシシラン、（アクリロキシメチル）メチルジメトキシシラン、等が挙げられる。 Examples of silane coupling agents include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, γ-glycidoxyp Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ -Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) Propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl L-chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2- Hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxy And silane.
　中でも、γ－メタクリロキシプロピルトリメトキシシラン、γ－メタクリロキシプロピルトリエトキシシラン、γ－アクリロキシプロピルトリメトキシシラン、γ－アクリロキシプロピルトリエトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、フェニルトリメトキシシラン、が好ましく、γ－メタクリロキシプロピルトリメトキシシランが最も好ましい。 Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.
　密着改良剤の添加量は、光硬化性組成物の全固形分中０．５質量％以上３０質量％以下が好ましく、０．７質量％以上２０質量％以下がより好ましい。 The addition amount of the adhesion improver is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 0.7% by mass or more and 20% by mass or less in the total solid content of the photocurable composition.
＜その他の添加剤＞
　更に、光硬化性組成物に対しては、硬化皮膜の物性を改良するために紫外線吸収剤、可塑剤、界面活性剤、感脂化剤等の公知の添加剤を加えてもよい。 <Other additives>
Furthermore, in order to improve the physical properties of the cured film, known additives such as ultraviolet absorbers, plasticizers, surfactants, and sensitizers may be added to the photocurable composition.
〔界面活性剤〕
　本発明の光硬化性組成物は、界面活性剤を含有してもよい。
　界面活性剤としては、アニオン系、カチオン系、ノニオン系又は両性のいずれでも使用することができるが、好ましい界面活性剤は、ノニオン界面活性剤である。
　ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、シリコーン系、フッ素系界面活性剤を挙げることができる。フッ素系界面活性剤、シリコーン系界面活性剤の例として具体的には、特開昭６２－３６６６３号、特開昭６１－２２６７４６号、特開昭６１－２２６７４５号、特開昭６２－１７０９５０号、特開昭６３－３４５４０号、特開平７－２３０１６５号、特開平８－６２８３４号、特開平９－５４４３２号、特開平９－５９８８号、特開２００１－３３０９５３号等の各公報記載の界面活性剤を挙げることができ、市販の界面活性剤を用いることもできる。また、以下商品名で、ＫＰ（信越化学工業（株）製）、ポリフロー（共栄社化学（株）製）、エフトップ（ＪＥＭＣＯ社製）、メガファック（ＤＩＣ（株）製）、フロラード（住友スリーエム（株）製）、アサヒガード、サーフロン（旭硝子（株）製）、ＰｏｌｙＦｏｘ（ＯＭＮＯＶＡ社製）、ＳＨ－８４００（東レ・ダウコーニング（株）製）等の各シリーズを挙げることができる。
　また、界面活性剤として、下記式（Ｋ－１）で表される構成単位Ａ及び構成単位Ｂを含み、テトラヒドロフラン（ＴＨＦ）を溶媒とした場合のゲルパーミエーションクロマトグラフィで測定されるポリスチレン換算の重量平均分子量（Ｍｗ）が１，０００以上１０，０００以下である共重合体を好ましい例として挙げることができる。 [Surfactant]
The photocurable composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of 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. . Specific examples of fluorine surfactants and silicone surfactants include JP-A Nos. 62-36663, 61-226746, 61-226745, and 62-170950. The interfaces described in JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2001-330953, etc. An activator can be mentioned and a commercially available surfactant can also be used. In addition, the following trade names are 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 (Sumitomo 3M) Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (manufactured by Toray Dow Corning Co., Ltd.), and the like.
Further, the surfactant includes a structural unit A and a structural unit B represented by the following formula (K-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.
Figure JPOXMLDOC01-appb-C000036
 （式（Ｋ－１）中、Ｒ401及びＲ403はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ402は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ404は水素原子又は炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐ及びｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。）
Figure JPOXMLDOC01-appb-C000036
 (In Formula (K-1), R 401 and R 403 each independently represent a hydrogen atom or a methyl group, R 402 represents a linear alkylene group having 1 to 4 carbon atoms, and R 404 represents 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, and p is 10 mass% to 80 mass%. A numerical value is represented, q represents a numerical value of 20 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.)
　上記Ｌは、下記式（Ｋ－２）で表される分岐アルキレン基であることが好ましい。式（Ｋ－２）におけるＲ405は、炭素数１以上３以下のアルキル基を表し、相溶性と被塗布面に対する濡れ性の点で、炭素数１以上３以下のアルキル基が好ましく、炭素数２又は３のアルキル基がより好ましい。ｐとｑとの和（ｐ＋ｑ）は、ｐ＋ｑ＝１００、すなわち、１００質量％であることが好ましい。 L is preferably a branched alkylene group represented by the following formula (K-2). R 405 in formula (K-2) represents an alkyl group having 1 to 3 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 sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　上記共重合体の重量平均分子量（Ｍｗ）は、１，５００以上５，０００以下がより好ましい。 The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
　これらの界面活性剤は、１種単独で又は２種以上を混合して使用することができる。
　本発明の光硬化性組成物における界面活性剤の添加量は、光硬化性組成物中の全固形分１００質量部に対して、１０質量部以下であることが好ましく、０．００１～１０質量部であることがより好ましく、０．０１～３質量部であることが更に好ましい。 These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the photocurable 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 photocurable composition. More preferably, the amount is 0.01 to 3 parts by mass.
〔現像促進剤〕
　本発明の光硬化性組成物は、現像促進剤を含有することができる。
　現像促進剤としては、現像促進効果のある任意の化合物を使用できるが、カルボキシル基、フェノール性水酸基、及び、アルキレンオキシ基よりなる群から選ばれた少なくとも１種の構造を有する化合物であることが好ましく、カルボキシル基又はフェノール性水酸基を有する化合物がより好ましく、フェノール性水酸基を有する化合物が最も好ましい。
　現像促進剤としては、特開２０１２－０４２８３７号公報の段落０１７１～０１７２の記載を参酌でき、かかる内容は本願明細書に組み込まれる。 [Development accelerator]
The photocurable composition of the present invention can contain a development accelerator.
As the development accelerator, any compound having a development acceleration effect can be used, and the development accelerator may be a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group. Preferably, a compound having a carboxyl group or a phenolic hydroxyl group is more preferable, and a compound having a phenolic hydroxyl group is most preferable.
As 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.
　現像促進剤は、１種を単独で用いてもよいし、２種以上を併用することも可能である。
　本発明の光硬化性組成物における現像促進剤の添加量は、感度と残膜率の観点から、光硬化性組成物の全固形分１００質量部に対し、０～３０質量部が好ましく、０．１～２０質量部がより好ましく、０．５～１０質量部であることが最も好ましい。 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 photocurable composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photocurable composition, from the viewpoint of sensitivity and residual film ratio. More preferably, it is 1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass.
〔可塑剤〕
　本発明の光硬化性組成物は、可塑剤を含有してもよい。
　可塑剤としては、例えば、ジブチルフタレート、ジオクチルフタレート、ジドデシルフタレート、ポリエチレングリコール、グリセリン、ジメチルグリセリンフタレート、酒石酸ジブチル、アジピン酸ジオクチル、トリアセチルグリセリンなどが挙げられる。
　本発明の光硬化性組成物における可塑剤の含有量は、成分Ｂを除く固形分１００質量部に対して、０．１～３０質量部であることが好ましく、１～１０質量部であることがより好ましい。 [Plasticizer]
The photocurable composition of the present invention may contain a plasticizer.
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The content of the plasticizer in the photocurable composition of the present invention is preferably 0.1 to 30 parts by mass and preferably 1 to 10 parts by mass with respect to 100 parts by mass of the solid content excluding Component B. Is more preferable.
　また、その他の添加剤としては特開２０１２－８２２３号公報の段落０１２０～０１２１に記載の熱ラジカル発生剤、国際公開第２０１１／１３６０７４号に記載の窒素含有化合物及び熱酸発生剤も用いることができる。 As other additives, 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.
２．架橋系
（成分Ｍ）アルカリ可溶性樹脂
　本発明の光硬化性組成物は、架橋系である場合、（成分Ｘ）硬化性成分として、（成分Ｍ）アルカリ可溶性樹脂を含有することが好ましい。成分Ｍとしては特に限定されないが、フェノール系樹脂であることが好ましい。
　フェノール系樹脂は、フェノール又は置換フェノールを原料として得られる樹脂であり、具体的には、（成分Ｍ－１）ポリヒドロキシスチレン類、（成分Ｍ－２）ノボラック樹脂、並びに、（成分Ｍ－３）部分的にアルキルエーテル化されたポリビニルフェノール、及び、部分的にアルキルエーテル化された水素添加ポリビニルフェノールが挙げられる。以下、それぞれについて説明する。 2. Crosslinking system (component M) alkali-soluble resin When the photocurable composition of this invention is a crosslinking system, it is preferable to contain (component M) alkali-soluble resin as a (component X) curable component. Component M is not particularly limited, but is preferably a phenolic resin.
The phenolic resin is a resin obtained using phenol or a substituted phenol as a raw material. Specifically, (Component M-1) polyhydroxystyrenes, (Component M-2) novolak resin, and (Component M-3) are used. ) Partially alkyl etherified polyvinylphenol and partially alkyl etherified hydrogenated polyvinylphenol. Each will be described below.
（成分Ｍ－１）ポリヒドロキシスチレン類
　本発明において、成分Ｍとして、（成分Ｍ－１）ポリヒドロキシスチレン類を使用してもよい。なお、ポリヒドロキシスチレン類とは、ヒドロキシスチレンの単独重合体、又は、他のモノマーとの共重合体であり、ヒドロキシスチレン単位の含有率が３０モル％以上のアルカリ可溶性の樹脂である。
　成分Ｍ－１は、ヒドロキシスチレン単位の含有率が、３０～１００モル％であるアルカリ可溶性樹脂であり、ヒドロキシスチレン単位の含有率は５０～１００モル％であることが好ましく、７０～１００モル％であることがより好ましく、９０～１００モル％であることが更に好ましい。ヒドロキシスチレン単位の含有率が３０モル％以上であると、アルカリ現像液に対する溶解性が良好であり、現像性、解像度に優れる。 (Component M-1) Polyhydroxystyrenes In the present invention, as Component M, (Component M-1) polyhydroxystyrenes may be used. Polyhydroxystyrenes are hydroxystyrene homopolymers or copolymers with other monomers, and are alkali-soluble resins having a hydroxystyrene unit content of 30 mol% or more.
Component M-1 is an alkali-soluble resin having a hydroxystyrene unit content of 30 to 100 mol%, and the hydroxystyrene unit content is preferably 50 to 100 mol%, preferably 70 to 100 mol%. More preferably, it is more preferably 90 to 100 mol%. When the content of hydroxystyrene units is 30 mol% or more, the solubility in an alkali developer is good, and the developability and resolution are excellent.
　成分Ｍ－１におけるヒドロキシスチレンとしては、ｏ－ヒドロキシスチレン、ｍ－ヒドロキシスチレン及びｐ－ヒドロキシスチレンが挙げられ、これらのヒドロキシスチレンは、単独で又は２種以上を混合して使用することができる。
　また、必要に応じてヒドロキシスチレンと他の不飽和モノマーとを共重合させてもよく、他の不飽和モノマーとしては、スチレン、α－メチルスチレン、ビニルトルエン、ビニルキシレン等の芳香族ビニル化合物；（メタ）アクリル酸、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、クロトン酸メチル、桂皮酸メチル、マレイン酸ジメチル、フマル酸ジメチル等の不飽和カルボン酸及びそのエステル類；（メタ）アクリロニトリル；シアン化ビニリデン、α－クロロアクリロニトリル等のシアン化ビニル化合物が例示される。これらの中でも、スチレン、メチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレートが好ましく、スチレン、メチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレートがより好ましく、スチレン、メチル（メタ）アクリレートが更に好ましい。他の不飽和モノマーは、単独で又は２種以上を混合して使用することができる。 Examples of hydroxystyrene in Component M-1 include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, and these hydroxystyrenes can be used alone or in admixture of two or more.
Further, if necessary, hydroxystyrene and other unsaturated monomers may be copolymerized. Examples of the other unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylxylene; (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, Unsaturated carboxylic acids such as benzyl (meth) acrylate, phenyl (meth) acrylate, methyl crotonate, methyl cinnamate, dimethyl maleate and dimethyl fumarate and esters thereof; (meth) acrylonitrile; vinylidene cyanide, α-chloro Examples are vinyl cyanide compounds such as acrylonitrile. Indicated. Among these, styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate are preferable, and styrene, methyl (meth) acrylate, n-Butyl (meth) acrylate and t-butyl (meth) acrylate are more preferable, and styrene and methyl (meth) acrylate are more preferable. Other unsaturated monomers can be used alone or in admixture of two or more.
　成分Ｍ－１の具体例としては、ポリ（ｏ－ヒドロキシスチレン）、ポリ（ｍ－ヒドロキシスチレン）、ポリ（ｐ－ヒドロキシスチレン）、ｐ－ヒドロキシスチレン／ｏ－ヒドロキシスチレン共重合体、ｐ－ヒドロキシスチレン／ｍ－ヒドロキシスチレン共重合体等のヒドロキシスチレン類の（共）重合体のほか、ｏ－ヒドロキシスチレン／スチレン共重合体、ｏ－ヒドロキシスチレン／α－メチルスチレン共重合体、ｍ－ヒドロキシスチレン／スチレン共重合体、ｍ－ヒドロキシスチレン／α－メチルスチレン共重合体、ｐ－ヒドロキシスチレン／スチレン共重合体、ｐ－ヒドロキシスチレン／α－メチルスチレン共重合体、ｐ－ヒドロキシスチレン／メチル（メタ）アクリレート共重合体、ｐ－ヒドロキシスチレン／エチル（メタ）アクリレート共重合体、ｐ－ヒドロキシスチレン／ｎ－プロピル（メタ）アクリレート共重合体、ｐ－ヒドロキシスチレン／ｎ－ブチル（メタ）アクリレート共重合体、ｐ－ヒドロキシスチレン／ｔ－ブチル（メタ）アクリレート共重合体、ｐ－ヒドロキシスチレン／ｎ－ヘキシル（メタ）アクリレート共重合体、ｐ－ヒドロキシスチレン／ベンジル（メタ）アクリレート共重合体、ｐ－ヒドロキシスチレン／フェニル（メタ）アクリレート共重合体、ｐ－ヒドロキシスチレン／メチルエタクリレート共重合体、ｐ－ヒドロキシスチレン／エチルエタクリレート共重合体、ｐ－ヒドロキシスチレン／ｎ－プロピルエメタアクリレート共重合体、ｐ－ヒドロキシスチレン／ｎ－ブチルエタクリレート共重合体、ｐ－ヒドロキシスチレン／ｔ－ブチルエタクリレート共重合体、ｐ－ヒドロキシスチレン／ｎ－ヘキシルエタクリレート共重合体、ｐ－ヒドロキシスチレン／ベンジルエタクリレート共重合体、ｐ－ヒドロキシスチレン／フェニルエタクリレート共重合体等を挙げることができる。 Specific examples of component M-1 include poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene), p-hydroxystyrene / o-hydroxystyrene copolymer, p-hydroxy. In addition to (co) polymers of hydroxystyrenes such as styrene / m-hydroxystyrene copolymers, o-hydroxystyrene / styrene copolymers, o-hydroxystyrene / α-methylstyrene copolymers, m-hydroxystyrene / Styrene copolymer, m-hydroxystyrene / α-methylstyrene copolymer, p-hydroxystyrene / styrene copolymer, p-hydroxystyrene / α-methylstyrene copolymer, p-hydroxystyrene / methyl (meta ) Acrylate copolymer, p-hydroxystyrene / ethyl (meth) acryl Copolymer, p-hydroxystyrene / n-propyl (meth) acrylate copolymer, p-hydroxystyrene / n-butyl (meth) acrylate copolymer, p-hydroxystyrene / t-butyl (meth) acrylate Copolymer, p-hydroxystyrene / n-hexyl (meth) acrylate copolymer, p-hydroxystyrene / benzyl (meth) acrylate copolymer, p-hydroxystyrene / phenyl (meth) acrylate copolymer, p- Hydroxystyrene / methyl ethacrylate copolymer, p-hydroxystyrene / ethyl ethacrylate copolymer, p-hydroxystyrene / n-propyl ethacrylate copolymer, p-hydroxystyrene / n-butyl ethacrylate Copolymer, p-hydroxystyrene / t-butyl ether Examples include acrylate copolymers, p-hydroxystyrene / n-hexyl ethacrylate copolymers, p-hydroxystyrene / benzyl ethacrylate copolymers, p-hydroxystyrene / phenyl ethacrylate copolymers, and the like. it can.
　また、成分Ｍ－１において、ヒドロキシスチレンに由来する水酸基の一部を、変性した変性ポリヒドロキシスチレン類を使用してもよい。より具体的には、上記ヒドロキシスチレン類に、ベンゼンスルホニルクロリド誘導体、ナフタレンスルホニルクロリド誘導体、ベンゼンカルボニルクロリド誘導体、ナフタレンカルボニルクロリド誘導体などを塩基性触媒下に反応させたものが例示される。この場合、ポリヒドロキシスチレン類１００質量部に対して、上記スルホニルクロリド誘導体やカルボニルクロリド誘導体が好ましくは１０～３０質量部、より好ましくは１５～２５質量部の割合で使用される。また、上記したスルホニルクロリド誘導体やカルボニルクロリド誘導体の具体例としては、ｐ－アセトアミノベンゼンスルホニルクロリド、ベンゼンスルホニルクロリド、ｐ－クロロベンゼンスルホニルクロリド、ナフチルベンゼンスルホニルクロリド、ｐ－アセトアミノベンゼンカルボニルクロリド、ベンゼンカルボニルクロリド、ｐ－クロロベンゼンカルボニルクロリド、ナフチルベンゼンカルボニルクロリドなどが挙げられる。 Further, in the component M-1, modified polyhydroxystyrenes obtained by modifying a part of the hydroxyl group derived from hydroxystyrene may be used. More specifically, those obtained by reacting the hydroxystyrenes with a benzenesulfonyl chloride derivative, a naphthalenesulfonyl chloride derivative, a benzenecarbonyl chloride derivative, a naphthalenecarbonyl chloride derivative or the like in a basic catalyst are exemplified. In this case, the sulfonyl chloride derivative or the carbonyl chloride derivative is preferably used in an amount of 10 to 30 parts by mass, more preferably 15 to 25 parts by mass with respect to 100 parts by mass of the polyhydroxystyrenes. Specific examples of the above sulfonyl chloride derivatives and carbonyl chloride derivatives include p-acetaminobenzenesulfonyl chloride, benzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, naphthylbenzenesulfonyl chloride, p-acetaminobenzenecarbonyl chloride, benzenecarbonyl. Examples include chloride, p-chlorobenzenecarbonyl chloride, naphthylbenzenecarbonyl chloride, and the like.
　また、成分Ｍ－１において、ヒドロキシスチレンに由来する単量体単位又は、これを変性した単量体単位のベンゼン環の一部を水素化してもよい。 In Component M-1, a part of the benzene ring of the monomer unit derived from hydroxystyrene or the monomer unit modified from this may be hydrogenated.
　これらの中で、成分Ｍ－１としては、ポリ（ｐ－ヒドロキシスチレン）、ｐ－ヒドロキシスチレン／スチレン共重合体、ｐ－ヒドロキシスチレン／メチルメタクリレート共重合体、ｐ－ヒドロキシスチレン／ｎ－ブチルアクリレート共重合体、ｐ－ヒドロキシスチレン／ｔ－ブチルメタクリレート共重合体等が特に好ましく、ポリ（ｐ－ヒドロキシスチレン）が最も好ましい。 Among these, as component M-1, poly (p-hydroxystyrene), p-hydroxystyrene / styrene copolymer, p-hydroxystyrene / methyl methacrylate copolymer, p-hydroxystyrene / n-butyl acrylate A copolymer, a p-hydroxystyrene / t-butyl methacrylate copolymer, and the like are particularly preferable, and poly (p-hydroxystyrene) is most preferable.
　本発明において、成分Ｍ－１は、単独で又は２種以上を混合して使用することができる。成分Ｍ－１の製造法としては、例えば（ｉ）ヒドロキシスチレンの水酸基を保護したモノマー、例えばブトキシカルボニルオキシスチレン、ブトキシスチレン、アセトキシスチレン、テトラヒドロピラニルオキシスチレン等を、場合により他の不飽和モノマーと共に、付加重合させたのち、酸触媒又はアルカリ触媒を作用させることにより、上記保護基を加水分解して、ヒドロキシスチレンの（共）重合体を得る方法、（ii）ヒドロキシスチレンを、場合により他の不飽和モノマーと共に、付加重合させる方法等を挙げることができるが、（ｉ）の方法が好ましい。上記付加重合は、例えばラジカル重合、アニオン重合、カチオン重合、熱重合等の適宜の方法により実施することができるが、アニオン重合又はカチオン重合による方法が、得られる樹脂の分散度を小さくできる点で好ましい。また、上記酸触媒としては、例えば塩酸、硫酸等の無機酸を挙げることができる。また、上記アルカリ触媒としては、例えば水酸化ナトリウム、水酸化カリウム等を挙げることができる。 In the present invention, Component M-1 can be used alone or in admixture of two or more. The production method of component M-1 includes, for example, (i) a monomer in which the hydroxyl group of hydroxystyrene is protected, such as butoxycarbonyloxystyrene, butoxystyrene, acetoxystyrene, tetrahydropyranyloxystyrene, and other unsaturated monomers depending on the case. In addition, after the addition polymerization, an acid catalyst or an alkali catalyst is allowed to act to hydrolyze the protective group to obtain a (co) polymer of hydroxystyrene. Although the method of addition polymerization can be mentioned with the unsaturated monomer, the method (i) is preferred. The above addition polymerization can be carried out by an appropriate method such as radical polymerization, anionic polymerization, cationic polymerization, thermal polymerization, etc., but the method based on anionic polymerization or cationic polymerization can reduce the degree of dispersion of the resulting resin. preferable. Examples of the acid catalyst include inorganic acids such as hydrochloric acid and sulfuric acid. Examples of the alkali catalyst include sodium hydroxide and potassium hydroxide.
（成分Ｍ－２）ノボラック樹脂
　本発明において、成分Ｍとして（成分Ｍ－２）ノボラック樹脂を使用することができる。
　ノボラック樹脂とは、フェノール系化合物とアルデヒドとを、酸触媒又はアルカリ触媒の存在下で縮合させることにより得られるものである。
　ノボラック樹脂の製造に用いられるフェノール系化合物は、フェノール性水酸基を有する芳香族化合物であり、例えば、フェノール、ｏ－、ｍ－又はｐ－クレゾール、２，３－、２，５－、３，４－又は３，５－キシレノール、２，３，５－トリメチルフェノール、２－、３－又は４－ｔｅｒｔ－ブチルフェノール、２－ｔｅｒｔ－ブチル－４－又は－５－メチルフェノール、２－、４－又は５－メチルレゾルシノール、２－、３－又は４－メトキシフェノール、２，３－、２，５－又は３，５－ジメトキシフェノール、２－メトキシレゾルシノール、４－ｔｅｒｔ－ブチルカテコール、２－、３－又は４－エチルフェノール、２，５－又は３，５－ジエチルフェノール、２，３，５－トリエチルフェノール、 ２－ナフトール、１，３－、１，５－又は１，７－ジヒドロキシナフタレン、キシレノールとヒドロキシベンズアルデヒドとの縮合により得られるポリヒドロキシトリフェニルメタン系化合物などが挙げられる。これらの中でも、フェノール、ｏ－クレゾール、ｍ－クレゾール及びｐ－クレゾールが好ましい。
　これらのフェノール系化合物は、それぞれ単独で、又は２種以上組み合わせて用いることができる。 (Component M-2) Novolak Resin In the present invention, (Component M-2) novolac resin can be used as Component M.
The novolak resin is obtained by condensing a phenolic compound and an aldehyde in the presence of an acid catalyst or an alkali catalyst.
The phenolic compound used for the production of the novolak resin is an aromatic compound having a phenolic hydroxyl group, for example, phenol, o-, m- or p-cresol, 2,3-, 2,5-, 3,4 -Or 3,5-xylenol, 2,3,5-trimethylphenol, 2-, 3- or 4-tert-butylphenol, 2-tert-butyl-4- or -5-methylphenol, 2-, 4- or 5-methylresorcinol, 2-, 3- or 4-methoxyphenol, 2,3-, 2,5- or 3,5-dimethoxyphenol, 2-methoxyresorcinol, 4-tert-butylcatechol, 2-, 3- Or 4-ethylphenol, 2,5- or 3,5-diethylphenol, 2,3,5-triethylphenol, 2-naphthol, 1,3-, 1 , 5- or 1,7-dihydroxynaphthalene, polyhydroxytriphenylmethane compounds obtained by condensation of xylenol and hydroxybenzaldehyde, and the like. Among these, phenol, o-cresol, m-cresol and p-cresol are preferable.
These phenolic compounds can be used alone or in combination of two or more.
　また、ノボラック樹脂の製造に用いられるアルデヒドは、分子中に少なくとも１つのアルデヒド基を有する化合物又は反応系において容易にアルデヒド基を生成する化合物であり、例えば、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ブチルアルデヒド、イソブチルアルデヒド、ピバルアルデヒド、ヘキシルアルデヒド、アクロレイン及びクロトンアルデヒドのような脂肪族アルデヒド類、シクロヘキサンアルデヒド、シクロペンタンアルデヒド、フルフラール及びフリルアクロレインのような脂環式アルデヒド類、ベンズアルデヒド、ｏ－、ｍ－又はｐ－メチルベンズアルデヒド、ｐ－エチルベンズアルデヒド、２，４－、２，５－、３，４－又は３，５－ジメチルベンズアルデヒド、ｏ－、ｍ－又はｐ－ヒドロキシベンズアルデヒド、ｏ－、ｍ－又はｐ－アニスアルデヒド及びバニリンのような芳香族アルデヒド類、フェニルアセトアルデヒド及びケイ皮アルデヒドのような芳香脂肪族アルデヒド類などが挙げられる。これらのアルデヒドも、それぞれ単独で、又は所望により２種以上組み合わせて用いることができる。これらの中では、工業的に入手しやすいことから、アセトアルデヒド又はホルムアルデヒドが好ましく、特にホルムアルデヒドが好ましい。 The aldehyde used for producing the novolak resin is a compound having at least one aldehyde group in the molecule or a compound that easily generates an aldehyde group in the reaction system. For example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, Aliphatic aldehydes such as isobutyraldehyde, pivalaldehyde, hexylaldehyde, acrolein and crotonaldehyde, cycloaliphatic aldehydes such as cyclohexanealdehyde, cyclopentanealdehyde, furfural and furylacrolein, benzaldehyde, o-, m- or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4- or 3,5-dimethylbenzaldehyde, o-, m- or p-hydroxy Lens aldehydes, o-, aromatic aldehydes such as m- or p- anisaldehyde and vanillin, include araliphatic aldehydes such as phenylacetaldehyde and cinnamaldehyde. These aldehydes can also be used alone or in combination of two or more as desired. Among these, acetaldehyde or formaldehyde is preferable because it is easily available industrially, and formaldehyde is particularly preferable.
　フェノール系化合物とアルデヒドとの縮合に用いられる酸触媒の例としては、塩酸、硫酸、過塩素酸及び燐酸のような無機酸、蟻酸、酢酸、シュウ酸、マロン酸、トリクロロ酢酸及びｐ－トルエンスルホン酸のような有機酸、酢酸亜鉛、塩化亜鉛及び酢酸マグネシウムのような二価金属塩などが挙げられる。また、アルカリ触媒としては、水酸化ナトリウム、水酸化カリウム、水酸化セシウム、炭酸ナトリウム、炭酸水素ナトリウム、アンモニア、水酸化テトラメチルアンモニウム、トリエチルアミン、モルホリン、ピリジンなどが挙げられる。
　これらの中でも、酸触媒を使用することが好ましく、酢酸、シュウ酸、マロン酸、ｐ－トルエンスルホン酸のような有機酸を使用することが好ましい。
　酸触媒又はアルカリ触媒は、それぞれ単独で、又は２種以上組み合わせて用いることができる。縮合反応は常法に従って行うことができ、例えば、６０～１２０℃の範囲の温度で２～３０時間程度行われる。 Examples of acid catalysts used for the condensation of phenolic compounds with aldehydes include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid and phosphoric acid, formic acid, acetic acid, oxalic acid, malonic acid, trichloroacetic acid and p-toluenesulfone Examples thereof include organic acids such as acids, divalent metal salts such as zinc acetate, zinc chloride and magnesium acetate. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia, tetramethylammonium hydroxide, triethylamine, morpholine, pyridine and the like.
Among these, it is preferable to use an acid catalyst, and it is preferable to use an organic acid such as acetic acid, oxalic acid, malonic acid, and p-toluenesulfonic acid.
The acid catalyst or alkali catalyst can be used alone or in combination of two or more. The condensation reaction can be carried out according to a conventional method, for example, at a temperature in the range of 60 to 120 ° C. for about 2 to 30 hours.
　重縮合に使用される反応溶媒としては、メタノール、エタノール、イソプロパノール、ｔ－ブチルアルコール等のアルコール類；メチルエチルケトン、メチルイソブチルケトン、メチルへキシルケトン、メチルヘプチルケトン、シクロヘキシルケトン等のケトン類；酢酸プロピル、酢酸ブチル、酢酸イソブチル、プロピオン酸メチル、乳酸メチル、酢酸プロピレングリコール等のエステル類；ジブチルエーテル、テトラヒドロフラン、テトラヒドロピラン、ジオキサン等のエーテル類、ベンゼン、トルエン、キシレン等の芳香族炭化水素類；ジクロロメタン、クロロホルム、四塩化炭素、ブロモホルム等のハロゲン化炭化水素類；ヘキサン、ヘプタン、デカン、石油エーテル等の炭化水素類が挙げられる。これらは１種又は２種以上を混合して使用することができる。また、反応系に水を共存させてもよく、水と互いに溶解しない溶媒の場合は、２層に分離した反応溶媒を用いてもよい。蒸留脱水等で水を除去してもよい。
　これらの中でも、ケトン類、エステル類、芳香族炭化水素類を反応溶媒として使用することが好ましい。 Reaction solvents used for polycondensation include alcohols such as methanol, ethanol, isopropanol, and t-butyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl hexyl ketone, methyl heptyl ketone, and cyclohexyl ketone; propyl acetate, Esters such as butyl acetate, isobutyl acetate, methyl propionate, methyl lactate, and propylene glycol acetate; ethers such as dibutyl ether, tetrahydrofuran, tetrahydropyran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; dichloromethane, Halogenated hydrocarbons such as chloroform, carbon tetrachloride, and bromoform; hydrocarbons such as hexane, heptane, decane, and petroleum ether. These can be used alone or in combination of two or more. In addition, water may coexist in the reaction system, and in the case of a solvent that does not dissolve in water, a reaction solvent separated into two layers may be used. Water may be removed by distillation dehydration or the like.
Among these, ketones, esters, and aromatic hydrocarbons are preferably used as the reaction solvent.
　（成分Ｍ）アルカリ可溶性樹脂の一部として、重量平均分子量９００以下のノボラック樹脂を含有させることは、解像度を向上させるうえで好ましい。このような低分子量ノボラック樹脂オリゴマーも、常法に従って、それぞれ上記したようなフェノール系化合物とアルデヒドとを酸触媒の存在下で縮合させることにより製造でき、その際、低分子量体が生成するような反応条件、例えば、酸触媒を原料フェノール系化合物に対して０.００１～０.０１モル倍程度と少なめに用い、反応時間を１～５時間程度と短めにすればよい。 (Component M) It is preferable to contain a novolak resin having a weight average molecular weight of 900 or less as part of the alkali-soluble resin in order to improve the resolution. Such a low molecular weight novolak resin oligomer can also be produced by condensing a phenolic compound and an aldehyde as described above in the presence of an acid catalyst according to a conventional method, in which case a low molecular weight product is produced. The reaction conditions, for example, the acid catalyst may be used as little as about 0.001 to 0.01 mole times the starting phenolic compound, and the reaction time may be shortened to about 1 to 5 hours.
　低分子量ノボラック樹脂オリゴマーをアルカリ可溶性樹脂の一部として用いる場合は、残りのアルカリ可溶性樹脂は、それより重量平均分子量の大きいもの、例えば、重量平均分子量２，０００以上であるものが適当である。特に、高分子量分主体のノボラック樹脂を併用することは、解像度を向上させるうえで一層好ましい。
　具体的には、ノボラック樹脂をＧＰＣで分析したときに、分子量１，０００以下の範囲のパターン面積が、未反応の原料フェノール系化合物を除く全パターン面積に対して２５％以下、更には２０％以下となるようにしたものが好ましい。ここでパターン面積は、２５４ｎｍのＵＶ検出器を用いて測定したものを意味する。このような高分子量分主体のノボラック樹脂は、例えば、縮合反応で得られるノボラック樹脂に分別などの操作を施すことにより製造できる。分別を行う場合は、ノボラック樹脂を、良溶媒、例えば、メタノールやエタノールのようなアルコール類、アセトンやメチルエチルケトン、メチルイソブチルケトンのようなケトン類、エチルセロソルブのようなグリコールエーテル類、エチルセロソルブアセテートのようなグリコールエーテルエステル類、テトラヒドロフランのようなエーテル類などに溶解し、この溶液を水中に注いで高分子量分を沈殿させる方法、あるいはこの溶液を、ペンタン、ヘキサン、ヘプタンのような貧溶媒と混合して高分子量分主体の下層を分液する方法などが採用できる。高分子量分主体のノボラック樹脂は、その重量平均分子量が５，０００以上、特に６，０００以上であるものが有利である。 When the low molecular weight novolak resin oligomer is used as a part of the alkali-soluble resin, the remaining alkali-soluble resin having a higher weight average molecular weight, for example, a weight average molecular weight of 2,000 or more is suitable. In particular, it is more preferable to use a novolak resin mainly composed of a high molecular weight component in order to improve the resolution.
Specifically, when the novolak resin is analyzed by GPC, the pattern area having a molecular weight of 1,000 or less is 25% or less, further 20% with respect to the total pattern area excluding the unreacted raw material phenol compound. The following is preferable. Here, the pattern area means that measured using a 254 nm UV detector. Such a novolak resin mainly composed of high molecular weight can be produced, for example, by subjecting the novolak resin obtained by the condensation reaction to an operation such as fractionation. In the case of fractionation, novolak resin is mixed with a good solvent, for example, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, methyl isobutyl ketone, glycol ethers such as ethyl cellosolve, and ethyl cellosolve acetate. Such as glycol ether esters, ethers such as tetrahydrofuran, etc., and this solution is poured into water to precipitate the high molecular weight, or this solution is mixed with a poor solvent such as pentane, hexane, heptane Thus, a method of separating the lower layer mainly composed of high molecular weight can be employed. As the novolak resin mainly composed of a high molecular weight, those having a weight average molecular weight of 5,000 or more, particularly 6,000 or more are advantageous.
（成分Ｍ－３）部分的にアルキルエーテル化されたポリビニルフェノール、及び、部分的にアルキルエーテル化された水素添加ポリビニルフェノール
　本発明において、成分Ｍとして、（成分Ｍ－３）部分的にアルキルエーテル化されたポリビニルフェノール（以下、成分Ｍ－３－１ともいう。）、及び、部分的にアルキルエーテル化された水素添加ポリビニルフェノール（以下、成分Ｍ－３－２ともいう。）を使用してもよい。
　ポリビニルフェノールを構成するビニルフェノールとしては、ビニル基と水酸基との位置関係は特に限定されないが、ｐ－ビニルフェノールであることが好ましい。成分Ｍ－３－１は、アルキルエーテル化率が１０～３０モル％であることが好ましく、１５～２２モル％がより好ましい。また、成分Ｍ－３－２は、アルキルエーテル化率が５～３０モル％であることが好ましく、８～２０モル％であることがより好ましい。成分Ｍ－３－１及び成分Ｍ－３－２は併用してもよく、混合割合は適宜選択すればよく、特に限定されない。 (Component M-3) Partially alkyletherified polyvinylphenol and Partially alkyletherified hydrogenated polyvinylphenol In the present invention, as Component M, (Component M-3) partially alkylether Polyvinyl alcohol (hereinafter also referred to as component M-3-1) and partially alkyl etherified hydrogenated polyvinyl phenol (hereinafter also referred to as component M-3-2). Also good.
The vinyl phenol constituting the polyvinyl phenol is not particularly limited in the positional relationship between the vinyl group and the hydroxyl group, but is preferably p-vinyl phenol. Component M-3-1 preferably has an alkyl etherification rate of 10 to 30 mol%, more preferably 15 to 22 mol%. Component M-3-2 preferably has an alkyl etherification rate of 5 to 30 mol%, more preferably 8 to 20 mol%. Component M-3-1 and Component M-3-2 may be used in combination, and the mixing ratio may be appropriately selected and is not particularly limited.
　アルキルエーテルとしては、直鎖又は分岐状のアルキルエーテルが挙げられ、炭素数は１～４であることが好ましく、メチルエーテル又はエチルエーテルが好ましい。 Examples of the alkyl ether include linear or branched alkyl ethers, preferably having 1 to 4 carbon atoms, and more preferably methyl ether or ethyl ether.
　ポリビニルフェノールは、例えば、ｔ－ブトキシスチレンの重合により得られるポリ（ｔ－ブトキシスチレン）を加水分解することによって製造できる。もちろん、このようにして製造され、各種の平均分子量や分散度を有するものが市販されているので、市販品をそのまま用いることもできる。
　成分Ｍ－３－１は、ポリビニルフェノールとハロゲン化アルキルとを、例えばＧ．Ｎ．Ｖｙａｓら著、Ｏｒｇ．Ｓｙｎｔｈｅｓｅｓ　Ｃｏｌｌ．　Ｖｏｌ．ＩＶ，８３６（１９６３）等に記載の方法で反応させることにより製造することができる。また、成分Ｍ－３－２は、例えば水素添加ポリビニルフェノールとハロゲン化アルキルとを、上記のＧ．Ｎ．Ｖｙａｓらの方法により製造することができる。水素添加ポリビニルフェノールはポリビニルフェノールを常法に従って水素添加することにより製造することができる。 Polyvinylphenol can be produced, for example, by hydrolyzing poly (t-butoxystyrene) obtained by polymerization of t-butoxystyrene. Of course, since products manufactured in this manner and having various average molecular weights and dispersities are commercially available, commercially available products can be used as they are.
Component M-3-1 includes polyvinylphenol and alkyl halides such as G.I. N. Vyas et al., Org. Syntheses Coll. Vol. IV, 836 (1963) and the like. Component M-3-2 includes, for example, hydrogenated polyvinylphenol and an alkyl halide, as described in G. N. It can be produced by the method of Vyas et al. Hydrogenated polyvinylphenol can be produced by hydrogenating polyvinylphenol according to a conventional method.
　成分Ｍ－１～Ｍ－３と共に、他のアルカリ可溶性樹脂、水溶性樹脂を使用してもよい。このようなアルカリ可溶性樹脂、水溶性樹脂としては線状有機ポリマーを用いることが好ましく、公知のものを任意に使用できる。例えば、水可溶性有機ポリマーを用いると水現像が可能になる。このような線状有機ポリマーとしては、側鎖にカルボン酸基を有するラジカル重合体、例えば特開昭５９－４４６１５号公報、特公昭５４－３４３２７号公報、特公昭５８－１２５７７号公報、特公昭５４－２５９５７号公報、特開昭５４－９２７２３号公報公報、特開昭５９－５３８３６号公報、特開昭５９－７１０４８号公報に記載されているもの、すなわち、カルボキシル基を有するモノマーを単独あるいは共重合させた樹脂、酸無水物基を有するモノマーを単独あるいは共重合させ酸無水物ユニットを加水分解若しくはハーフエステル化若しくはハーフアミド化させた樹脂、エポキシ樹脂を不飽和モノカルボン酸及び酸無水物で変性させたエポキシアクリレート等が挙げられる。カルボキシル基を有するモノマーとしては、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、４－カルボキシルスチレン等が挙げられ、酸無水物基を有するモノマーとしては、無水マレイン酸等が挙げられる。
　また、同様に側鎖にカルボン酸基を有する酸性セルロース誘導体がある。この他に水酸基を有する重合体に環状酸無水物を付加させたものなどが有用である。また、ビニルフェノール樹脂、イソプロペニルフェノール樹脂、イソプロペニルフェノールとスチレンとの共重合体（共重合体のイソプロペニルフェノールの割合は５０モル％以上が好ましい。）、部分的にｔ－ブトキシカルボニルオキシ化されたポリビニルフェノール、あるいは水素添加ポリビニルフェノール等が挙げられる。
　成分Ｍ－１～成分Ｍ－３と併用する場合、成分Ｍ－１～成分Ｍ－３の合計量が成分Ｍ全体の５０質量％以上であることが好ましく、６５質量％以上であることがより好ましく、８０質量％以上であることが更に好ましい。 Other alkali-soluble resins and water-soluble resins may be used together with the components M-1 to M-3. As such an alkali-soluble resin and a water-soluble resin, it is preferable to use a linear organic polymer, and a known one can be arbitrarily used. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such a linear organic polymer include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. No. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, monomers having a carboxyl group alone or Resin obtained by copolymerization, resin having acid anhydride group alone or copolymerized, and acid anhydride unit is hydrolyzed, half-esterified or half-amidated, epoxy resin is unsaturated monocarboxylic acid and acid anhydride And epoxy acrylate modified with 1. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxyl styrene. Examples of the monomer having an acid anhydride group include maleic anhydride. Can be mentioned.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful. Further, vinylphenol resin, isopropenylphenol resin, a copolymer of isopropenylphenol and styrene (the proportion of isopropenylphenol in the copolymer is preferably 50 mol% or more), partially t-butoxycarbonyloxylation Polyvinylphenol, hydrogenated polyvinylphenol, and the like.
When used in combination with Component M-1 to Component M-3, the total amount of Component M-1 to Component M-3 is preferably 50% by mass or more, more preferably 65% by mass or more of the entire component M. Preferably, it is 80 mass% or more.
　本発明の光硬化性組成物は、（成分Ｍ）アルカリ可溶性樹脂として、成分Ｍ－１～成分Ｍ－３と共に、又は、単独で、カルド樹脂を含有してもよい。カルド樹脂を用いることで、屈折率の高い膜を得ることができるため、好ましい。
　カルド樹脂とは、カルド構造、すなわち、環状構造を構成している４級炭素原子に二つの環状構造が結合した骨格構造、を有する樹脂である。カルド構造の一般的なものはフルオレン環にベンゼン環が結合したものである。
　環状構造を構成している４級炭素原子に二つの環状構造が結合した骨格構造の具体例としては、フルオレン骨格、ビスフェノールフルオレン骨格、ビスアミノフェニルフルオレン骨格、エポキシ基を有するフルオレン骨格、アクリル基を有するフルオレン骨格等が挙げられる。
　カルド樹脂は、このカルド構造を有する骨格がそれに結合している官能基間の反応等により重合して形成される。カルド樹脂は、主鎖と嵩高い側鎖が一つの元素で繋がれた構造（カルド構造）をもち、主鎖に対してほぼ垂直方向に環状構造を有している。 The photocurable composition of the present invention may contain a cardo resin as (Component M) alkali-soluble resin, together with Component M-1 to Component M-3, or alone. Use of a cardo resin is preferable because a film having a high refractive index can be obtained.
The cardo resin is a resin having a cardo structure, that is, a skeletal structure in which two cyclic structures are bonded to quaternary carbon atoms constituting the cyclic structure. A common cardo structure is a fluorene ring bonded with a benzene ring.
Specific examples of the skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and an acrylic group. And a fluorene skeleton having the same.
The cardo resin is formed by polymerizing a skeleton having the cardo structure by a reaction between functional groups bonded thereto. The cardo resin has a structure in which a main chain and bulky side chains are connected by one element (cardo structure), and has a ring structure in a direction substantially perpendicular to the main chain.
　カルド構造を有する単量体は、例えば、ビス（グリシジルオキシフェニル）フルオレン型エポキシ樹脂；ビスフェノールフルオレン型エポキシ樹脂とアクリル酸との縮合物；９，９－ビス（４－ヒドロキシフェニル）フルオレン、９，９－ビス（４－ヒドロキシ－３－メチルフェニル）フルオレン等のカルド構造含有ビスフェノ－ル類；９，９－ビス（シアノメチル）フルオレン等の９，９－ビス（シアノアルキル）フルオレン類；９，９－ビス（３－アミノプロピル）フルオレン等の９，９－ビス（アミノアルキル）フルオレン類；等が挙げられる。
　カルド樹脂は、カルド構造を有する単量体を重合して得られる重合体であるが、その他の共重合可能な単量体との共重合体であってもよい。
　上記単量体の重合方法は、常法に従えばよく、例えば、開環重合法や付加重合法等が採用される。 Monomers having a cardo structure include, for example, bis (glycidyloxyphenyl) fluorene type epoxy resin; condensate of bisphenolfluorene type epoxy resin and acrylic acid; 9,9-bis (4-hydroxyphenyl) fluorene, Cardio structure-containing bisphenols such as 9-bis (4-hydroxy-3-methylphenyl) fluorene; 9,9-bis (cyanoalkyl) fluorenes such as 9,9-bis (cyanomethyl) fluorene; -9,9-bis (aminoalkyl) fluorenes such as bis (3-aminopropyl) fluorene;
The cardo resin is a polymer obtained by polymerizing a monomer having a cardo structure, but may be a copolymer with other copolymerizable monomers.
The polymerization method of the monomer may be according to a conventional method, and for example, a ring-opening polymerization method or an addition polymerization method is employed.
　カルド樹脂の一例として、下記式（Ｚ－１）で表される化合物と、下記式（Ｚ－２）で表される化合物と、ピロメリット酸無水物、及び、テレフタル酸やその酸塩化物から選択される少なくとも１種と、を共重合させることにより得られるポリエステル系カルド樹脂や、下記式（Ｚ－３）で表される化合物も挙げることができる。 As an example of a cardo resin, from a compound represented by the following formula (Z-1), a compound represented by the following formula (Z-2), pyromellitic anhydride, terephthalic acid and its acid chloride Mention may also be made of polyester-based cardo resins obtained by copolymerizing at least one selected from the above, and compounds represented by the following formula (Z-3).
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
 （式（Ｚ－２）中、Ｒ10は、酸素、カルボニル基、テトラフルオロエチレン基、又は、単結合を表す。）
Figure JPOXMLDOC01-appb-C000039
 (In the formula (Z-2), R 10 represents oxygen, a carbonyl group, a tetrafluoroethylene group, or a single bond.)
Figure JPOXMLDOC01-appb-C000040
 （式（Ｚ－３）中、Ｒ1及びＲ2は置換基を表す。）
Figure JPOXMLDOC01-appb-C000040
 (In formula (Z-3), R 1 and R 2 represent a substituent.)
　成分Ｍ－１の重量平均分子量は、１，０００～１００，０００であることが好ましく、２，０００～５０，０００であることがより好ましく、５，０００～３０，０００であることが更に好ましい。
　成分Ｍ－２の重量平均分子量は、２００～２０，０００であることが好ましく、３００～１０，０００であることがより好ましく、５００～１０，０００であることが更に好ましい。
　成分Ｍ－３の重量平均分子量は、１，０００～１００，０００であることが好ましく、２，０００～５０，０００であることがより好ましく、５，０００～３０，０００であることが更に好ましい。
　本発明において重量平均分子量は、ＧＰＣ法により分子量既知のポリスチレン換算にて求められる。 The weight average molecular weight of Component M-1 is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 5,000 to 30,000. .
The weight average molecular weight of Component M-2 is preferably 200 to 20,000, more preferably 300 to 10,000, and still more preferably 500 to 10,000.
The weight average molecular weight of Component M-3 is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 5,000 to 30,000. .
In the present invention, the weight average molecular weight is determined in terms of polystyrene having a known molecular weight by the GPC method.
　本発明の光硬化性組成物中における成分Ｍの含有量は、成分Ｂを除く光硬化性組成物の全固形分に対して、１０～９９．９質量％であることが好ましく、２５～９８質量％であることがより好ましく、３５～９５質量％であることが更に好ましい。含有量がこの範囲であると、現像した際のパターン形成性が良好となり、また、より高屈折率の硬化物が得られる。なお、光硬化性組成物の固形分量とは、溶剤などの揮発性成分を除いた量を表す。
　また、本発明の光硬化性組成物中における成分Ｍを含む重合体（樹脂）成分の総含有量は、光硬化性組成物の全固形分に対して、２０～９９．９質量％であることが好ましく、５０～９８質量％であることがより好ましく、７０～９５質量％であることが更に好ましい。上記範囲であると、現像した際のパターン形成性が良好となり、また、より高屈折率の硬化物が得られる。 The content of Component M in the photocurable composition of the present invention is preferably 10 to 99.9% by mass with respect to the total solid content of the photocurable composition excluding Component B, preferably 25 to 98. More preferably, it is more preferably 35% to 95% by mass. When the content is within this range, the pattern formability during development is good, and a cured product having a higher refractive index can be obtained. The solid content of the photocurable composition represents an amount excluding volatile components such as a solvent.
The total content of the polymer (resin) component including the component M in the photocurable composition of the present invention is 20 to 99.9% by mass with respect to the total solid content of the photocurable composition. It is preferably 50 to 98% by mass, more preferably 70 to 95% by mass. When it is in the above range, the pattern formability at the time of development becomes good, and a cured product having a higher refractive index can be obtained.
（成分Ｎ）架橋剤
　本発明の光硬化性組成物が架橋系である場合、（成分Ｘ）硬化性成分として、（成分Ｎ）架橋剤を含有することが好ましい。架橋剤としては、（成分Ｎ－１）下記式（Ｌ）で表される基を有する化合物を含有することが好ましい。成分Ｎ－１は架橋剤として機能し、成分Ｍ同士を架橋する。なお、成分Ａは、式（Ｌ）で表される基を有しないことが好ましい。 (Component N) Crosslinking agent When the photocurable composition of the present invention is a crosslinking system, it is preferable to contain (Component N) a crosslinking agent as the (Component X) curable component. The crosslinking agent preferably contains (Component N-1) a compound having a group represented by the following formula (L). Component N-1 functions as a crosslinking agent and crosslinks components M together. In addition, it is preferable that the component A does not have group represented by a formula (L).
Figure JPOXMLDOC01-appb-C000041
 （式（Ｌ）中、Ｘ1及びＸ2はそれぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基又はアシル基を表し、Ｙは水素原子又は一価の置換基を表し、＊は連結位置を表し、芳香環を構成する炭素原子、複素環を構成する窒素原子又は炭素原子、あるいは、２級又は３級窒素原子と連結する。）
Figure JPOXMLDOC01-appb-C000041
 (In formula (L), X 1 and X 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an acyl group, and Y represents a hydrogen atom or a monovalent substituent. * Represents a connecting position, and is connected to a carbon atom constituting an aromatic ring, a nitrogen atom or a carbon atom constituting a heterocyclic ring, or a secondary or tertiary nitrogen atom.)
　式（Ｌ）中、Ｘ1及びＸ2はそれぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基又はアシル基を表し、アルキル基としては、炭素数１～１２のアルキル基であることが好ましく、炭素数１～６のアルキル基であることがより好ましく、メチル基又はエチル基であることが更に好ましい。シクロアルキル基としては、炭素数３～２０のシクロアルキル基であることが好ましく、炭素数５～１０のシクロアルキル基であることが好ましい。アルケニル基及びアルキニル基は、炭素数２～１２であることが好ましく、炭素数２～６であることがより好ましく、炭素数２～４であることが更に好ましい。アリール基は、炭素数６～２０であることが好ましく、炭素数６～１０であることがより好ましく、フェニル基であることが特に好ましい。アシル基は、炭素数１～６であることが好ましく、炭素数１（ホルミル基）、炭素数２（アセチル基）又は炭素数３（プロピオニル基）であることがより好ましい。
　これらの中でも、Ｘ1及びＸ2は、水素原子、メチル基又はエチル基であることが好ましく、水素原子であることが特に好ましい。 In the formula (L), X 1 and X 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or an acyl group, and the alkyl group has 1 to 12 carbon atoms. An alkyl group is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group or ethyl group is still more preferred. The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, and more preferably a cycloalkyl group having 5 to 10 carbon atoms. The alkenyl group and alkynyl group preferably have 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably a phenyl group. The acyl group preferably has 1 to 6 carbon atoms, more preferably 1 carbon (formyl group), 2 carbon atoms (acetyl group), or 3 carbon atoms (propionyl group).
Among these, X 1 and X 2 are preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.
　式（Ｌ）中、Ｙは水素原子又は一価の置換基を表し、一価の置換基としては、アルキル基（好ましくは炭素数１～６、より好ましくは１～４、更に好ましくはメチル基又はエチル基、特に好ましくはメチル基）、アルケニル基（好ましくは炭素数２～１２、より好ましくは炭素数２～６、更に好ましくは炭素数２～４）、アルキニル基（好ましくは炭素数２～１２、より好ましくは炭素数２～６、更に好ましくは炭素数２～４）、シクロアルキル基（好ましくは炭素数３～２０、より好ましくは炭素数５～１０）、アリール基（好ましくは炭素数６～２０、より好ましくは６～１０）、ハロアルキル基（好ましくは炭素数１～６、より好ましくは炭素数１～４，更に好ましくは炭素数１又は２）、アシル基（好ましくは炭素数１～６、より好ましくは炭素数１～３、更に好ましくは炭素数１（アセチル基））、アルキルスルホニル基（好ましくは炭素数１～６、より好ましくは１～４、更に好ましくは１又は２）、アリールスルホニル基（好ましくは炭素数６～２０、より好ましくは炭素数６～１０）、及び複素環基が挙げられる。これらの基は更に置換基を有していてもよい。置換基としては、水酸基、シアノ基、チオール基等が挙げられる。
　これらの中でも、Ｙは水素原子、アルキル基、又はアシル基であることが好ましく、水素原子又はアルキル基であることがより好ましい。 In formula (L), Y represents a hydrogen atom or a monovalent substituent, and the monovalent substituent includes an alkyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably a methyl group). Or an ethyl group, particularly preferably a methyl group, an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms), an alkynyl group (preferably having 2 to 2 carbon atoms). 12, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms), an aryl group (preferably a carbon number) 6 to 20, more preferably 6 to 10), a haloalkyl group (preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 or 2 carbon atoms), an acyl group (preferably 1 carbon atom) ~ 6, better Or an alkylsulfonyl group (preferably 1 to 6, more preferably 1 to 4, more preferably 1 or 2), an arylsulfonyl group. (Preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), and heterocyclic groups. These groups may further have a substituent. Examples of the substituent include a hydroxyl group, a cyano group, and a thiol group.
Among these, Y is preferably a hydrogen atom, an alkyl group, or an acyl group, and more preferably a hydrogen atom or an alkyl group.
　式（Ｌ）で表される基は、置換基を有していてもよいヒドロキシメチル基、置換基を有していてもよいアルコキシメチル基、又は置換基を有していてもよいアシルオキシメチル基（例えば、アセトキシメチル基）であることが好ましい。アルコキシメチル基としては、メトキシメチル基が特に好ましい。ヒドロキシメチル基又はアルコキシメチル基であることがより好ましく、ヒドロキシメチル基（－ＣＨ2ＯＨ）、メトキシメチル基（－ＣＨ2－Ｏ－ＣＨ3）又はエトキシメチル基（－ＣＨ2－Ｏ－ＣＨ2ＣＨ3）であることが更に好ましく、ヒドロキシメチル基又はメトキシメチル基であることが特に好ましく、メトキシメチル基であることが最も好ましい。 The group represented by the formula (L) is a hydroxymethyl group which may have a substituent, an alkoxymethyl group which may have a substituent, or an acyloxymethyl group which may have a substituent. (For example, an acetoxymethyl group) is preferable. As the alkoxymethyl group, a methoxymethyl group is particularly preferable. It is more preferably a hydroxymethyl group or an alkoxymethyl group, and a hydroxymethyl group (—CH 2 OH), a methoxymethyl group (—CH 2 —O—CH 3 ), or an ethoxymethyl group (—CH 2 —O—CH 2). CH 3 ) is more preferable, hydroxymethyl group or methoxymethyl group is particularly preferable, and methoxymethyl group is most preferable.
　式（Ｌ）で表される基は、芳香環を構成する炭素原子、複素環を構成する窒素原子又は炭素原子、あるいは、２級又は３級窒素原子と連結する。芳香環を構成する炭素原子、複素環を構成する窒素原子又は炭素原子、あるいは、複素環に結合した窒素原子と連結することが好ましい。
　すなわち、式（Ｌ）で表される基は、芳香環又は複素環に直接又は連結基を介して結合していることが好ましく、連結基を介している場合には、連結基の窒素原子に結合しており、直接結合する場合には、炭素原子又は窒素原子に結合していることが好ましい。
　成分Ｎ－１は、式（Ｌ）で表される基を少なくとも１つ有しており、２つ以上有することが好ましく、３～６つ有することがより好ましい。 The group represented by the formula (L) is linked to a carbon atom constituting an aromatic ring, a nitrogen atom or a carbon atom constituting a heterocyclic ring, or a secondary or tertiary nitrogen atom. It is preferable to link to a carbon atom constituting an aromatic ring, a nitrogen atom or carbon atom constituting a heterocyclic ring, or a nitrogen atom bonded to the heterocyclic ring.
That is, the group represented by the formula (L) is preferably bonded to an aromatic ring or a heterocyclic ring directly or via a linking group, and in the case of being connected to a linking group, When bonded and directly bonded, it is preferably bonded to a carbon atom or a nitrogen atom.
Component N-1 has at least one group represented by the formula (L), preferably two or more, more preferably 3 to 6.
　ここで、上記複素環は、複素芳香環であってもよく、非芳香族複素環であってもよい。また、芳香環及び複素環は、単環であっても多環であってもよく、特に限定されない。また、多環構造は縮合環であってもよく、有橋式環であってもよく、また、スピロ環であってもよい。更に、２以上の単環が単結合によって連結した形態であってもよい。 Here, the heterocycle may be a heteroaromatic ring or a non-aromatic heterocycle. In addition, the aromatic ring and the heterocyclic ring may be monocyclic or polycyclic and are not particularly limited. The polycyclic structure may be a condensed ring, a bridged ring, or a spiro ring. Further, two or more single rings may be connected by a single bond.
　これらの中でも、成分Ｎ－１は式（Ｌ）で表される基がウレイレン基を構成する窒素原子に結合したウレア系化合物、式（Ｌ）で表される基がグリコールラウリルの環上の窒素原子に連結したグリコールラウリル系化合物、式（Ｌ）で表される基がトリアジン環に結合した窒素原子に連結したトリアジン系化合物、又は、式（Ｌ）で表される基が芳香環上に置換したフェノール系化合物であることが好ましい。これらの中でも、成分Ｎ－１がグリコールラウリル系化合物、又は、トリアジン系化合物であることが好ましく、トリアジン系化合物であることがより好ましい。なお、トリアジン系化合物の中でも、成分Ｎ－１はメラミン系化合物であることが特に好ましい。すなわち、成分Ｎ－１は、トリアジン環に結合したアミノ基を構成する窒素原子に式（Ｌ）で表される基が結合したメラミン系化合物であることが特に好ましい。 Among these, component N-1 is a urea compound in which the group represented by the formula (L) is bonded to the nitrogen atom constituting the ureylene group, and the group represented by the formula (L) is nitrogen on the ring of glycol lauryl. A glycol lauryl compound linked to an atom, a triazine compound linked to a nitrogen atom in which a group represented by formula (L) is bound to a triazine ring, or a group represented by formula (L) is substituted on an aromatic ring Preference is given to phenolic compounds. Among these, component N-1 is preferably a glycol lauryl compound or a triazine compound, and more preferably a triazine compound. Of the triazine compounds, component N-1 is particularly preferably a melamine compound. That is, component N-1 is particularly preferably a melamine compound in which a group represented by the formula (L) is bonded to a nitrogen atom constituting an amino group bonded to a triazine ring.
　トリアジン系化合物としては、下記式（Ｉ）又は（ＩＩ）で表される化合物であることが好ましく、式（ＩＩ）で表されるメラミン系化合物であることが特に好ましい。 The triazine compound is preferably a compound represented by the following formula (I) or (II), and particularly preferably a melamine compound represented by formula (II).
Figure JPOXMLDOC01-appb-C000042
 （式（Ｉ）中、Ｒ1は水素原子、アルキル基、アリール基、アルコキシ基、又はアリールオキシ基を表し、Ｌは式（Ｌ）で表される基を表す。）
Figure JPOXMLDOC01-appb-C000042
 (In the formula (I), R 1 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and L represents a group represented by the formula (L).)
Figure JPOXMLDOC01-appb-C000043
 （式（ＩＩ）中、Ｒ2及びＲ3はそれぞれ独立に水素原子又は式（Ｌ）で表される基を表し、Ｌは式（Ｌ）で表される基を表す。）
Figure JPOXMLDOC01-appb-C000043
 (In Formula (II), R 2 and R 3 each independently represent a hydrogen atom or a group represented by Formula (L), and L represents a group represented by Formula (L).)
　式（Ｉ）中、Ｒ1としてのアルキル基及びアルコキシ基は、炭素数１～１２であることが好ましく、１～６であることがより好ましく、１又は２であることがより好ましい。Ｒ1としてのアリール基又はアリールオキシ基は、炭素数６～２０であることが好ましく、６～１０であることがより好ましく、６又は１０であることが更に好ましく、６（フェニル基又はフェノキシ基）であることが特に好ましい。上記のアルキル基、アリール基、複素芳香族基、アルコキシ基、アリールオキシ基は置換基を有していてもよく、置換基としては、アルキル基、水酸基、アリール基、が例示される。
　これらの中でも、式（Ｉ）中、Ｒ1としてはアリール基が好ましく、フェニル基が特に好ましい。 In formula (I), the alkyl group and alkoxy group as R 1 preferably have 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 or 2. The aryl group or aryloxy group as R 1 preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, still more preferably 6 or 10, and 6 (phenyl group or phenoxy group). Is particularly preferred. The alkyl group, aryl group, heteroaromatic group, alkoxy group, and aryloxy group may have a substituent, and examples of the substituent include an alkyl group, a hydroxyl group, and an aryl group.
Among these, in formula (I), R 1 is preferably an aryl group, and a phenyl group is particularly preferable.
　式（Ｉ）及び式（ＩＩ）中、Ｌは式（Ｌ）で表される基を表し、好ましい範囲は上述した通りである。 In formula (I) and formula (II), L represents a group represented by formula (L), and a preferred range is as described above.
　トリアジン系化合物である成分Ｎ－１の具体例としては、ヘキサメチロールメラミン、ペンタメチロールメラミン、テトラメチロールメラミン、ヘキサメトキシメチルメラミン、ペンタメトキシメチルメラミン、テトラメトキシメチルメラミン、ヘキサエトキシメチルメラミン、テトラメチロールベンゾグアナミン、テトラメトキシメチルベンゾグアナミン、トリメトキシメチルベンゾグアナミン、テトラエトキシメチルベンゾグアナミンが例示される。 Specific examples of component N-1 which is a triazine compound include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, tetramethylol benzoguanamine. , Tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, and tetraethoxymethylbenzoguanamine.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　更に、成分Ｎ－１としては以下の化合物も好ましく例示される。
（ｂ－１２）２，６－ビス（ヒドロキシメチル）－４－メチルフェノール、
（ｂ－１３）４－ｔ－ブチル－２，６－ビス（ヒドロキシメチル）フェノール、
（ｂ－１４）５－エチル－１，３－ビス（ヒドロキシメチル）ペルヒドロ－１，３，５－トリアジン－２－オン（通称Ｎ－エチルジメチロールトリアゾン）又は（ｂ－１５）そのジメチルエーテル体、
（ｂ－１６）ジメチロールトリメチレン尿素又は（ｂ－１７）そのジメチルエーテル体、
（ｂ－１８）３，５－ビス（ヒドロキシメチル）ペルヒドロ－１，３，５－オキサジアジン－４－オン（通称ジメチロールウロン）又は（ｂ－１９）そのジメチルエーテル体、
（ｂ－２０）テトラメチロールグリオキザールジウレイン又は（ｂ－２１）そのテトラメチルエーテル体。 Furthermore, as the component N-1, the following compounds are also preferably exemplified.
(B-12) 2,6-bis (hydroxymethyl) -4-methylphenol,
(B-13) 4-tert-butyl-2,6-bis (hydroxymethyl) phenol,
(B-14) 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or (b-15) its dimethyl ether ,
(B-16) dimethylol trimethylene urea or (b-17) its dimethyl ether form,
(B-18) 3,5-bis (hydroxymethyl) perhydro-1,3,5-oxadiazin-4-one (commonly called dimethyloluron) or (b-19) a dimethyl ether thereof,
(B-20) tetramethylol glyoxal diurein or (b-21) tetramethyl ether thereof.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　更に、成分Ｎ－１として、上市されている製品を使用してもよく、例えば、ニカラックＭＷ－３０ＨＭ、ニカラックＭＷ－３９０、ニカラックＭＷ－１００ＬＭ、ニカラックＭＸ－７５０ＬＭ、ニカラックＭＸ－２７０、ニカラックＭＸ－２８０、ニカラックＭＸ－２９０（以上、（株）三和ケミカル製）が挙げられる。 Furthermore, as the component N-1, a commercially available product may be used. For example, Nicarak MW-30HM, Nicarak MW-390, Nicarac MW-100LM, Nicarax MX-750LM, Nicarac MX-270, Nicarac MX- 280, Nicalak MX-290 (manufactured by Sanwa Chemical Co., Ltd.).
　成分Ｎは、低分子化合物であることが好ましく、分子量（分子量分布を有する場合には、重量平均分子量）は、１，０００以下であることが好ましい。１００～８００であることがより好ましく、２００～５００であることが更に好ましい。
　重量平均分子量が上記範囲内であると、硬化性に優れる。 Component N is preferably a low molecular compound, and the molecular weight (in the case of having a molecular weight distribution, the weight average molecular weight) is preferably 1,000 or less. It is more preferably 100 to 800, and further preferably 200 to 500.
When the weight average molecular weight is within the above range, the curability is excellent.
　また、成分Ｎは、１種単独で使用してもよいし、２種以上を併用することもできる。
　本発明の光硬化性組成物における成分Ｎの含有量は、本発明の光硬化性組成物の全固形分に対して、０．１～２０質量％であることが好ましく、０．５～１５質量％であることがより好ましく、０．５～１０質量％であることが更に好ましい。上記範囲であると、硬化性に優れ、また、解像度に優れる。 Moreover, the component N may be used individually by 1 type, and can also use 2 or more types together.
The content of component N in the photocurable composition of the present invention is preferably 0.1 to 20% by mass, and preferably 0.5 to 15%, based on the total solid content of the photocurable composition of the present invention. More preferably, it is more preferably 0.5 to 10% by mass. Within the above range, the curability is excellent and the resolution is excellent.
（成分Ｏ）酸発生剤
　本発明の光硬化性組成物は、架橋系である場合、（成分Ｘ）硬化性成分として、（成分Ｏ）酸発生剤を含有することが好ましい。本発明において、（成分Ｏ）酸発生剤は、光酸発生剤であることが好ましく、波長３００ｎｍ以上、より好ましくは波長３００～４５０ｎｍの活性光線に感応し、酸を発生する化合物が好ましいが、その化学構造に制限されるものではない。また、波長３００ｎｍ以上の活性光線に直接感応しない酸発生剤についても、増感剤と併用することによって波長３００ｎｍ以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく用いることができる。本発明で使用される酸発生剤としては、ｐＫａが４以下の酸を発生する酸発生剤が好ましく、ｐＫａが３以下の酸を発生する酸発生剤がより好ましく、ｐＫａが２以下の酸を発生する酸発生剤が最も好ましい。また、ｐＫａは、－１５以上であることが好ましい。 (Component O) Acid generator When the photocurable composition of the present invention is a crosslinking system, it is preferable to contain (Component O) an acid generator as the (Component X) curable component. In the present invention, the (Component O) acid generator is preferably a photoacid generator, preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, more preferably a wavelength of 300 to 450 nm, and generates an acid. The chemical structure is not limited. In addition, an acid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be combined with a sensitizer as long as 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 the sensitizer. Can be preferably used. The acid generator used in the present invention is preferably an acid generator that generates an acid having a pKa of 4 or less, more preferably an acid generator that generates an acid having a pKa of 3 or less, and an acid having a pKa of 2 or less. The acid generator that is generated is most preferred. Further, pKa is preferably −15 or more.
　光酸発生剤の例として、トリクロロメチル－ｓ－トリアジン類、スルホニウム塩やヨードニウム塩、第四級アンモニウム塩類、ジアゾメタン化合物、イミドスルホネート化合物、及び、オキシムスルホネート化合物などを挙げることができる。これらの中でも、絶縁性及び感度の観点から、オキシムスルホネート化合物を用いることが好ましい。これら酸発生剤は、１種単独又は２種類以上を組み合わせて使用することができる。トリクロロメチル－ｓ－トリアジン類、ジアリールヨードニウム塩類、トリアリールスルホニウム塩類、第四級アンモニウム塩類、及び、ジアゾメタン誘導体の具体例としては、特開２０１１－２２１４９４号公報の段落００８３～００８８に記載の化合物が例示できる。 Examples of the photoacid generator 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 and sensitivity. These acid generators can be used singly or in combination of two or more. Specific examples of 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.
　オキシムスルホネート化合物、すなわち、オキシムスルホネート構造を有する化合物としては、下記式（Ｃ１）で表されるオキシムスルホネート構造を含有する化合物が好ましく例示できる。 Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following formula (C1).
Figure JPOXMLDOC01-appb-C000046
 （式（Ｃ１）中、Ｒ21は、アルキル基又はアリール基を表し、波線部分は他の基との結合箇所を表す。）
Figure JPOXMLDOC01-appb-C000046
 (In the formula (C1), R 21 represents an alkyl group or an aryl group, and a wavy line represents a bonding site with another group.)
　いずれの基も置換されてもよく、Ｒ21におけるアルキル基は直鎖状でも分岐状でも環状でもよい。許容される置換基は以下に説明する。
　Ｒ21のアルキル基としては、炭素数１～１０の、直鎖状又は分岐状アルキル基が好ましい。Ｒ21のアルキル基は、炭素数６～１１のアリール基、炭素数１～１０のアルコキシ基、又は、シクロアルキル基（７，７－ジメチル－２－オキソノルボルニル基などの有橋式脂環基を含む、好ましくはビシクロアルキル基等）で置換されてもよい。
　Ｒ21のアリール基としては、炭素数６～１１のアリール基が好ましく、フェニル基又はナフチル基がより好ましい。Ｒ21のアリール基は、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基又はハロゲン原子で置換されてもよい。 Any group may be substituted, and the alkyl group in R 21 may be linear, branched or cyclic. Acceptable substituents are described below.
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.
As the 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.
　上記式（Ｃ１）で表されるオキシムスルホネート構造を含有する上記化合物は、下記式（Ｃ２）で表されるオキシムスルホネート化合物であることも好ましい。 The above compound containing an oxime sulfonate structure represented by the above formula (C1) is also preferably an oxime sulfonate compound represented by the following formula (C2).
Figure JPOXMLDOC01-appb-C000047
 （式（Ｃ２）中、Ｒ42は、アルキル基又はアリール基を表し、Ｘは、アルキル基、アルコキシ基又はハロゲン原子を表し、ｍ４は、０～３の整数を表し、ｍ４が２又は３であるとき、複数のＸは同一でも異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000047
 (In the formula (C2), 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, and m4 is 2 or 3. In some cases, multiple Xs may be the same or different.)
　Ｘとしてのアルキル基は、炭素数１～４の直鎖状又は分岐状アルキル基が好ましい。
　Ｘとしてのアルコキシ基は、炭素数１～４の直鎖状又は分岐状アルコキシ基が好ましい。
　Ｘとしてのハロゲン原子は、塩素原子又はフッ素原子が好ましい。
　ｍ４は、０又は１が好ましい。上記式（Ｂ２）中、ｍ４が１であり、Ｘがメチル基であり、Ｘの置換位置がオルト位であり、Ｒ42が炭素数１～１０の直鎖状アルキル基、７，７－ジメチル－２－オキソノルボルニルメチル基、又は、ｐ－トルイル基である化合物が特に好ましい。 The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1. In the above 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.
　上記式（Ｃ１）で表されるオキシムスルホネート構造を含有する化合物は、下記式（Ｃ３）で表されるオキシムスルホネート化合物であることも好ましい。 The compound containing an oxime sulfonate structure represented by the above formula (C1) is also preferably an oxime sulfonate compound represented by the following formula (C3).
Figure JPOXMLDOC01-appb-C000048
 （式（Ｃ３）中、Ｒ43は式（Ｃ２）におけるＲ42と同義であり、Ｘ1は、ハロゲン原子、水酸基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、シアノ基又はニトロ基を表し、ｎ４は０～５の整数を表す。）
Figure JPOXMLDOC01-appb-C000048
 (In formula (C3), R 43 has the same meaning as R 42 in formula (C2), and X 1 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and n4 represents an integer of 0 to 5.)
　上記式（Ｃ３）におけるＲ43としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－オクチル基、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロ－ｎ－プロピル基、パーフルオロ－ｎ－ブチル基、ｐ－トリル基、４－クロロフェニル基又はペンタフルオロフェニル基が好ましく、ｎ－オクチル基が特に好ましい。
　Ｘ1としては、炭素数１～５のアルコキシ基が好ましく、メトキシ基がより好ましい。
　ｎ４としては、０～２の整数が好ましく、０又は１が特に好ましい。 As R 43 in the above formula (C3), 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.
　上記式（Ｃ３）で表される化合物の具体例としては、α－（メチルスルホニルオキシイミノ）ベンジルシアニド、α－（エチルスルホニルオキシイミノ）ベンジルシアニド、α－（ｎ－プロピルスルホニルオキシイミノ）ベンジルシアニド、α－（ｎ－ブチルスルホニルオキシイミノ）ベンジルシアニド、α－（４－トルエンスルホニルオキシイミノ）ベンジルシアニド、α－〔（メチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（エチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（ｎ－プロピルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（ｎ－ブチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（４－トルエンスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリルを挙げることができる。 Specific examples of the compound represented by the above formula (C3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α -[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4-methoxy Phenyl] acetonitrile, α-[(4-to Can be exemplified ene sulfonyl) -4-methoxyphenyl] acetonitrile.
　好ましいオキシムスルホネート化合物の具体例としては、下記化合物（ｉ）～（ｖｉｉｉ）等が挙げられ、１種単独で使用、又は、２種類以上を併用することができる。化合物（ｉ）～（ｖｉｉｉ）は、市販品として、入手することができる。また、他の種類の（成分Ｏ）酸発生剤と組み合わせて使用することもできる。 Specific examples of preferable oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used singly or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. It can also be used in combination with other types of (component O) acid generators.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　上記式（Ｃ１）で表されるオキシムスルホネート構造を含有する化合物としては、下記式（ＯＳ－１）で表される化合物であることも好ましい。 The compound containing an oxime sulfonate structure represented by the above formula (C1) is also preferably a compound represented by the following formula (OS-1).
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　上記式（ＯＳ－１）中、Ｒ101は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基、又は、ヘテロアリール基を表す。Ｒ102は、アルキル基、又は、アリール基を表す。
　Ｘ101は－Ｏ－、－Ｓ－、－ＮＨ－、－ＮＲ105－、－ＣＨ2－、－ＣＲ106Ｈ－、又は、－ＣＲ105Ｒ107－を表し、Ｒ105～Ｒ107はアルキル基、又は、アリール基を表す。
　Ｒ121～Ｒ124はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基、又は、アリール基を表す。Ｒ121～Ｒ124のうち２つは、それぞれ互いに結合して環を形成してもよい。
　Ｒ121～Ｒ124としてはそれぞれ独立に、水素原子、ハロゲン原子、又は、アルキル基が好ましく、また、Ｒ121～Ｒ124のうち少なくとも２つが互いに結合してアリール基を形成する態様もまた、好ましく挙げられる。中でも、Ｒ121～Ｒ124がいずれも水素原子である態様が感度の観点から好ましい。
　既述の官能基は、いずれも、更に置換基を有していてもよい。 In the above 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.
　上記式（ＯＳ－１）で表される化合物は、下記式（ＯＳ－２）で表される化合物であることがより好ましい。 The compound represented by the above formula (OS-1) is more preferably a compound represented by the following formula (OS-2).
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　上記式（ＯＳ－２）中、Ｒ101、Ｒ102、Ｒ121～Ｒ124は、それぞれ式（ＯＳ－１）におけるものと同義であり、好ましい例もまた同様である。
　これらの中でも、上記式（ＯＳ－１）及び上記式（ＯＳ－２）におけるＲ101がシアノ基、又は、アリール基である態様がより好ましく、上記式（ＯＳ－２）で表され、Ｒ101がシアノ基、フェニル基又はナフチル基である態様が最も好ましい。 In the above 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.
Among these, 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.
　また、本発明におけるオキシムスルホネート化合物において、オキシムやベンゾチアゾール環の立体構造（Ｅ，Ｚ等）についてはそれぞれ、どちらか一方であっても、混合物であってもよい。 In the oxime sulfonate compound of the present invention, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
　本発明に好適に用いうる上記式（ＯＳ－１）で表される化合物の具体例としては、特開２０１１－２２１４９４号公報の段落０１２８～０１３２に記載の化合物（例示化合物ｂ－１～ｂ－３４）が挙げられるが、本発明はこれに限定されない。 Specific examples of the compound represented by the formula (OS-1) that can be suitably used in the present invention include compounds described in paragraphs 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b- 34), but the present invention is not limited to this.
　本発明では、上記式（Ｃ１）で表されるオキシムスルホネート構造を含有する化合物としては、下記式（ＯＳ－３）、下記式（ＯＳ－４）又は下記式（ＯＳ－５）で表されるオキシムスルホネート化合物であることが好ましい。 In the present invention, the compound having an oxime sulfonate structure represented by the above formula (C1) 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.
Figure JPOXMLDOC01-appb-C000052
 （式（ＯＳ－３）～式（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28はそれぞれ独立に、アルキル基、アリール基又はヘテロアリール基を表し、Ｒ23、Ｒ26及びＲ29はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、Ｒ24、Ｒ27及びＲ30はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表し、Ｘ1～Ｘ3はそれぞれ独立に、酸素原子又は硫黄原子を表し、ｎ1～ｎ3はそれぞれ独立に、１又は２を表し、ｍ1～ｍ3はそれぞれ独立に、０～６の整数を表す。）
Figure JPOXMLDOC01-appb-C000052
 (In the formulas (OS-3) to (OS-5), R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group, and R 23 , R 26 and R 29 are Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxy group. Represents a sulfonyl group, X 1 to X 3 each independently represents an oxygen atom or a sulfur atom, n 1 to n 3 each independently represents 1 or 2, and m 1 to m 3 each independently represents 0 Represents an integer of ~ 6)
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28におけるアルキル基、アリール基又はヘテロアリール基は、置換基を有していてもよい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28におけるアルキル基としては、置換基を有していてもよい総炭素数１～３０のアルキル基であることが好ましい。
　また、上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28におけるアリール基としては、置換基を有してもよい総炭素数６～３０のアリール基が好ましい。
　また、上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28におけるヘテロアリール基としては、置換基を有してもよい総炭素数４～３０のヘテロアリール基が好ましい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28におけるヘテロアリール基は、少なくとも１つの環が複素芳香環であればよく、例えば、複素芳香環とベンゼン環とが縮環していてもよい。 In the above formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R 22 , R 25 and R 28 may have a substituent.
In the above formulas (OS-3) to (OS-5), 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.
In the above formulas (OS-3) to (OS-5), 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. .
In the above formulas (OS-3) to (OS-5), 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.
In the above formulas (OS-3) to (OS-5), 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.
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ23、Ｒ26及びＲ29は、水素原子、アルキル基又はアリール基であることが好ましく、水素原子又はアルキル基であることがより好ましい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、化合物中に２以上存在するＲ23、Ｒ26及びＲ29のうち、１つ又は２つがアルキル基、アリール基又はハロゲン原子であることが好ましく、１つがアルキル基、アリール基又はハロゲン原子であることがより好ましく、１つがアルキル基であり、かつ残りが水素原子であることが特に好ましい。 In the above formulas (OS-3) to (OS-5), 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. .
In the above formulas (OS-3) to (OS-5), 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.
　Ｒ23、Ｒ26及びＲ29におけるアルキル基としては、置換基を有してもよい総炭素数１～１２のアルキル基であることが好ましく、置換基を有してもよい総炭素数１～６のアルキル基であることがより好ましい。 The alkyl group for R 23 , R 26 and R 29 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.
　Ｒ23、Ｒ26及びＲ29におけるアリール基としては、置換基を有してもよい総炭素数６～３０のアリール基であることが好ましい。 The aryl group for R 23 , R 26 and R 29 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｘ1～Ｘ3はそれぞれ独立に、Ｏ又はＳを表し、Ｏであることが好ましい。
　上記式（ＯＳ－３）～（ＯＳ－５）において、Ｘ1～Ｘ3を環員として含む環は、５員環又は６員環である。
　上記式（ＯＳ－３）～（ＯＳ－５）中、ｎ1～ｎ3はそれぞれ独立に、１又は２を表し、Ｘ1～Ｘ3がＯである場合、ｎ1～ｎ3はそれぞれ独立に、１であることが好ましく、また、Ｘ1～Ｘ3がＳである場合、ｎ1～ｎ3はそれぞれ独立に、２であることが好ましい。 In the above formulas (OS-3) to (OS-5), X 1 to X 3 each independently represents O or S, and is preferably O.
In the above formulas (OS-3) to (OS-5), the ring containing X 1 to X 3 as a ring member is a 5-membered ring or a 6-membered ring.
In the formulas (OS-3) to (OS-5), 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.
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27及びＲ30はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表す。その中でも、Ｒ24、Ｒ27及びＲ30はそれぞれ独立に、アルキル基又はアルキルオキシ基であることが好ましい。
　Ｒ24、Ｒ27及びＲ30におけるアルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基及びアルコキシスルホニル基は、置換基を有していてもよい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27及びＲ30におけるアルキル基としては、置換基を有していてもよい総炭素数１～３０のアルキル基であることが好ましい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27及びＲ30におけるアルキルオキシ基としては、置換基を有してもよい総炭素数１～３０のアルキルオキシ基であることが好ましい。 In the above formulas (OS-3) to (OS-5), 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. To express. Among these, 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.
In the above formulas (OS-3) to (OS-5), 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.
In the above formulas (OS-3) to (OS-5), the alkyloxy group in R 24 , R 27 and R 30 is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. It is preferable.
　また、上記式（ＯＳ－３）～（ＯＳ－５）中、ｍ1～ｍ3はそれぞれ独立に、０～６の整数を表し、０～２の整数であることが好ましく、０又は１であることがより好ましく、０であることが特に好ましい。
　また、上記式（ＯＳ－３）～（ＯＳ－５）のそれぞれの置換基について、特開２０１１－２２１４９４号公報の段落００９２～０１０９に記載の（ＯＳ－３）～（ＯＳ－５）の置換基の好ましい範囲も同様に好ましい。 In the above formulas (OS-3) to (OS-5), 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.
In addition, for each substituent of the above formulas (OS-3) to (OS-5), the substitution of (OS-3) to (OS-5) described in paragraphs 0092 to 0109 of JP2011-221494A The preferred range of groups is likewise preferred.
　また、上記式（Ｃ１）で表されるオキシムスルホネート構造を含有する化合物は、下記式（ＯＳ－６）～（ＯＳ－１１）のいずれかで表されるオキシムスルホネート化合物であることが特に好ましい。 The compound containing an oxime sulfonate structure represented by the above formula (C1) is particularly preferably an oxime sulfonate compound represented by any one of the following formulas (OS-6) to (OS-11).
Figure JPOXMLDOC01-appb-C000053
 （式（ＯＳ－６）～（ＯＳ－１１）中、Ｒ301～Ｒ306はアルキル基、アリール基又はヘテロアリール基を表し、Ｒ307は、水素原子又は臭素原子を表し、Ｒ308～Ｒ310、Ｒ313、Ｒ316及びＲ318はそれぞれ独立に、水素原子、炭素数１～８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、Ｒ311及びＲ314はそれぞれ独立に、水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、Ｒ312、Ｒ315、Ｒ317及びＲ319はそれぞれ独立には、水素原子又はメチル基を表す。）
Figure JPOXMLDOC01-appb-C000053
 (In the formulas (OS-6) to (OS-11), R 301 to R 306 represent an alkyl group, an aryl group, or a heteroaryl group, R 307 represents a hydrogen atom or a bromine atom, and R 308 to R 310 , R 313 , R 316 and R 318 each independently 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, and R 312 , R 315 , R 317 and R 319 each independently represent a hydrogen atom or a methyl group. )
　上記式（ＯＳ－６）～（ＯＳ－１１）における好ましい範囲は、特開２０１１－２２１４９４号公報の段落０１１０～０１１２に記載される（ＯＳ－６）～（ＯＳ－１１）の好ましい範囲と同様である。 Preferred ranges in the above formulas (OS-6) to (OS-11) are the same as the preferred ranges of (OS-6) to (OS-11) described in paragraphs 0110 to 0112 of JP2011-221494A. It is.
　上記式（ＯＳ－３）～上記式（ＯＳ－５）で表されるオキシムスルホネート化合物の具体例としては、特開２０１１－２２１４９４号公報の段落０１１４～０１２０に記載の化合物が挙げられるが、本発明は、これらに限定されるものではない。 Specific examples of the oxime sulfonate compounds represented by the 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.
　本発明の光硬化性組成物において、（成分Ｏ）酸発生剤は、光硬化性組成物中の成分Ｍを含む重合体（樹脂）成分１００質量部に対して、０．１～１０質量部使用することが好ましく、０．５～１０質量部使用することがより好ましい。
　また、成分Ｏは光硬化性組成物の固形分（ただし、金属酸化物粒子を除く）に対し、０．１～１０質量％であることが好ましく、０．５～１０質量％であることがより好ましい。
　また、成分Ｏは、１種単独で使用してもよいし、２種以上を併用することもできる。 In the photocurable composition of the present invention, (Component O) the acid generator is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (resin) component containing Component M in the photocurable composition. It is preferable to use 0.5 to 10 parts by mass.
Component O is preferably 0.1 to 10% by mass, and preferably 0.5 to 10% by mass, based on the solid content of the photocurable composition (excluding metal oxide particles). More preferred.
Moreover, the component O may be used individually by 1 type, and can also use 2 or more types together.
（成分Ｐ）酸化防止剤
　本発明の光硬化性組成物は、架橋系の場合、（成分Ｐ）酸化防止剤を含有してもよい。酸化防止剤としては、公知の酸化防止剤を含有することができる。酸化防止剤を添加することにより、硬化膜の着色を防止できる、又は、分解による膜厚減少を低減でき、また、耐熱透明性に優れるという利点がある。
　このような酸化防止剤としては、例えば、リン系酸化防止剤、アミド類、ヒドラジド類、ヒンダードアミン系酸化防止剤、イオウ系酸化防止剤、フェノール系酸化防止剤、アスコルビン酸類、硫酸亜鉛、糖類、亜硝酸塩、亜硫酸塩、チオ硫酸塩、ヒドロキシルアミン誘導体等を挙げることができる。これらの中では、硬化膜の着色、膜厚減少の観点から特にフェノール系酸化防止剤、アミド系酸化防止剤、ヒドラジド系酸化防止剤、イオウ系酸化防止剤が好ましい。これらは１種単独で用いてもよいし、２種以上を混合してもよい。
　フェノール系酸化防止剤の市販品としては、例えば、アデカスタブＡＯ－１５、アデカスタブＡＯ－１８、アデカスタブＡＯ－２０、アデカスタブＡＯ－２３、アデカスタブＡＯ－３０、アデカスタブＡＯ－３７、アデカスタブＡＯ－４０、アデカスタブＡＯ－５０、アデカスタブＡＯ－５１、アデカスタブＡＯ－６０、アデカスタブＡＯ－７０、アデカスタブＡＯ－８０、アデカスタブＡＯ－３３０、アデカスタブＡＯ－４１２Ｓ、アデカスタブＡＯ－５０３、アデカスタブＡ－６１１、アデカスタブＡ－６１２、アデカスタブＡ－６１３、アデカスタブＰＥＰ－４Ｃ、アデカスタブＰＥＰ－８、アデカスタブＰＥＰ－８Ｗ、アデカスタブＰＥＰ－２４Ｇ、アデカスタブＰＥＰ－３６、アデカスタブＰＥＰ－３６Ｚ、アデカスタブＨＰ－１０、アデカスタブ２１１２、アデカスタブ２６０、アデカスタブ５２２Ａ、アデカスタブ１１７８、アデカスタブ１５００、アデカスタブＣ、アデカスタブ１３５Ａ、アデカスタブ３０１０、アデカスタブＴＰＰ、アデカスタブＣＤＡ－１、アデカスタブＣＤＡ－６、アデカスタブＺＳ－２７、アデカスタブＺＳ－９０、アデカスタブＺＳ－９１（以上、（株）ＡＤＥＫＡ製）、イルガノックス２４５ＦＦ、イルガノックス１０１０ＦＦ、イルガノックス１０１０、イルガノックスＭＤ１０２４、イルガノックス１０３５ＦＦ、イルガノックス１０３５、イルガノックス１０９８、イルガノックス１３３０、イルガノックス１５２０Ｌ、イルガノックス３１１４、イルガノックス１７２６、イルガフォス１６８、イルガモッド２９５（ＢＡＳＦ社製）、チヌビン４０５（ＢＡＳＦ社製）などが挙げられる。中でも、アデカスタブＡＯ－６０、アデカスタブＡＯ－８０、イルガノックス１７２６、イルガノックス１０３５、イルガノックス１０９８、チヌビン４０５を好適に使用することができる。 (Component P) Antioxidant The photocurable composition of the present invention may contain (Component P) an antioxidant in the case of a crosslinking system. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
Examples of such 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. Among these, 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. -50, 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), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Company, Ltd.), Tinuvin 405 (manufactured by BASF), and the like. Among them, ADK STAB AO-60, ADK STAB AO-80, Irganox 1726, Irganox 1035, Irganox 1098, and Tinuvin 405 can be preferably used.
　酸化防止剤の含有量は、光硬化性組成物の全固形分に対して、０．１～１０質量％であることが好ましく、０．２～５質量％であることがより好ましく、０．５～４質量％であることが特に好ましい。この範囲にすることで、形成された膜の十分な透明性が得られ、かつ、パターン形成時の感度も良好となる。
　また、酸化防止剤以外の添加剤として、「高分子添加剤の新展開」（（株）日刊工業新聞社）に記載の各種紫外線吸収剤や、金属不活性化剤等を本発明の光硬化性組成物に添加してもよい。 The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photocurable 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.
In addition, as an additive other than the antioxidant, various ultraviolet absorbers described in “New Development of Polymer Additives” (Nikkan Kogyo Shimbun Co., Ltd.), metal deactivators, etc. are photocured according to the present invention. May be added to the composition.
（成分Ｑ）塩基性化合物
　本発明の光硬化性組成物は、架橋系の場合、（成分Ｑ）塩基性化合物を含有してもよい。（成分Ｑ）塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、カルボン酸の第四級アンモニウム塩等が挙げられる。これらの具体例としては、特開２０１１－２２１４９４号公報の段落０２０４～０２０７に記載の化合物が挙げられる。 (Component Q) Basic Compound The photocurable composition of the present invention may contain (Component Q) a basic compound in the case of a crosslinking system. (Component Q) 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.
　具体的には、脂肪族アミンとしては、例えば、トリメチルアミン、ジエチルアミン、トリエチルアミン、ジ－ｎ－プロピルアミン、トリ－ｎ－プロピルアミン、ジ－ｎ－ペンチルアミン、トリ－ｎ－ペンチルアミン、ジエタノールアミン、トリエタノールアミン、ジシクロヘキシルアミン、ジシクロヘキシルメチルアミンなどが挙げられる。
　芳香族アミンとしては、例えば、アニリン、ベンジルアミン、Ｎ，Ｎ－ジメチルアニリン、ジフェニルアミンなどが挙げられる。
　複素環式アミンとしては、例えば、ピリジン、２－メチルピリジン、４－メチルピリジン、２－エチルピリジン、４－エチルピリジン、２－フェニルピリジン、４－フェニルピリジン、Ｎ－メチル－４－フェニルピリジン、４－ジメチルアミノピリジン、イミダゾール、ベンズイミダゾール、４－メチルイミダゾール、２－フェニルベンズイミダゾール、２，４，５－トリフェニルイミダゾール、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、８－オキシキノリン、ピラジン、ピラゾール、ピリダジン、プリン、ピロリジン、ピペリジン、ピペラジン、モルホリン、４－メチルモルホリン、Ｎ－シクロヘキシル－Ｎ’－［２－（４－モルホリニル）エチル］チオ尿素、１，５－ジアザビシクロ［４．３．０］－５－ノネン、１，８－ジアザビシクロ［５．３．０］－７－ウンデセンなどが挙げられる。
　第四級アンモニウムヒドロキシドとしては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラ－ｎ－ブチルアンモニウムヒドロキシド、テトラ－ｎ－ヘキシルアンモニウムヒドロキシドなどが挙げられる。
　カルボン酸の第四級アンモニウム塩としては、例えば、テトラメチルアンモニウムアセテート、テトラメチルアンモニウムベンゾエート、テトラ－ｎ－ブチルアンモニウムアセテート、テトラ－ｎ－ブチルアンモニウムベンゾエートなどが挙げられる。 Specific examples of the aliphatic amine 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.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
　本発明に用いることができる塩基性化合物は、１種単独で使用しても、２種以上を併用してもよい。
　本発明の光硬化性組成物における塩基性化合物の含有量は、光硬化性組成物中の全固形分１００質量部に対して、０．００１～３質量部であることが好ましく、０．００５～１質量部であることがより好ましい。 The 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 photocurable 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 photocurable composition. More preferred is 1 part by mass.
（成分Ｒ）酸増殖剤
　本発明の光硬化性組成物は、架橋系の場合、感度向上を目的に、（成分Ｒ）酸増殖剤を用いることができる。
　本発明に用いることができる酸増殖剤は、酸触媒反応によって更に酸を発生して反応系内の酸濃度を上昇させることができる化合物であり、酸が存在しない状態では安定に存在する化合物である。このような化合物は、１回の反応で１つ以上の酸が増えるため、反応の進行に伴って加速的に反応が進むが、発生した酸自体が自己分解を誘起するため、ここで発生する酸の強度は、酸解離定数、ｐＫａとして３以下であることが好ましく、２以下であることが特に好ましい。
　酸増殖剤の具体例としては、特開平１０－１５０８号公報の段落０２０３～０２２３、特開平１０－２８２６４２号公報の段落００１６～００５５、及び、特表平９－５１２４９８号公報第３９頁１２行目～第４７頁２行目に記載の化合物を挙げることができる。
　本発明で用いることができる酸増殖剤としては、酸発生剤から発生した酸によって分解し、ジクロロ酢酸、トリクロロ酢酸、メタンスルホン酸、ベンゼンスルホン酸、トリフルオロメタンスルホン酸、フェニルホスホン酸などのｐＫａが３以下の酸を発生させる化合物を挙げることができる。
　具体的には、以下の化合物等を挙げることができる。 (Component R) Acid Proliferating Agent In the case of the crosslinking system, the photocurable composition of the present invention can use (Component R) 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.
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.
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
　酸増殖剤の光硬化性組成物への含有量は、酸発生剤１００質量部に対して、１０～１，０００質量部とすることが、露光部と未露光部との溶解コントラストの観点から好ましく、２０～５００質量部とすることが更に好ましい。 The content of the acid multiplication agent in the photocurable composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the acid generator, from the viewpoint of dissolution contrast between the exposed part and the unexposed part. The amount is preferably 20 to 500 parts by mass.
＜その他の成分＞
　本発明の光硬化性組成物には、架橋系の場合、上記成分に加えて、必要に応じて、増感剤、共増感剤、密着改良剤を好ましく加えることができる。更に、紫外線吸収剤、界面活性剤、現像促進剤、可塑剤、金属不活性化剤や、熱ラジカル発生剤、熱酸発生剤、増粘剤、及び、有機又は無機の沈殿防止剤などの公知の添加剤を加えることができる。
　これらの中で、増感剤、共増感剤、密着改良剤、紫外線吸収剤、界面活性剤、現像促進剤及び可塑剤は、重合系において説明したそれぞれと同様のものを使用することができる。 <Other ingredients>
In the case of a crosslinking system, a sensitizer, a co-sensitizer, and an adhesion improver can be preferably added to the photocurable composition of the present invention, if necessary, in addition to the above components. Furthermore, known UV absorbers, surfactants, development accelerators, plasticizers, metal deactivators, thermal radical generators, thermal acid generators, thickeners, and organic or inorganic precipitation inhibitors Additives can be added.
Among these, sensitizers, co-sensitizers, adhesion improvers, ultraviolet absorbers, surfactants, development accelerators, and plasticizers can be the same as those described in the polymerization system. .
（物性）
＜ヘイズ＞
　本発明の光硬化性組成物を膜厚１μｍに製膜したときのヘイズが２％以下であることが好ましい。ヘイズが２％以下であると透明性に優れる。
　なお、膜厚１μｍに製膜するとは、光硬化性組成物の層を形成し、これを加熱して溶剤を除去し、その後露光硬化した後の膜厚が１μｍであることを意味する。また、露光硬化の後に、更にベ－ク処理がある場合は、ベ－ク処理後の膜厚が１μｍであることを意味する。
　ヘイズは１％以下であることがより好ましく、０．５％以下であることが更に好ましい。ヘイズの下限は特に限定されず、０％以上であればよく、達成可能性の観点から、０．０１％以上であることが好ましく、０．０５％以上であることがより好ましい。 (Physical properties)
<Haze>
The haze when the photocurable composition of the present invention is formed to a film thickness of 1 μm is preferably 2% or less. When the haze is 2% or less, the transparency is excellent.
In addition, forming into a film thickness of 1 micrometer means that the film thickness after forming the layer of a photocurable composition, heating this, removing a solvent, and carrying out exposure hardening after that is 1 micrometer. Further, when there is a baking process after the exposure curing, it means that the film thickness after the baking process is 1 μm.
The haze is more preferably 1% or less, and further preferably 0.5% or less. The lower limit of the haze is not particularly limited and may be 0% or more, and is preferably 0.01% or more and more preferably 0.05% or more from the viewpoint of achievability.
＜屈折率＞
　本発明の光硬化性組成物は、波長５８９ｎｍにおける屈折率が１．６５以上であることが好ましい。屈折率が１．６５以上であると、例えばタッチパネル材料に用いたときに、ＩＴＯのパターン見えの改良効果が見られる。なお、屈折率は、光硬化性組成物の層を形成し、これを加熱して溶剤を除去し、その後露光硬化したものの屈折率を意味する。また、更にベーク処理がある場合は、ベーク処理後の屈折率を意味する。
　屈折率は１．７０以上であることがより好ましく、１．７５以上であることが更に好ましい。
　屈折率の上限は特に限定されないが、２．５０以下であることが好ましく、２．３０以下であることがより好ましく、２．１０以下であることが更に好ましい。 <Refractive index>
The photocurable composition of the present invention preferably has a refractive index of 1.65 or more at a wavelength of 589 nm. When the refractive index is 1.65 or more, for example, when used for a touch panel material, an effect of improving the ITO pattern appearance can be seen. The refractive index means the refractive index of a layer formed by forming a photocurable composition layer, heating it to remove the solvent, and then exposing and curing. Further, when there is a baking process, it means the refractive index after the baking process.
The refractive index is more preferably 1.70 or more, still more preferably 1.75 or more.
The upper limit of the refractive index is not particularly limited, but is preferably 2.50 or less, more preferably 2.30 or less, and even more preferably 2.10 or less.
（硬化膜の製造方法）
　次に、本発明の硬化膜の製造方法を説明する。
　本発明の硬化膜の製造方法は、以下の（１）～（４）の工程を含むことが好ましい。
　（１）本発明の光硬化性組成物を基板上に塗布する塗布工程；
　（２）塗布された組成物から溶剤を除去する溶剤除去工程；
　（３）溶剤が除去された組成物を活性光線によりパターン状に露光する露光工程；
　（４）未露光部の組成物を水性現像液により除去して現像する現像工程。
　また、以下の（５）の工程を含むことが好ましい。
　（５）現像された組成物を熱処理する熱処理工程。
　以下に各工程を順に説明する。 (Method for producing cured film)
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (4).
(1) A coating process for coating the photocurable composition of the present invention on a substrate;
(2) a solvent removal step of removing the solvent from the applied composition;
(3) An exposure step of exposing the composition from which the solvent has been removed to a pattern with actinic rays;
(4) A developing step in which the composition in the unexposed area is removed with an aqueous developer and developed.
Moreover, it is preferable to include the following process (5).
(5) A heat treatment step of heat-treating the developed composition.
Each step will be described below in order.
　（１）の塗布工程では、本発明の光硬化性組成物を基板上に塗布して溶剤を含む湿潤膜とすることが好ましい。光硬化性脂組成物を基板へ塗布する前にアルカリ洗浄やプラズマ洗浄といった基板の洗浄を行うことが好ましく、更に基板洗浄後にヘキサメチルジシラザンで基板表面を処理することがより好ましい。この処理を行うことにより、光硬化性組成物の基板への密着性が向上する。ヘキサメチルジシラザンで基板表面を処理する方法としては、特に限定されないが、例えば、ヘキサメチルジシラザン蒸気に中に基板を晒しておく方法等が挙げられる。
　上記の基板としては、無機基板、樹脂、樹脂複合材料、ＩＴＯ、Ｃｕ基板、ポリエチレンテレフタレート、セルローストリアセテート（ＴＡＣ）などのプラスチック基板が挙げられる。
　無機基板としては、例えばガラス、石英、シリコーン、シリコンナイトライド、及び、それらのような基板上にモリブデン、チタン、アルミ、銅などを蒸着した複合基板が挙げられる。
　樹脂としては、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリスチレン、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリアリレート、アリルジグリコールカーボネート、ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリベンズアゾール、ポリフェニレンサルファイド、ポリシクロオレフィン、ノルボルネン樹脂、ポリクロロトリフルオロエチレン等のフッ素樹脂、液晶ポリマー、アクリル樹脂、エポキシ樹脂、シリコーン樹脂、アイオノマー樹脂、シアネート樹脂、架橋フマル酸ジエステル樹脂、環状ポリオレフィン、芳香族エーテル樹脂、マレイミド－オレフィン樹脂、セルロース、エピスルフィド樹脂等の合成樹脂からなる基板が挙げられる。
　これらの基板は、上記の形態のまま用いられる場合は少なく、最終製品の形態によって、例えばＴＦＴ素子のような多層積層構造が形成されている場合が通常である。
　基板への塗布方法は特に限定されず、例えば、インクジェット法、スリットコート法、スプレー法、ロールコート法、回転塗布法、流延塗布法、スリットアンドスピン法等の方法を用いることができる。更に、特開２００９－１４５３９５号公報に記載されているような、所謂プリウェット法を適用することも可能である。
　塗布膜厚は特に限定されるものではなく、用途に応じた膜厚で塗布することができるが、０．５～１０μｍの範囲で使用されることが好ましい。 In the coating step (1), it is preferable to apply the photocurable composition of the present invention on a substrate to form a wet film containing a solvent. Before applying the photocurable fat composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesion of the photocurable composition to the substrate is improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, resin composite materials, ITO, Cu substrates, polyethylene terephthalate, and plastic substrates such as cellulose triacetate (TAC).
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester resin, cyclic polyolefin, Is it a synthetic resin such as aromatic ether resin, maleimide-olefin resin, cellulose, episulfide resin, etc. A substrate made of, and the like.
These substrates are rarely used in the above-described form, and usually have a multilayer laminated structure such as a TFT element formed depending on the form of the final product.
The coating method on the substrate is not particularly limited, and for example, a method such as an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method 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 μm.
　（２）の溶剤除去工程では、適用された上記の膜から、減圧（バキューム）及び／又は加熱により、溶剤を除去して基板上に乾燥塗膜を形成させる。溶剤除去工程の加熱条件は、好ましくは７０～１３０℃で３０～３００秒間程度である。温度と時間が上記範囲である場合、パターンの密着性が良好で、かつ残渣も低減できる。 (2) In 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.
　（３）の露光工程では、塗膜を設けた基板に所定のパターンを有するマスクを介して、活性光線を照射する。例えば架橋系では、この工程では、酸発生剤が分解し酸が発生する。また、ラジカル系では、重合開始剤からラジカルが発生する。
　活性光線による露光光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ＬＥＤ光源、エキシマレーザー発生装置などを用いることができ、ｇ線（４３６ｎｍ）、ｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）などの波長３００ｎｍ以上４５０ｎｍ以下の波長を有する活性光線が好ましく使用できる。また、必要に応じて長波長カットフィルター、短波長カットフィルター、バンドパスフィルターのような分光フィルターを通して照射光を調整することもできる。
　露光装置としては、ミラープロジェクションアライナー、ステッパー、スキャナー、プロキシミティ、コンタクト、マイクロレンズアレイ、レーザー露光など各種方式の露光機を用いることができる。
　架橋系では、酸触媒の生成した領域において、架橋反応を加速させるために、露光後加熱処理：Post Exposure Bake（以下、「ＰＥＢ」ともいう。）を行うことができる。ＰＥＢにより、より架橋反応を促進することができる。ＰＥＢを行う場合の温度は、３０℃以上１３０℃以下であることが好ましく、４０℃以上１１０℃以下がより好ましく、５０℃以上１００℃以下が特に好ましい。
　ただし、必ずしもＰＥＢを行うことなく、露光によりネガ画像を形成することもできる。 In the exposure step (3), the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. For example, in a crosslinking system, in this step, the acid generator is decomposed to generate an acid. In the radical system, radicals are generated from the polymerization initiator.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used, and 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. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
In the crosslinking system, post-exposure heat treatment (Post Exposure Bake) (hereinafter also referred to as “PEB”) can be performed in order to accelerate the crosslinking reaction in the region where the acid catalyst is generated. PEB can further promote the crosslinking reaction. 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.
However, a negative image can be formed by exposure without necessarily performing PEB.
　（４）の現像工程では、未露光部をアルカリ性現像液を用いて除去することにより現像する。未露光部領域を除去することにより、ネガ画像が形成する。
　現像工程で使用する現像液には、塩基性化合物が含まれることが好ましい。塩基性化合物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物類；炭酸ナトリウム、炭酸カリウム、炭酸セシウムなどのアルカリ金属炭酸塩類；重炭酸ナトリウム、重炭酸カリウムなどのアルカリ金属重炭酸塩類；テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ジエチルジメチルアンモニウムヒドロキシド等のテトラアルキルアンモニウムヒドロキシド類；コリン等の（ヒドロキシアルキル）トリアルキルアンモニウムヒドロキシド類；ケイ酸ナトリウム、メタケイ酸ナトリウムなどのケイ酸塩類；エチルアミン、プロピルアミン、ジエチルアミン、トリエチルアミン等のアルキルアミン類；ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類；１，８－ジアザビシクロ－［５．４．０］－７－ウンデセン、１，５－ジアザビシクロ－［４．３．０］－５－ノネン等の脂環式アミン類を使用することができる。また、上記アルカリ類の水溶液にメタノールやエタノールなどの水溶性有機溶剤や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。
　これらのうち、水酸化ナトリウム、水酸化カリウム、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、コリン（２－ヒドロキシエチルトリメチルアンモニウムヒドロキシド）が好ましい。
　また、上記アルカリ類の水溶液にメタノールやエタノールなどの水溶性有機溶剤や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。
　現像液のｐＨは、好ましくは１０．０～１４．０である。
　現像時間は、好ましくは３０～５００秒間であり、また、現像の手法は液盛り法、ディップ法等のいずれでもよい。現像後は、流水洗浄を３０～３００秒間行い、所望のパターンを形成させることができる。
　現像の後に、リンス工程を行うこともできる。リンス工程では、現像後の基板を純水などで洗うことで、付着している現像液除去、現像残渣除去を行う。リンス方法は公知の方法を用いることができる。例えばシャワーリンスやディップリンスなどを挙げることができる。 In the developing step (4), development is performed by removing an unexposed portion using an alkaline developer. By removing the unexposed area, a negative image is formed.
The developer used in the development step preferably contains a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and diethyldimethylammonium hydroxide; Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as dimethyl alcohol; alcohol amines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] Cycloaliphatic amines such as 5-nonene can be used. 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.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be 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.
　架橋系及び重合系共に、（５）の熱処理工程（ポストベーク）を有することが好ましい。架橋系では、（５）の熱処理工程（ポストベーク）で、得られたネガ画像を加熱することにより、酸基、例えば、カルボキシル基又はフェノール性水酸基を生成させ、架橋性基、架橋剤等と架橋させることにより、更に強固な硬化膜を形成することができる。また、重合系では露光時に反応せずに残った重合性化合物が、熱により重合反応を起こすことにより、更に強固な硬化膜が形成される。この加熱は、ホットプレートやオーブン等の加熱装置を用いて、所定の温度、例えば１８０℃～２５０℃で所定の時間、例えばホットプレート上なら５～９０分間、オーブンならば３０～１２０分間、加熱処理をすることが好ましい。重合反応又は架橋反応を進行させることにより、耐熱性、硬度等に優れた保護膜や層間絶縁膜を形成することができる。また、加熱処理を行う際は窒素雰囲気下で行うことにより透明性を向上させることもできる。プラスチック基板を用いたときは、８０℃～１４０℃で５分～１２０分間、加熱処理をすることが好ましい。
　熱処理工程（ポストベーク）の前に、比較的低温でベークを行った後に熱処理工程を行うこともできる（ミドルベーク工程の追加）。ミドルベークを行う場合は、９０～１５０℃で１～６０分加熱した後に、２００℃以上の高温でポストベークすることが好ましい。また、ミドルベーク、ポストベークを３段階以上の多段階に分けて加熱することもできる。このようなミドルベーク、ポストベークの工夫により、パターンのテーパー角を調整することができる。これらの加熱は、ホットプレート、オーブン、赤外線ヒーターなど、公知の加熱方法を使用することができる。
　なお、ポストベークに先立ち、パターンを形成した基板に活性光線により全面再露光（ポスト露光）した後、ポストベークすることにより露光部分に存在する酸発生剤から酸を発生させ、架橋工程を更に促進する触媒として機能させることができ、膜の硬化反応を促進することができる。ポスト露光工程を含む場合の好ましい露光量としては、１００～３，０００ｍＪ／ｃｍ2が好ましく、１００～５００ｍＪ／ｃｍ2が特に好ましい。 Both the crosslinking system and the polymerization system preferably have the heat treatment step (post bake) of (5). In the cross-linking system, by heating the negative image obtained in the heat treatment step (post-bake) of (5), an acid group, for example, a carboxyl group or a phenolic hydroxyl group is generated, and a crosslinkable group, a crosslinking agent, etc. By crosslinking, a stronger cured film can be formed. Further, in the polymerization system, the polymerizable compound remaining without reacting at the time of exposure causes a polymerization reaction by heat, thereby forming a stronger cured film. 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. It is preferable to process. By proceeding the polymerization reaction or the crosslinking reaction, a protective film and an interlayer insulating film excellent in heat resistance, hardness, etc. can be formed. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere. When a plastic substrate is used, heat treatment is preferably performed at 80 to 140 ° C. for 5 to 120 minutes.
Prior to the heat treatment step (post-bake), the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step). When middle baking is performed, 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. Further, middle baking and post baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate is re-exposed with actinic rays (post-exposure) and post-baked to generate acid from the acid generator present in the exposed area, further accelerating the crosslinking process. It can function as a catalyst that promotes the film curing reaction. 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.
　更に、本発明の光硬化性組成物より得られた硬化膜は、ドライエッチングレジストとして使用することもできる。硬化膜をドライエッチングレジストとして使用する場合、エッチング処理としてはアッシング、プラズマエッチング、オゾンエッチングなどのドライエッチング処理を行うことができる。 Furthermore, the cured film obtained from the photocurable composition of the present invention can also be used as a dry etching resist. When the cured film is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
（硬化膜）
　本発明の硬化膜は、本発明の光硬化性組成物を硬化して得られた硬化膜である。
　本発明の硬化膜は、層間絶縁膜として好適に用いることができる。また、本発明の硬化膜は、本発明の硬化膜の形成方法により得られた硬化膜であることが好ましい。
　本発明の光硬化性組成物により、絶縁性に優れ、高温でベークされた場合においても高い透明性を有する層間絶縁膜が得られる。本発明の光硬化性組成物を用いてなる層間絶縁膜は、高い透明性を有し、硬化膜物性に優れるため、有機ＥＬ表示装置や液晶表示装置の用途に有用である。 (Cured film)
The cured film of the present invention is a cured film obtained by curing the photocurable composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
With the photocurable composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at a high temperature can be obtained. The interlayer insulating film formed using the photocurable composition of the present invention has high transparency and excellent cured film properties, and thus is useful for applications of organic EL display devices and liquid crystal display devices.
（硬化物及びその製造方法）
　本発明の硬化物は、本発明の光硬化性組成物を硬化して得られた硬化物であり、上記のように、その形状は、膜でなくともよく、任意の形状であればよい。
　本発明の硬化物の製造方法は、特に制限はないが、少なくとも以下の工程（ａ）～（ｃ）をこの順に含むことが好ましい。
　（ａ）本発明の光硬化性組成物を基板上に塗布する塗布工程；
　（ｂ）塗布された組成物から溶剤を除去する溶剤除去工程；
　（ｃ）溶剤が除去された組成物に活性光線を照射する露光工程。 (Hardened product and manufacturing method thereof)
The hardened | cured material of this invention is a hardened | cured material obtained by hardening | curing the photocurable composition of this invention, As mentioned above, the shape does not need to be a film | membrane, What is necessary is just arbitrary shapes.
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.
(A) A coating step of coating the photocurable composition of the present invention on a substrate;
(B) a solvent removal step of removing the solvent from the applied composition;
(C) An exposure step of irradiating the composition from which the solvent has been removed with actinic rays.
　工程（ａ）及び工程（ｂ）はそれぞれ、上記塗布工程及び上記溶剤除去工程と同義であり、好ましい態様も同様である。
　工程（ｃ）は、上記露光工程と同様の工程であり、好ましい態様も同様である。 Process (a) and process (b) are synonymous with the said application | coating process and the said solvent removal process, respectively, A preferable aspect is also the same.
Step (c) is the same step as the above exposure step, and the preferred embodiment is also the same.
　本発明の硬化物又は硬化膜は、マイクロレンズ、光導波路、反射防止膜、ＬＥＤ用封止材及びＬＥＤ用チップコート材等の光学部材、又は、タッチパネルに使用される配線電極の視認性低減用硬化物として好適に用いることができる。
　また、本発明の硬化物又は硬化膜は、例えば、後述するような、液晶表示装置又は有機ＥＬ装置等における平坦化膜や層間絶縁膜、カラーフィルターの保護膜、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサー、ＭＥＭＳ（Micro Electro Mechanical Systems）デバイスの構造部材等に好適に用いることができる。 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. Can be suitably used for spacers for holding the substrate constant, structural members of MEMS (Micro Electro Mechanical Systems) devices, and the like.
（液晶表示装置）
　本発明の液晶表示装置は、本発明の硬化膜を具備することを特徴とする。
　本発明の液晶表示装置としては、本発明の光硬化性組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の液晶表示装置を挙げることができる。
　例えば、本発明の液晶表示装置が具備するＴＦＴ（Thin-Film Transistor）の具体例としては、アモルファスシリコン－ＴＦＴ、低温ポリシリコン－ＴＦＴ、酸化物半導体ＴＦＴ等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのＴＦＴに組み合わせて好ましく用いることができる。
　また、本発明の液晶表示装置が取りうる液晶駆動方式としてはＴＮ（Twisted Nematic）方式、ＶＡ（Virtical Alignment）方式、ＩＰＳ（In-Place-Switching）方式、ＦＦＳ（Frings Field Switching）方式、ＯＣＢ（Optical Compensated Bend）方式などが挙げられる。
　パネル構成においては、ＣＯＡ（Color Filter on Allay）方式の液晶表示装置でも本発明の硬化膜を用いることができ、例えば、特開２００５－２８４２９１号公報に記載の有機絶縁膜（１１５）や、特開２００５－３４６０５４号公報に記載の有機絶縁膜（２１２）として用いることができる。
　また、本発明の液晶表示装置が取りうる液晶配向膜の具体的な配向方式としてはラビング配向法、光配向方などが挙げられる。また、特開２００３－１４９６４７号公報や特開２０１１－２５７７３４号公報に記載のＰＳＡ（Polymer Sustained Alignment）技術によってポリマー配向支持されていてもよい。
　また、本発明の光硬化性組成物及び本発明の硬化膜は、上記用途に限定されず種々の用途に使用することができる。例えば、平坦化膜や層間絶縁膜以外にも、カラーフィルターの保護膜や、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや固体撮像素子においてカラーフィルター上に設けられるマイクロレンズ等に好適に用いることができる。 (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 flattening film or an interlayer insulating film formed using the photocurable composition of the present invention, and known liquid crystal display devices having various structures. Can be mentioned.
For example, 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.
Further, 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.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Allay) type liquid crystal display device. For example, 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.
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in Japanese Patent Application Laid-Open Nos. 2003-149647 and 2011-257734.
Moreover, the photocurable composition of this invention and the cured film of this invention are not limited to the said use, but can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
　図１は、アクティブマトリックス方式の液晶表示装置１０の一例を示す概念的断面図である。このカラー液晶表示装置１０は、背面にバックライトユニット１２を有する液晶パネルであって、液晶パネルは、偏光フィルムが貼り付けられた２枚のガラス基板１４，１５の間に配置されたすべての画素に対応するＴＦＴ１６の素子が配置されている。ガラス基板上に形成された各素子には、硬化膜１７中に形成されたコンタクトホール１８を通して、画素電極を形成するＩＴＯ透明電極１９が配線されている。ＩＴＯ透明電極１９の上には、液晶２０の層とブラックマトリックスを配置したＲＧＢカラーフィルター２２が設けられている。
　バックライトの光源としては、特に限定されず公知の光源を用いることができる。例えば白色ＬＥＤ、青色・赤色・緑色などの多色ＬＥＤ、蛍光灯（冷陰極管）、有機ＥＬなどを挙げることができる。
　また、液晶表示装置は、３Ｄ（立体視）型のものとしたり、タッチパネル型のものとしたりすることも可能である。更にフレキシブル型にすることも可能であり、特開２０１１－１４５６８６号公報に記載の第２相間絶縁膜（４８）や、特開２００９－２５８７５８号公報に記載の相間絶縁膜（５２０）として用いることができる。 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. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, 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.
（有機ＥＬ表示装置）
　本発明の有機ＥＬ表示装置は、本発明の硬化膜を具備することを特徴とする。
　本発明の有機ＥＬ表示装置としては、本発明の光硬化性組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の各種有機ＥＬ表示装置や液晶表示装置を挙げることができる。
　例えば、本発明の有機ＥＬ表示装置が具備するＴＦＴ（Thin-Film Transistor）の具体例としては、アモルファスシリコン－ＴＦＴ、低温ポリシリコン－ＴＦＴ、酸化物半導体ＴＦＴ等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのＴＦＴに組み合わせて好ましく用いることができる。
　図２は、有機ＥＬ表示装置の一例の構成概念図である。ボトムエミッション型の有機ＥＬ表示装置における基板の模式的断面図を示し、平坦化膜４を有している。
　ガラス基板６上にボトムゲート型のＴＦＴ１を形成し、このＴＦＴ１を覆う状態でＳｉ3Ｎ4から成る絶縁膜３が形成されている。絶縁膜３に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してＴＦＴ１に接続される配線２（高さ１．０μｍ）が絶縁膜３上に形成されている。配線２は、ＴＦＴ１間、又は、後の工程で形成される有機ＥＬ素子とＴＦＴ１とを接続するためのものである。
　更に、配線２の形成による凹凸を平坦化するために、配線２による凹凸を埋め込む状態で絶縁膜３上に平坦化層４が形成されている。
　平坦化膜４上には、ボトムエミッション型の有機ＥＬ素子が形成されている。すなわち、平坦化膜４上に、ＩＴＯからなる第一電極５が、コンタクトホール７を介して配線２に接続させて形成されている。また、第一電極５は、有機ＥＬ素子の陽極に相当する。
　第一電極５の周縁を覆う形状の絶縁膜８が形成されており、この絶縁膜８を設けることによって、第一電極５とこの後の工程で形成する第二電極との間のショートを防止することができる。
　更に、図２には図示していないが、所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設け、次いで、基板上方の全面にＡｌから成る第二電極を形成し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止し、各有機ＥＬ素子にこれを駆動するためのＴＦＴ１が接続されてなるアクティブマトリックス型の有機ＥＬ表示装置が得られる。 (Organic EL display device)
The organic EL display device of the present invention 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 photocurable composition of the present invention, and various known organic materials having various structures. An EL display device and a liquid crystal display device can be given.
For example, specific examples of 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 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.
　本発明の光硬化性組成物は、硬化性及び硬化膜特性に優れるため、ＭＥＭＳデバイスの構造部材として、本発明の光硬化性組成物を用いて形成されたレジストパターンを隔壁としたり、機械駆動部品の一部として組み込んで使用される。このようなＭＥＭＳ用デバイスとしては、例えば、ＳＡＷ（surface acoustic wave）フィルター、ＢＡＷ（bulk acoustic wave）フィルター、ジャイロセンサー、ディスプレイ用マイクロシャッター、イメージセンサー、電子ペーパー、インクジェットヘッド、バイオチップ、封止剤等の部品が挙げられる。より具体的な例は、特表２００７－５２２５３１号公報、特開２００８－２５０２００号公報、特開２００９－２６３５４４号公報等に例示されている。 Since the photocurable composition of the present invention is excellent in curability and cured film properties, a resist pattern formed using the photocurable composition of the present invention as a partition as a structural member of a MEMS device, or a mechanical drive Used as part of the part. Such 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.
　本発明の光硬化性組成物は、平坦性や透明性に優れるため、例えば、特開２０１１－１０７４７６号公報の図２に記載のバンク層（１６）及び平坦化膜（５７）、特開２０１０－９７９３号公報の図４（ａ）に記載の隔壁（１２）及び平坦化膜（１０２）、特開２０１０－２７５９１号公報の図１０に記載のバンク層（２２１）及び第３層間絶縁膜（２１６ｂ）、特開２００９－１２８５７７号公報の図４（ａ）に記載の第２層間絶縁膜（１２５）及び第３層間絶縁膜（１２６）、特開２０１０－１８２６３８号公報の図３に記載の平坦化膜（１２）及び画素分離絶縁膜（１４）などの形成に用いることもできる。この他、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや、ファクシミリ、電子複写機、固体撮像素子等のオンチップカラーフィルターの結像光学系あるいは光ファイバコネクタのマイクロレンズにも好適に用いることができる。 Since the photocurable 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) described 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. 4 (a) of JP2009-128577A, and described in FIG. 3 of JP2010-182638A. It can also be used to form a planarization film (12), a pixel isolation insulating film (14), and the like. In addition, spacers for maintaining the thickness of the liquid crystal layer in a liquid crystal display device, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.
　また、本発明の光硬化性組成物は、透明性や屈折率に優れるため、マイクロレンズやプリズム用の部材、光取り出し用の部材として好適に使用される。例えば、ディスプレイ用のフラットパネルの、バックライトユニット中で用いられる、プリズム用の部材やプリズムと導光板との接合用の部材として用いることができる。また、例えば、有機ＥＬディスプレイの光取り出し効率の改善用の部材としても用いることができる。 Further, since the photocurable composition of the present invention is excellent in transparency and refractive index, it is suitably used as a member for microlenses and prisms and a member for extracting light. For example, it can be used as a prism member or a member for joining a prism and a light guide plate used in a backlight unit of a flat panel for display. For example, it can be used as a member for improving the light extraction efficiency of an organic EL display.
（タッチパネル表示装置）
　本発明のタッチパネル表示装置は、本発明の硬化膜を有する静電容量型入力装置を具備する。また、本発明の静電容量型入力装置は、本発明の硬化膜を有することを特徴とする。
　本発明の静電容量型入力装置は、前面板と、上記前面板の非接触側に、少なくとも下記（１）～（５）の要素を有し、下記（４）が本発明の硬化物であることが好ましい。
　（１）マスク層
　（２）複数のパッド部分が接続部分を介して第一の方向に延在して形成された複数の第一の透明電極パターン
　（３）上記第一の透明電極パターンと電気的に絶縁され、上記第一の方向に交差する方向に延在して形成された複数のパッド部分からなる複数の第二の透明電極パターン
　（４）上記第一の透明電極パターンと上記第二の透明電極パターンとを電気的に絶縁する絶縁層
　（５）上記第一の透明電極パターン及び上記第二の透明電極パターンの少なくとも一方に電気的に接続され、上記第一の透明電極パターン及び上記第二の透明電極パターンとは別の導電性要素
　本発明の静電容量型入力装置は、更に上記（１）～（５）の要素の全て又は一部を覆うように透明保護層を設置することが好ましく、上記透明保護層が本発明の硬化膜であることがより好ましい。 (Touch panel display)
The touch panel display device of the present invention includes a capacitive input device having the cured film of the present invention. Moreover, the capacitance-type input device of the present invention has the cured 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, and the following (4) is the cured 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. (4) The first transparent electrode pattern and the second An insulating layer that electrically insulates the transparent electrode pattern of (5) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and the first transparent electrode pattern and the above Conductive element different from the second transparent electrode pattern In the capacitive input device of the present invention, 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.
　まず、静電容量型入力装置の構成について説明する。図３は、静電容量型入力装置の構成を示す断面図である。図３において静電容量型入力装置３０は、前面板３１と、マスク層３２と、第一の透明電極パターン３３と、第二の透明電極パターン３４と、絶縁層３５と、導電性要素３６と、透明保護層３７と、から構成されている。 First, the configuration of the capacitive input device will be described. FIG. 3 is a cross-sectional view showing the configuration of the capacitive input device. In FIG. 3, 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.
　前面板３１は、ガラス基板等の透光性基板で構成されており、コーニング社のゴリラガラスに代表される強化ガラスなどを用いることができる。また、図３において、前面板３１の各要素が設けられている側を非接触面と称する。本発明の静電容量型入力装置３０においては、前面板３１の接触面（非接触面の反対の面）に指などを接触などさせて入力が行われる。以下、前面板を、「基材」と称する場合がある。 The front plate 31 is 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. Hereinafter, the front plate may be referred to as a “base material”.
　また、前面板３１の非接触面上にはマスク層３２が設けられている。マスク層３２は、タッチパネル前面板の非接触側に形成された表示領域周囲の額縁状のパターンであり、引回し配線等が見えないようにするために形成される。
　本発明の静電容量型入力装置には、図４に示すように、前面板３１の一部の領域（図４においては入力面以外の領域）を覆うようにマスク層３２が設けられている。更に、前面板３１には、図４に示すように一部に開口部３８を設けることができる。開口部３８には、押圧によるメカニカルなスイッチを設置することができる。 A 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.
In the capacitive input device of the present invention, as shown in FIG. 4, 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). . Further, 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.
　図５に示すように、前面板３１の接触面には、複数のパッド部分が接続部分を介して第一の方向に延在して形成された複数の第一の透明電極パターン３３と、第一の透明電極パターン３３と電気的に絶縁され、第一の方向に交差する方向に延在して形成された複数のパッド部分からなる複数の第二の透明電極パターン３４と、第一の透明電極パターン３３と第二の透明電極パターン３４を電気的に絶縁する絶縁層３５とが形成されている。上記第一の透明電極パターン３３と、第二の透明電極パターン３４と、後述する導電性要素３６とは、例えば、ＩＴＯ（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ）やＩＺＯ（Ｉｎｄｉｕｍ　Ｚｉｎｃ　Ｏｘｉｄｅ）などの透光性の導電性金属酸化膜で作製することができる。このような金属膜としては、ＩＴＯ膜；Ａｌ、Ｚｎ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｏ等の金属膜；ＳｉＯ2等の金属酸化膜などが挙げられる。この際、各要素の、膜厚は１０～２００ｎｍとすることができる。また、焼成により、アモルファスのＩＴＯ膜を多結晶のＩＴＯ膜とするため、電気的抵抗を低減することもできる。また、上記第一の透明電極パターン３３と、第二の透明電極パターン３４と、後述する導電性要素３６とは、上記導電性繊維を用いた光硬化性組成物を有する光硬化性転写材料を用いて製造することもできる。その他、ＩＴＯ等によって第一の導電性パターン等を形成する場合には、特許第４５０６７８５号公報の段落［００１４］～［００１６］等を参考にすることができる。 As shown in FIG. 5, on the contact surface of the front plate 31, a plurality of first transparent electrode patterns 33 formed with a plurality of pad portions extending in the first direction via the connection portions, A plurality of second transparent electrode patterns 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. Examples of such metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO 2 . At this time, the film thickness of each element can be set to 10 to 200 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced. In addition, the first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36, which will be described later, are a photocurable transfer material having a photocurable composition using the conductive fibers. It can also be manufactured. In addition, when the first conductive pattern or the like is formed of ITO or the like, paragraphs [0014] to [0016] of Japanese Patent No. 4506785 can be referred to.
　また、第一の透明電極パターン３３及び第二の透明電極パターン３４の少なくとも一方は、前面板３１の非接触面及びマスク層３２の前面板３１とは逆側の面の両方の領域にまたがって設置することができる。図３においては、第二の透明電極パターンが、前面板３１の非接触面及びマスク層３２の前面板３１とは逆側の面の両方の領域にまたがって設置されている図が示されている。 In addition, 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. In 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.
　図５を用いて第一の透明電極パターン３３及び第二の透明電極パターン３４について説明する。図５は、本発明における第一の透明電極パターン及び第二の透明電極パターンの一例を示す説明図である。図５に示すように、第一の透明電極パターン３３は、パッド部分３３ａが接続部分３３ｂを介して第一の方向に延在して形成されている。また、第二の透明電極パターン３４は、第一の透明電極パターン３３と絶縁層３５によって電気的に絶縁されており、第一の方向に交差する方向（図５における第二の方向）に延在して形成された複数のパッド部分によって構成されている。ここで、第一の透明電極パターン３３を形成する場合、上記パッド部分３３ａと接続部分３３ｂとを一体として作製してもよいし、接続部分３３ｂのみを作製して、パッド部分３３ａと第二の透明電極パターン３４とを一体として作製（パターニング）してもよい。パッド部分３３ａと第二の透明電極パターン３４とを一体として作製（パターニング）する場合、図５に示すように接続部分３３ｂの一部とパッド部分３３ａの一部とが連結され、かつ、絶縁層３５によって第一の透明電極パターン３３と第二の透明電極パターン３４とが電気的に絶縁されるように各層が形成される。 The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. FIG. 5 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention. As shown in FIG. 5, 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. Here, when the first transparent electrode pattern 33 is 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). When 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.
　図３において、マスク層３２の前面板３１とは逆側の面側には導電性要素３６が設置されている。導電性要素３６は、第一の透明電極パターン３３及び第二の透明電極パターン３４の少なくとも一方に電気的に接続され、かつ、第一の透明電極パターン３３及び第二の透明電極パターン３４とは別の要素である。図３においては、導電性要素３６が第二の透明電極パターン３４に接続されている図が示されている。 In FIG. 3, 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. In FIG. 3, a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.
　また、図３においては、各構成要素の全てを覆うように透明保護層３７が設置されているが、透明保護層３７は、各構成要素の一部のみを覆うように構成されていてもよい。絶縁層３５と透明保護層３７とは、同一材料であってもよいし、異なる材料であってもよい。 In FIG. 3, the transparent protective layer 37 is provided so as to cover all of the components, but the transparent protective layer 37 may be configured to cover only a part of the components. . The insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.
＜静電容量型入力装置、及び、静電容量型入力装置を具備したタッチパネル表示装置＞
　本発明の製造方法によって得られる静電容量型入力装置、及び当該静電容量型入力装置を構成要素として備えたタッチパネル表示装置は、『最新タッチパネル技術』（２００９年７月６日発行（株）テクノタイムズ）、三谷雄二監修、“タッチパネルの技術と開発”、シーエムシー出版（２００４，１２）、ＦＰＤ　Ｉｎｔｅｒｎａｔｉｏｎａｌ　２００９　Ｆｏｒｕｍ　Ｔ－１１講演テキストブック、Ｃｙｐｒｅｓｓ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ　Ｃｏｒｐｏｒａｔｉｏｎ　アプリケーションノートＡＮ２２９２等に開示されている構成を適用することができる。 <Capacitance type input device and touch panel display device provided with capacitance type input device>
The capacitive input device obtained by the manufacturing method of the present invention and the touch panel display device including the capacitive input device as a constituent element are “latest touch panel technology” (issued July 6, 2009). 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.
（転写材料）
　次に、本発明の転写材料について説明する。転写材料は、支持体（仮支持体）上に設けた硬化性樹脂層を最終的な基体上に貼付し、支持体（仮支持体）を剥がし、硬化性樹脂層を画像により露光し、現像するものである。
　本発明の転写材料は、特開平５－７２７２４号公報に記載されている転写材料、すなわち一体型となったフイルムを用いて形成することが好ましい。一体型フイルムの構成の例としては、支持体（仮支持体）／熱可塑性樹脂層／中間層／硬化性樹脂層／保護フイルムを、この順に積層した構成が挙げられるがこれに限定されず、支持体上に少なくとも本発明の光硬化性組成物を少なくとも１層製膜させていればよい。すなわち、本発明の転写材料は、前述の本発明の光硬化性組成物を用いることによって光硬化性層を設けることが必須である。なお、光硬化性組成物よりなる層を設け、必要に応じて溶剤を除去することによって、製膜することができる。 (Transfer material)
Next, the transfer material of the present invention will be described. For the transfer material, a curable resin layer provided on a support (temporary support) is pasted on the final substrate, the support (temporary support) is peeled off, the curable resin layer is exposed with an image, and developed. To do.
The transfer material of the present invention is preferably formed using the transfer material described in JP-A-5-72724, that is, an integral film. Examples of the structure of the integral film include a structure in which a support (temporary support) / thermoplastic resin layer / intermediate layer / curable resin layer / protective film is laminated in this order, but is not limited thereto. It is sufficient that at least one layer of the photocurable composition of the present invention is formed on the support. That is, it is essential for the transfer material of the present invention to provide a photocurable layer by using the above-described photocurable composition of the present invention. In addition, it can form into a film by providing the layer which consists of a photocurable composition, and removing a solvent as needed.
＜支持体（仮支持体）＞
　本発明において仮支持体としては、可撓性を有し、加圧若しくは加圧及び加熱下においても著しい変形、収縮若しくは伸びを生じないことが必要である。そのような支持体の例としては、ポリエチレンテレフタレートフィルム、トリ酢酸セルロースフィルム、ポリスチレンフィルム、ポリカーボネートフィルム等を挙げることができ、中でも２軸延伸ポリエチレンテレフタレートフィルムが特に好ましい。 <Support (temporary support)>
In the present invention, the temporary support is required to be flexible and not to cause significant deformation, shrinkage or elongation even under pressure or pressure and heating. Examples of such a support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.
＜熱可塑性樹脂層＞
　熱可塑性樹脂層に用いる成分としては、特開平５－７２７２４号公報に記載されている有機高分子物質が好ましく、ヴイカーＶｉｃａｔ法（具体的にはアメリカ材料試験法エーエステーエムデーＡＳＴＭＤ１２３５によるポリマー軟化点測定法）による軟化点が約８０℃以下の有機高分子物質より選ばれることが特に好ましい。具体的には、ポリエチレン、ポリプロピレンなどのポリオレフィン、エチレンと酢酸ビニルあるいはそのケン化物のようなエチレン共重合体、エチレンとアクリル酸エステルあるいはそのケン化物、ポリ塩化ビニル、塩化ビニルと酢酸ビニル及びそのケン化物のような塩化ビニル共重合体、ポリ塩化ビニリデン、塩化ビニリデン共重合体、ポリスチレン、スチレンと（メタ）アクリル酸エステルあるいはそのケン化物のようなスチレン共重合体、ポリビニルトルエン、ビニルトルエンと（メタ）アクリル酸エステルあるいはそのケン化物のようなビニルトルエン共重合体、ポリ（メタ）アクリル酸エステル、（メタ）アクリル酸ブチルと酢酸ビニル等の（メタ）アクリル酸エステル共重合体、酢酸ビニル共重合体ナイロン、共重合ナイロン、Ｎ－アルコキシメチル化ナイロン、Ｎ－ジメチルアミノ化ナイロンのようなポリアミド樹脂等の有機高分子が挙げられる。なお、熱可塑性樹脂層の乾燥厚さは、２～３０μｍが好ましく、５～２０μｍがより好ましく、７～１６μｍが更に好ましい。 <Thermoplastic resin layer>
The component used in the thermoplastic resin layer is preferably an organic polymer substance described in JP-A-5-72724, and is a polymer softening point according to the Viker Vicat method (specifically, American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferred that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer United nylon, copolymer nylon, - alkoxymethyl nylon, and organic polymers of the polyamide resin such as N- dimethylamino nylon. The dry thickness of the thermoplastic resin layer is preferably 2 to 30 μm, more preferably 5 to 20 μm, and even more preferably 7 to 16 μm.
＜中間層＞
　本発明の転写材料においては、複数の塗布層の塗布時、及び塗布後の保存時における成分の混合を防止する目的から、中間層を設けることが好ましい。中間層としては、特開平５－７２７２４号公報に「分離層」として記載されている、酸素遮断機能のある酸素遮断膜を用いることが好ましく、この場合、露光時感度がアップし、露光機の時間負荷が減り、生産性が向上する。
　酸素遮断膜としては、低い酸素透過性を示し、水又はアルカリ水溶液に分散又は溶解するものが好ましく、公知のものの中から適宜選択することができる。これらのうち、特に好ましいのは、ポリビニルアルコールとポリビニルピロリドンとの組み合わせである。なお、中間層の乾燥厚さは、０．２～５μｍが好ましく、０．５～３μｍがより好ましく、１～２．５μｍが更に好ましい。 <Intermediate layer>
In the transfer material of the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. Time load is reduced and productivity is improved.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Of these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable. The dry thickness of the intermediate layer is preferably 0.2 to 5 μm, more preferably 0.5 to 3 μm, and even more preferably 1 to 2.5 μm.
＜保護フイルム＞
　硬化性樹脂層の上には、貯蔵の際の汚染や損傷から保護するために薄い保護フイルムを設けることが好ましい。保護フイルムは仮支持体と同じか又は類似の材料からなってもよいが、硬化性樹脂層から容易に分離されねばならない。保護フイルム材料としては例えばシリコーン紙、ポリオレフィン若しくはポリテトラフルオロエチレンシートが適当である。なお、保護フイルムの厚さは、４～４０μｍが好ましく、５～３０μｍがより好ましく、１０～２５μｍが更に好ましい。 <Protective film>
It is preferable to provide a thin protective film on the curable resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the curable resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material. The thickness of the protective film is preferably 4 to 40 μm, more preferably 5 to 30 μm, and still more preferably 10 to 25 μm.
＜転写材料の作製方法＞
　本発明の転写材料は、仮支持体上に熱可塑性樹脂層の添加剤を溶解した塗布液（熱可塑性樹脂層用塗布液）を塗布し、乾燥することにより熱可塑性樹脂層を設け、その後熱可塑性樹脂層上に熱可塑性樹脂層を溶解しない溶剤からなる中間層材料の溶液を塗布、乾燥し、その後硬化性樹脂層を、中間層を溶解しない溶剤で塗布、乾燥して設けることにより作製することができる。
　また、上記の仮支持体上に熱可塑性樹脂層及び中間層を設けたシート、及び保護フイルム上に硬化性樹脂層を設けたシートを用意し、中間層と硬化性樹脂層が接するように相互に貼り合わせることによっても、更には、上記の仮支持体上に熱可塑性樹脂層を設けたシート、及び保護フイルム上に硬化性樹脂層及び中間層を設けたシートを用意し、熱可塑性樹脂層と中間層が接するように相互に貼り合わせることによっても、作製することができる。
　なお、上記作製方法における塗布は、公知の塗布装置等によって行うことができる。 <Method for producing transfer material>
The transfer material of the present invention is provided with a thermoplastic resin layer by applying a coating solution (a coating solution for a thermoplastic resin layer) in which a thermoplastic resin layer additive is dissolved on a temporary support, followed by drying. An intermediate layer material solution made of a solvent that does not dissolve the thermoplastic resin layer is applied on the plastic resin layer, dried, and then the curable resin layer is applied by applying a solvent that does not dissolve the intermediate layer and then dried. be able to.
In addition, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the curable resin layer on the protective film are prepared, and the intermediate layer and the curable resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a curable resin layer and an intermediate layer on a protective film are prepared, and a thermoplastic resin layer is prepared. It can also be produced by sticking them together so that the intermediate layer is in contact with it.
Note that the coating in the above production method can be performed by a known coating apparatus or the like.
　以下に実施例を挙げて本発明を更に具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。なお、特に断りのない限り、「部」、「％」は質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.
　以下の実施例において、以下の符号はそれぞれ以下の化合物を表す。
（２つ以上の窒素原子を有する複素環化合物） In the following examples, the following symbols represent the following compounds, respectively.
(Heterocyclic compound having two or more nitrogen atoms)
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
－比較化合物Ｈ－１～Ｈ－３－ Comparative compounds H-1 to H-3-
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
（金属酸化物粒子）
　ＴＴＯ－５１（Ｃ）：二酸化チタン（表面処理：Ａｌ（ＯＨ）3／ステアリン酸、平均一次粒径：１０～３０ｎｍ）、石原産業（株）製
　ＴＴＯ－５１（Ａ）：二酸化チタン（表面処理：Ａｌ（ＯＨ）3、平均一次粒径：１０～３０ｎｍ）、石原産業（株）製 (Metal oxide particles)
TTO-51 (C): Titanium dioxide (surface treatment: Al (OH) 3 / stearic acid, average primary particle size: 10 to 30 nm), manufactured by Ishihara Sangyo Co., Ltd. TTO-51 (A): Titanium dioxide (surface treatment) : Al (OH) 3 , average primary particle size: 10 to 30 nm), manufactured by Ishihara Sangyo Co., Ltd.
（分散剤）
　ＤＩＳＰＥＲＢＹＫ－１１１：ビックケミー・ジャパン製
　ＤＩＳＰＥＲＢＹＫ－２００１：ビックケミー・ジャパン製
　ソルスパース４１０００：日本ルーブリゾール社製
　化合物１：下記構造の化合物（重量平均分子量３，３００）のＰＧＭＥＡ３０％溶液 (Dispersant)
DISPERBYK-111: manufactured by Big Chemie Japan DISPERBYK-2001: manufactured by Big Chemie Japan Solsperse 41000: manufactured by Nihon Lubrizol Corporation Compound 1: PGMEA 30% solution of a compound having the following structure (weight average molecular weight 3,300)
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
　化合物２：下記構造の化合物（重量平均分子量３，０００）のＰＧＭＥＡ３０％溶液 Compound 2: PGMEA 30% solution of a compound having the following structure (weight average molecular weight 3,000)
Figure JPOXMLDOC01-appb-C000058
 　化合物２中、Ｐ１：Ｐ２（質量比）＝９８：２である。
Figure JPOXMLDOC01-appb-C000058
 In Compound 2, P1: P2 (mass ratio) = 98: 2.
（重合性化合物）
　モノマー（Ｍ－１）：ジペンタエリスリトールヘキサアクリレート
　モノマー（Ｍ－２）：ＮＫエステルＡ－ＢＰＥＦ（９，９－ビス［４－（２－アクリロイルオキシエトキシ）フェニル］フルオレン、新中村化学（株）製）
　モノマー（Ｍ－３）：トリス（２－アクリロイロキシエチル）ホスフェート (Polymerizable compound)
Monomer (M-1): Dipentaerythritol hexaacrylate Monomer (M-2): NK ester A-BPEF (9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, Shin-Nakamura Chemical Co., Ltd. Made)
Monomer (M-3): Tris (2-acryloyloxyethyl) phosphate
（光重合開始剤）
　Ｉ－１:Ｉｒｇａｃｕｒｅ　ＯＸＥ　０１（下記構造、ＢＡＳＦ製） (Photopolymerization initiator)
I-1: Irgacure OXE 01 (the following structure, manufactured by BASF)
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
（架橋剤）
　架橋剤（Ｋ－１）：ニカラック　ＭＷ－１００ＬＭ（下記構造、三和ケミカル（株）製） (Crosslinking agent)
Cross-linking agent (K-1): Nicalak MW-100LM (the following structure, manufactured by Sanwa Chemical Co., Ltd.)
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
（酸発生剤）
　Ｂ－１：下記構造で表される光酸発生剤 (Acid generator)
B-1: Photoacid generator represented by the following structure
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
（ポリマー）
　ポリマー（Ｐ－１）：下記ポリマー（重量平均分子量３０，０００）のＰＧＭＥＡ３０ｗｔ％溶液（なお、下記の重合比は、モル比を意味する。） (polymer)
Polymer (P-1): PGMEA 30 wt% solution of the following polymer (weight average molecular weight 30,000) (The following polymerization ratio means molar ratio.)
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
　ポリマー（Ｐ－２）：下記ポリマー（重量平均分子量３０，０００）のＰＧＭＥＡ３０ｗｔ％溶液 Polymer (P-2): PGMEA 30 wt% solution of the following polymer (weight average molecular weight 30,000)
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
　ポリマー（Ｐ－３）：下記の方法で合成したポリマー（重量平均分子量１７，５００、ＰＧＭＥＡ３１ｗｔ％溶液）
＜合成法＞
　冷却管、撹拌機を備えたフラスコに、２，２’－アゾビス（２，４－ジメチルバレロニトリル）７質量部、プロピレングリコールモノメチルエーテルアセテート２２０質量部を仕込み、引き続きメタクリル酸２５質量部、ジシクロペンタニルメタクリレート３５質量部、β－メチルグリシジルメタクリレート４０質量部、α－メチルスチレンダイマー１．５質量部を仕込んで、窒素置換しながら緩やかに撹拌を始めた。その後反応溶液の温度を７０℃に上昇させ、この温度にて５時間重合することにより、共重合体を含む固形分濃度３１．２質量％の重合体溶液を得た。 Polymer (P-3): polymer synthesized by the following method (weight average molecular weight 17,500, PGMEA 31 wt% solution)
<Synthesis method>
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of propylene glycol monomethyl ether acetate, followed by 25 parts by mass of methacrylic acid, dicyclo 35 parts by mass of pentanyl methacrylate, 40 parts by mass of β-methylglycidyl methacrylate, and 1.5 parts by mass of α-methylstyrene dimer were charged, and gently stirring was started while replacing with nitrogen. Thereafter, the temperature of the reaction solution was raised to 70 ° C., and polymerization was carried out at this temperature for 5 hours to obtain a polymer solution containing a copolymer and having a solid content concentration of 31.2% by mass.
　ポリマー（Ｐ－４）：マルカリンカーＭ（ポリヒドロキシスチレン、重量平均分子量１８，０００、丸善化学（株）製）のＰＧＭＥＡ４０ｗｔ％溶液
　ポリマー（Ｐ－５）：ＰＲ５４０４６（ノボラック樹脂、ｍ－クレゾール／ｐ－クレゾール＝６０／４０、住友デュレス（株）製）のＰＧＭＥＡ４０ｗｔ％溶液 Polymer (P-4): PGMEA 40 wt% solution of Marcalinker M (polyhydroxystyrene, weight average molecular weight 18,000, manufactured by Maruzen Chemical Co., Ltd.) Polymer (P-5): PR54046 (novolak resin, m-cresol / p -Cresol = 60/40, manufactured by Sumitomo Durres Co., Ltd.) PGMEA 40 wt% solution
（溶剤）
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート (solvent)
PGMEA: Propylene glycol monomethyl ether acetate
＜分散液Ｄ１の調製＞
　下記組成の分散液を調合し、これをジルコニアビーズ（０．３ｍｍφ）１７，０００部と混合し、ペイントシェーカーを用いて１２時間分散を行った。ジルコニアビ－ズ（０．３ｍｍφ）をろ別し、分散液Ｄ１を得た。
・二酸化チタン（石原産業（株）製、商品名：ＴＴＯ－５１（Ｃ）、平均一次粒径：１０～３０ｎｍ）：１，８７５部
・分散剤（ＤＩＳＰＥＲＢＹＫ－１１１：ビックケミー・ジャパン（株）製の３０％ＰＧＭＥＡ溶液）：２，２００部
・溶剤（ＰＧＭＥＡ）：３，４２５部 <Preparation of dispersion D1>
A dispersion having the following composition was prepared, mixed with 17,000 parts of zirconia beads (0.3 mmφ), and dispersed for 12 hours using a paint shaker. Zirconia beads (0.3 mmφ) were filtered off to obtain dispersion D1.
・ Titanium dioxide (made by Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C), average primary particle size: 10-30 nm): 1,875 parts ・ Dispersant (DISPERBYK-111: manufactured by Big Chemie Japan) 30% PGMEA solution): 2,200 parts ・ Solvent (PGMEA): 3,425 parts
＜分散液Ｄ２～Ｄ１０の調製＞
　二酸化チタン粒子及び分散剤を下記表１の化合物に変更した以外は分散液Ｄ１と同様にして分散液Ｄ２～Ｄ１０を調製した。 <Preparation of dispersions D2 to D10>
Dispersions D2 to D10 were prepared in the same manner as the dispersion D1, except that the titanium dioxide particles and the dispersant were changed to the compounds shown in Table 1 below.
＜分散液Ｄ１１の調製＞
　下記組成に変更した以外は分散液Ｄ１と同様に調製して、分散液Ｄ１１を得た。
・二酸化チタン（石原産業（株）製、商品名：ＴＴＯ－５１（Ｃ）、平均一次粒径：１０～３０ｎｍ）：１，８７５部
・化合物１（Ｍｗ＝３，３００、３０％ＰＧＭＥＡ溶液）：２，２００部
・複素環化合物　Ｆ－１：１８７．５部
・溶剤（ＰＧＭＥＡ）：３，２３７．５部 <Preparation of dispersion D11>
A dispersion D11 was obtained in the same manner as the dispersion D1, except that the composition was changed to the following composition.
Titanium dioxide (Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C), average primary particle size: 10 to 30 nm): 1,875 partsCompound 1 (Mw = 3,300, 30% PGMEA solution) : 2,200 parts ・ Heterocyclic compound F-1: 187.5 parts ・ Solvent (PGMEA): 3,237.5 parts
＜分散液Ｄ１２の調製＞
　下記組成に変更した以外は分散液Ｄ１と同様に調製して、分散液Ｄ１２を得た。
・二酸化チタン（石原産業（株）製、商品名：ＴＴＯ－５１（Ｃ）、平均一次粒径：１０～３０ｎｍ）：１，８７５部
・化合物１（Ｍｗ＝３，３００、３０％ＰＧＭＥＡ溶液）：２，８２９部
・溶剤（ＰＧＭＥＡ）：２，７９６部 <Preparation of dispersion D12>
A dispersion D12 was obtained in the same manner as the dispersion D1 except that the composition was changed to the following composition.
Titanium dioxide (Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C), average primary particle size: 10 to 30 nm): 1,875 partsCompound 1 (Mw = 3,300, 30% PGMEA solution) : 2,829 parts · Solvent (PGMEA): 2,796 parts
Figure JPOXMLDOC01-appb-T000064
Figure JPOXMLDOC01-appb-T000064
（実施例１）
＜光硬化性組成物の調製＞
　上記で得られた二酸化チタン分散液を用いて、下記組成となるように各成分を混合し、実施例１の光硬化性組成物を得た。
・プロピレングリコールモノメチルエーテルアセテート：３６２．３部
・ポリマー（Ｐ－１）（３０ｗｔ％）：９４．２部
・ジペンタエリスリトールヘキサアクリレート（Ｍ－１）：３７．７部
・オキシム系光重合開始剤（Ｉ－１）：５．６７部
・パーフルオロアルキル含有ノニオン界面活性剤（Ｆ－５５４、ＤＩＣ（株）製の２．０％ＰＧＭＥＡ溶液）：０．２５部
・分散液Ｄ１：５００．０部
・複素環化合物　Ｆ－５：５．００部 (Example 1)
<Preparation of photocurable composition>
Each component was mixed so that it might become the following composition using the titanium dioxide dispersion liquid obtained above, and the photocurable composition of Example 1 was obtained.
Propylene glycol monomethyl ether acetate: 362.3 parts Polymer (P-1) (30 wt%): 94.2 parts Dipentaerythritol hexaacrylate (M-1): 37.7 parts Oxime-based photopolymerization initiator (I-1): 5.67 parts-perfluoroalkyl-containing nonionic surfactant (F-554, 2.0% PGMEA solution manufactured by DIC Corporation): 0.25 parts-Dispersion D1: 500.0 Parts / heterocyclic compounds F-5: 5.00 parts
（実施例２～２２、２５～２６、比較例１～４）
　分散液、複素環化合物、及びポリマーを下記表２のものに変更した以外は実施例１と同様にして光硬化性組成物を得た。 (Examples 2 to 22, 25 to 26, Comparative Examples 1 to 4)
A photocurable composition was obtained in the same manner as in Example 1 except that the dispersion, the heterocyclic compound, and the polymer were changed to those shown in Table 2 below.
（実施例２３）
　以下の組成となるように各成分を混合して、実施例２３の光硬化性組成物を得た。
・プロピレングリコールモノメチルエーテルアセテート：３６２．３部
・ポリマー（Ｐ－１）：９４．２部
・モノマー（Ｍ－２）：１２．６部
・モノマー（Ｍ－１）：２５．１部
・オキシム系光重合開始剤（Ｉ－１）：５．６７部
・パーフルオロアルキル含有ノニオン界面活性剤（Ｆ－５５４、ＤＩＣ（株）製の２．０％ＰＧＭＥＡ溶液）：０．２５部
・分散液Ｄ５：５００．０部
・複素環化合物　Ｆ－５：５．００部 (Example 23)
Each component was mixed so that it might become the following compositions, and the photocurable composition of Example 23 was obtained.
Propylene glycol monomethyl ether acetate: 362.3 parts Polymer (P-1): 94.2 parts Monomer (M-2): 12.6 parts Monomer (M-1): 25.1 parts Oxime series Photopolymerization initiator (I-1): 5.67 parts-Perfluoroalkyl-containing nonionic surfactant (F-554, 2.0% PGMEA solution manufactured by DIC Corporation): 0.25 parts-Dispersion D5 : 500.0 parts ・ Heterocyclic compound F-5: 5.00 parts
（実施例２４）
　以下の組成となるように各成分を混合して、実施例２４の光硬化性組成物を得た。
・プロピレングリコールモノメチルエーテルアセテート：３６２．３部
・ポリマー（Ｐ－３）：９４．２部
・モノマー（Ｍ－３）：３７．７部
・オキシム系光重合開始剤（Ｉ－１）：５．６７部
・パーフルオロアルキル含有ノニオン界面活性剤（Ｆ－５５４、ＤＩＣ（株）製の２．０％ＰＧＭＥＡ溶液）：０．２５部
・分散液Ｄ５：５００．０部
・複素環化合物　Ｆ－５：５．００部 (Example 24)
Each component was mixed so that it might become the following compositions, and the photocurable composition of Example 24 was obtained.
Propylene glycol monomethyl ether acetate: 362.3 parts Polymer (P-3): 94.2 parts Monomer (M-3): 37.7 parts Oxime photopolymerization initiator (I-1): 5. 67 parts perfluoroalkyl-containing nonionic surfactant (F-554, 2.0% PGMEA solution manufactured by DIC Corporation): 0.25 parts Dispersion D5: 500.0 parts Heterocyclic compound F-5 : 5.00 parts
（評価）
＜ヘイズ（透明性）の評価＞
　１００ｍｍ×１００ｍｍのガラス基板（商品名：ＸＧ、コーニング社製）上に、得られた光硬化性組成物を乾燥膜厚が２．０μｍとなるようにスピンコーターにて塗布し、８０℃のホットプレート上で１２０秒乾燥（プリベーク）した。次に、ｇｈｉ線高圧水銀灯露光機を用いて、エネルギー強度２０ｍＷ／ｃｍ2、２００ｍＪ／ｃｍ2にて全面露光した。更に、塗布膜を１２０℃のオーブンで１５分加熱処理（ポストベーク）を施した。このようにして得られた硬化膜のヘイズを日本電色工業（株）製ＮＤＨ－５０００にて膜面を上にして、プラスチック製品試験方法（ＪＩＳ　Ｋ７１３６・ＪＩＳ　Ｋ７３６１・ＡＳＴＭ　Ｄ１００３）に準拠し、曇り度（ヘイズ値）を測定した。
　なお、ヘイズ値とは、全光線透過光に対する拡散透過光の割合（％）で表される値を指す。ヘイズ値が小さいほど、透明性が高いことを表す。
　　　１：ヘイズ値　０．５％未満
　　　２：ヘイズ値　０．５％以上　０．７％未満
　　　３：ヘイズ値　０．７％以上　１．０％未満
　　　４：ヘイズ値　１．０％以上　２．０％未満
　　　５：ヘイズ値　２．０％以上 (Evaluation)
<Evaluation of haze (transparency)>
On a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning), the obtained photocurable composition was applied with a spin coater so as to have a dry film thickness of 2.0 μm. The plate was dried (pre-baked) for 120 seconds. Next, the entire surface 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. Furthermore, the coating film was heat-treated (post-baked) for 15 minutes in an oven at 120 ° C. The haze of the cured film thus obtained is NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd., with the film surface facing upward, in accordance with the plastic product test method (JIS K7136, JIS K7361, ASTM D1003), The haze (haze value) was measured.
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.
1: Haze value of less than 0.5% 2: Haze value of 0.5% or more and less than 0.7% 3: Haze value of 0.7% or more and less than 1.0% 4: Haze value of 1.0% or more and 2.0% Less than 5: Haze value 2.0% or more
＜現像残渣評価＞
　１００ｍｍ×１００ｍｍのガラス基板（商品名：ＸＧ、コーニング社製）上に、得られた光硬化性組成物を膜厚１．０μｍとなるようにスピンコーターにて塗布し、９０℃のホットプレート上で１２０秒乾燥（プリベーク）した。
　次いで、０．５質量％のＫＯＨ水溶液により２３℃で３０秒間浸液盛り法にて現像し、更に超純水で１０秒間リンスした。ガラス基板を光学顕微鏡で観察し、膜の現像残り（残渣）の有無を評価した。なお、評価基準は、以下に示す通りである。
　　　１：残渣なし
　　　２：わずかに残渣あり
　　　３：残渣あり <Development residue evaluation>
The obtained photocurable 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 μm, and on a hot plate at 90 ° C. 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 30 seconds by immersion, and further rinsed with ultrapure water for 10 seconds. The glass substrate was observed with an optical microscope, and the presence or absence of a development residue (residue) of the film was evaluated. The evaluation criteria are as shown below.
1: No residue 2: Slightly residue 3: Residue
＜屈折率の評価＞
　得られた光硬化性組成物を、スピナーを用いてシリコンウエハ基板上に塗布し、８０℃で１２０秒乾燥することによって厚さ０．５μｍの膜を形成した。この基板を、超高圧水銀灯を用いて２００ｍＪ／ｃｍ2（ｉ線で測定）で露光した。その後、オーブンにて２２０℃分で４５分加熱した。
　エリプソメーターＶＵＶ－ＶＡＳＥ（ジェー・エー・ウーラム・ジャパン（株）製）を用いて、５８９ｎｍでの硬化膜の屈折率を測定した。屈折率が高いほうが好ましく、１．７０以上がより好ましい。 <Evaluation of refractive index>
The obtained photocurable 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 μm. This substrate was exposed at 200 mJ / cm 2 (measured by i-line) using an ultrahigh pressure mercury lamp. Then, it heated at 220 degreeC minutes for 45 minutes in oven.
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.
＜解像性評価＞
　ヘキサメチルジシラザン（ＨＭＤＳ）を用いて、３分処理した１００ｍｍ×１００ｍｍのガラス基板（商品名：ＸＧ、コーニング社製）上に、得られた光硬化性組成物を膜厚２．０μｍとなるようにスピンコーターにて塗布し、９０℃のホットプレート上で１２０秒乾燥（プリベーク）した。
　次に、ｇｈｉ線高圧水銀灯露光機を用いて、エネルギー強度２０ｍＷ／ｃｍ2、２００ｍＪ／ｃｍ2にて、ラインアンドスペース１：１の１％～６０％グラデーション付きマスクを介して露光した。
　次に、０．５％のＫＯＨ水溶液により２３℃で１５秒間浸液盛り法にて現像し、更に超純水で１０秒間リンスした。続いて２２０℃４５分加熱してパターンを得た。このパターンを光学顕微鏡で観察した。
　この操作をマスクのラインアンドスペースの幅５０μｍから開始し、１０μｍまでは、５μｍずつ、１０μｍ以下は、幅を１μｍずつ狭めていき、最適露光量部分のきれいにパターン作製できた最小幅を解像度とした。１～３が実用範囲であり、１又は２が好ましい。
　　　１：解像度が５μｍ以下であった。
　　　２：解像度が５μｍを超え１０μｍ以下であった。
　　　３：解像度が１０μｍを超え５０μｍ以下であった。
　　　４：マスクのラインアンドスペースの幅５０μｍでパターンを形成できなかった。 <Resolution evaluation>
The resulting photocurable composition has a thickness of 2.0 μm on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) treated with hexamethyldisilazane (HMDS) for 3 minutes. As described above, the coating was applied by a spin coater and dried (prebaked) for 120 seconds on a hot plate at 90 ° C.
Next, using 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 .
Next, 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 μm, and until 10 μm, the width is reduced by 5 μm by 10 μm, and the width is reduced by 1 μm. . 1 to 3 is a practical range, and 1 or 2 is preferable.
1: The resolution was 5 μm or less.
2: The resolution was more than 5 μm and 10 μm or less.
3: The resolution was more than 10 μm and 50 μm or less.
4: A pattern could not be formed with a mask line and space width of 50 μm.
＜ＩＴＯパターン視認性の評価＞
　１００ｍｍ×１００ｍｍのガラス基板（商品名：ＸＧ、コーニング社製）上に、あらかじめＩＴＯのパターンを形成しておき、得られた光硬化性組成物を膜厚１．０μｍとなるようにスピンコーターにて塗布し、９０℃のホットプレート上で１２０秒乾燥（プリベーク）した。
　次に、基板全面にｇｈｉ線高圧水銀灯露光機を用いて、エネルギー強度２０ｍＷ／ｃｍ2、２００ｍＪ／ｃｍ2にて、露光した。
　続いて２２０℃４５分加熱してＩＴＯパターン上に光硬化性脂組成物の乾燥膜を設けた。得られた基板を明室内において肉眼で、傾斜をかけながら観察し、ＩＴＯパターン上に光硬化性組成物を設けなかった時と比較して、視認性の評価を行った。なお、評価基準は、ＩＴＯのパターンが見えにくいほどよい。１又は２が実用範囲である。
　　　１：ＩＴＯのパターンがほぼ見えない。
　　　２：ＩＴＯのパターンが薄ら見える。
　　　３：ＩＴＯのパターンがはっきり見える。 <Evaluation of ITO pattern visibility>
An ITO pattern is formed in advance on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning), and the obtained photocurable composition is applied to a spin coater so as to have a film thickness of 1.0 μm. 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.
Then, it heated at 220 degreeC for 45 minutes, and provided the dry film | membrane of the photocurable fat composition on the ITO pattern. The obtained substrate was observed with the naked eye in a bright room while tilting, and the visibility was evaluated as compared with the case where the photocurable composition was not provided on the ITO pattern. Note that 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.
（実施例２７）
　以下の組成となるように各成分を混合して、実施例２７の光硬化性組成物を得た。
・プロピレングリコールモノメチルエーテルアセテート：３２１．４部
・ポリマー（Ｐ－４）：１６２．１部
・架橋剤（Ｋ－１）：１０．５部
・光酸発生剤（Ｂ－１）：５．６７部
・パーフルオロアルキル含有ノニオン界面活性剤（Ｆ－５５４、ＤＩＣ（株）製の２．０％ＰＧＭＥＡ溶液）：０．２５部
・分散液Ｄ５：５００．０部
・複素環化合物　Ｆ－５：５．００部 (Example 27)
Each component was mixed so that it might become the following compositions, and the photocurable composition of Example 27 was obtained.
Propylene glycol monomethyl ether acetate: 321.4 parts Polymer (P-4): 162.1 parts Crosslinking agent (K-1): 10.5 parts Photo acid generator (B-1): 5.67 Parts perfluoroalkyl-containing nonionic surfactant (F-554, 2.0% PGMEA solution manufactured by DIC Corporation): 0.25 parts Dispersion D5: 500.0 parts Heterocyclic compound F-5: 5.00 parts
（実施例２８）
　ポリマー（Ｐ－４）をポリマー（Ｐ－５）に変更した以外は実施例２７と同様にして実施例２８の光硬化性組成物を得た。 (Example 28)
A photocurable composition of Example 28 was obtained in the same manner as in Example 27 except that the polymer (P-4) was changed to the polymer (P-5).
（比較例５）
　成分Ａとして複素環化合物Ｆ－５を添加しなかった以外は、実施例２７と同様にして比較例５の光硬化性組成物を得た。 (Comparative Example 5)
A photocurable composition of Comparative Example 5 was obtained in the same manner as in Example 27 except that the heterocyclic compound F-5 was not added as Component A.
（評価）
　以下に示す評価以外は、実施例１と同様にして評価を行った。
＜現像残渣評価＞
　１００ｍｍ×１００ｍｍのガラス基板（商品名：ＸＧ、コーニング社製）上に、得られた光硬化性組成物を膜厚１．０μｍとなるようにスピンコーターにて塗布し、９０℃のホットプレート上で１２０秒乾燥（プリベーク）した。
　次いで、２．３８質量％のテトラメチルアンモニウムヒドロキソド水溶液により２３℃で３０秒間浸液盛り法にて現像し、更に超純水で１０秒間リンスした。ガラス基板を光学顕微鏡で観察し、膜の現像残り（残渣）の有無を評価した。なお、評価基準は、以下に示す通りである。
　　　１：残渣なし
　　　２：わずかに残渣あり
　　　３：残渣あり (Evaluation)
The evaluation was performed in the same manner as in Example 1 except for the evaluation shown below.
<Development residue evaluation>
The obtained photocurable 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 μm, and on a hot plate at 90 ° C. And dried for 120 seconds (pre-baked).
Subsequently, the film was developed with a 2.38 mass% aqueous tetramethylammonium hydroxide solution at 23 ° C. for 30 seconds by immersion, and further rinsed with ultrapure water for 10 seconds. The glass substrate was observed with an optical microscope, and the presence or absence of a development residue (residue) of the film was evaluated. The evaluation criteria are as shown below.
1: No residue 2: Slightly residue 3: Residue
＜解像性評価＞
　ヘキサメチルジシラザン（ＨＭＤＳ）を用いて、３分処理した１００ｍｍ×１００ｍｍのガラス基板（商品名：ＸＧ、コーニング社製）上に、得られた光硬化性組成物を膜厚２．０μｍとなるようにスピンコーターにて塗布し、９０℃のホットプレート上で１２０秒乾燥（プリベーク）した。
　次に、ｇｈｉ線高圧水銀灯露光機を用いて、エネルギー強度２０ｍＷ／ｃｍ2、２００ｍＪ／ｃｍ2にて、ラインアンドスペース１：１の１％～６０％グラデーション付きマスクを介して露光した。その後、１１０℃で９０秒の加熱処理を行った。
　次に、２．３８質量％のテトラメチルアンモニウムヒドロキソド水溶液により２３℃で１５秒間浸液盛り法にて現像し、更に超純水で１０秒間リンスした。続いて２２０℃４５分加熱してパターンを得た。このパターンを光学顕微鏡で観察した。
　この操作をマスクのラインアンドスペースの幅５０μｍから開始し、１０μｍまでは、５μｍずつ、１０μｍ以下は、幅を１μｍずつ狭めていき、最適露光量部分のきれいにパターン作製できた最小幅を解像度とした。１又は２が実用範囲である。
　　　１：解像度が５μｍ以下であった。
　　　２：解像度が５μｍを超え１０μｍ以下であった。
　　　３：解像度が１０μｍを超え５０μｍ以下であった。
　　　４：マスクのラインアンドスペースの幅５０μｍでパターンを形成できなかった。 <Resolution evaluation>
The resulting photocurable composition has a thickness of 2.0 μm on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning) treated with hexamethyldisilazane (HMDS) for 3 minutes. As described above, the coating was applied by a spin coater and dried (prebaked) for 120 seconds on a hot plate at 90 ° C.
Next, using 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 . Thereafter, heat treatment was performed at 110 ° C. for 90 seconds.
Next, 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. 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 μm, and until 10 μm, the width is reduced by 5 μm by 10 μm, and the width is reduced by 1 μm. . 1 or 2 is a practical range.
1: The resolution was 5 μm or less.
2: The resolution was more than 5 μm and 10 μm or less.
3: The resolution was more than 10 μm and 50 μm or less.
4: A pattern could not be formed with a mask line and space width of 50 μm.
Figure JPOXMLDOC01-appb-T000065
Figure JPOXMLDOC01-appb-T000065
（実施例２９）
　特許第３３２１００３号公報の図１に記載のアクティブマトリクス型液晶表示装置において、層間絶縁膜として硬化膜１７を以下のようにして形成し、実施例２９の液晶表示装置を得た。すなわち、特許第３３２１００３号公報の００５８段落の基板と層間絶縁膜１７の濡れ性を向上させる前処理として、基板をヘキサメチルジシラザン（ＨＭＤＳ）蒸気下に３０秒曝し、その後、実施例４の光硬化性組成物を基板上にスピン塗布し、ホットプレート上でプリベーク（９０℃／１２０秒）して溶剤を揮発させ、膜厚３μｍの光硬化性組成物層を形成した。次に、得られた光硬化性組成物層を、キヤノン（株）製　ＭＰＡ　５５００ＣＦ（高圧水銀灯）を用いて、１０μｍφのホールパターン形成用のマスクを介して４０ｍＪ／ｃｍ2（エネルギー強度：２０ｍＷ／ｃｍ2、ｉ線）となるよう露光した。そして、露光後の光硬化性組成物層を、アルカリ現像液（０．４％のテトラメチルアンモニウムヒドロキシド水溶液）で２３℃／６０秒間パドル現像した後、超純水で２０秒リンスした。続いて超高圧水銀灯を用いて積算照射量が３００ｍＪ／ｃｍ2（エネルギー強度：２０ｍＷ／ｃｍ2、ｉ線）となるように全面露光し、その後、この基板をオーブンにて２３０℃で３０分加熱して硬化膜を得た。
　上記光硬化性組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。 (Example 29)
In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3312003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 29 was obtained. That is, as a pretreatment for improving the wettability between the substrate and the interlayer insulating film 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the light of Example 4 was used. The curable composition was spin-coated on a substrate, pre-baked on a hot plate (90 ° C./120 seconds) to evaporate the solvent, and a 3 μm-thick photocurable composition layer was formed. Next, the obtained photocurable composition layer was subjected to 40 mJ / cm 2 (energy intensity: 20 mW / mm) through a mask for forming a 10 μmφ hole pattern using an MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. cm 2 , i-line). The photocurable composition layer after the exposure was subjected to paddle development at 23 ° C./60 seconds with an alkaline developer (0.4% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
The applicability when applying the photocurable composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and baking.
（実施例３０）
　実施例２９と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、露光装置をキヤノン（株）製　ＭＰＡ　５５００ＣＦ（高圧水銀灯）から、Ｎｉｋｏｎ（株）製ＦＸ－８０３Ｍ（ｇｈ－Ｌｉｎｅ　ステッパー）に変更した。得られた液晶表示装置の性能は、実施例２９と同様に良好であった。 (Example 30)
A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the exposure apparatus was changed from MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The performance of the obtained liquid crystal display device was as good as in Example 29.
（実施例３１）
　実施例２９と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、露光装置をキヤノン（株）製　ＭＰＡ　５５００ＣＦ（高圧水銀灯）から、（株）ブイ・テクノロジー製の「ＡＥＧＩＳ」を使用し、波長３５５ｎｍ、パルス幅６ｎｓｅｃに変更した。得られた液晶表示装置の性能は、実施例２９と同様に良好であった。 (Example 31)
A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the exposure apparatus was changed from Canon's MPA 5500CF (high pressure mercury lamp) to “AEGIS” manufactured by Buoy Technology Co., Ltd., to a wavelength of 355 nm and a pulse width of 6 nsec. The performance of the obtained liquid crystal display device was as good as in Example 29.
（実施例３２）
　実施例２９と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、基板の前処理であるヘキサメチルジシラザン（ＨＭＤＳ）処理を省いて、実施例１の光硬化性組成物を塗布した。得られた硬化膜は、パターンの欠けや剥がれのない良好な状態であった。また、液晶表示装置としての性能も実施例２９と同様に良好であった。これは本発明の組成物が基板との密着性に優れるためであると思われる。生産性を向上させる観点では、上記基板の前処理の工程を省くことも好ましい。 (Example 32)
A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the photocurable composition of Example 1 was applied without the hexamethyldisilazane (HMDS) treatment, which was a pretreatment of the substrate. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. This is presumably because the composition of the present invention has excellent adhesion to the substrate. From the viewpoint of improving productivity, it is also preferable to omit the substrate pretreatment step.
（実施例３３）
　実施例２９と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、プリベーク後に減圧乾燥工程（ＶＣＤ）を導入した。得られた硬化膜は、パターンの欠けや剥がれのない良好な状態であった。また、液晶表示装置としての性能も実施例２９と同様に良好であった。組成物の固形分濃度や膜厚に応じて、塗布ムラを抑制する観点から、減圧乾燥工程を導入することも好ましい。 (Example 33)
A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, a vacuum drying step (VCD) was introduced after pre-baking. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. It is also preferable to introduce a reduced-pressure drying step from the viewpoint of suppressing coating unevenness according to the solid content concentration and the film thickness of the composition.
（実施例３４）
　使用する光硬化性組成物を実施例２７の光硬化性組成物へ変更し、又は、実施例２９と以下のプロセスを変更して、同様の液晶表示装置を得た。すなわち、マスク露光してから現像工程の間にＰＥＢ工程（露光後加熱処理工程、９０℃、１分）を導入した。得られた硬化膜は、パターンの欠けや剥がれのない良好な状態であった。また、液晶表示装置としての性能も実施例２９と同様に良好であった。寸法安定性を高める観点では、ＰＥＢ工程を導入することも好ましい。 (Example 34)
The photocurable composition to be used was changed to the photocurable composition of Example 27, or the same process as in Example 29 was changed to obtain a similar liquid crystal display device. That is, a PEB process (post-exposure heat treatment process, 90 ° C., 1 minute) was introduced between the mask exposure and the development process. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. From the viewpoint of improving dimensional stability, it is also preferable to introduce a PEB process.
（実施例３５）
　実施例２９と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、アルカリ現像液を０．４％のテトラメチルアンモニウムヒドロキシド水溶液から２．３８％のテトラメチルアンモニウムヒドロキシド水溶液に変更した。得られた硬化膜は、パターンの欠けや剥がれのない良好な状態であった。また、液晶表示装置としての性能も実施例２９と同様に良好であった。これは本発明の組成物が基板との密着性に優れるためであると思われる。 (Example 35)
A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 2.38% tetramethylammonium hydroxide aqueous solution. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
（実施例３６）
　実施例２９と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、アルカリ現像方法をパドル現像からシャワー現像に変更した。得られた硬化膜は、パターンの欠けや剥がれのない良好な状態であった。また、液晶表示装置としての性能も実施例２９と同様に良好であった。これは本発明の組成物が基板との密着性に優れるためであると思われる。 (Example 36)
A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the alkali development method was changed from paddle development to shower development. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
（実施例３７）
　実施例２９と以下のプロセスのみ変更して、同様の液晶表示装置を得た。すなわち、アルカリ現像液を０．４％のテトラメチルアンモニウムヒドロキシド水溶液から０．０４％のＫＯＨ水溶液に変更た。得られた硬化膜は、パターンの欠けや剥がれのない良好な状態であった。また、液晶表示装置としての性能も実施例２９と同様に良好であった。これは本発明の組成物が基板との密着性に優れるためであると思われる。 (Example 37)
A liquid crystal display device similar to that of Example 29 was changed to obtain a similar liquid crystal display device. That is, the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution. The obtained cured film was in a good state with no chipping or peeling of the pattern. Further, the performance as a liquid crystal display device was as good as in Example 29. This is presumably because the composition of the present invention has excellent adhesion to the substrate.
　得られた液晶表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
（実施例３８）
　薄膜トランジスター（ＴＦＴ）を用いた有機ＥＬ表示装置を以下の方法で作製した（図２参照）。
　ガラス基板６上にボトムゲート型のＴＦＴ１を形成し、このＴＦＴ１を覆う状態でＳｉ3Ｎ4からなる絶縁膜３を形成した。次に、この絶縁膜３に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してＴＦＴ１に接続される配線２（高さ１．０μｍ）を絶縁膜３上に形成した。この配線２は、ＴＦＴ１間、又は、後の工程で形成される有機ＥＬ素子とＴＦＴ１とを接続するためのものである。 (Example 38)
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. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
　更に、配線２の形成による凹凸を平坦化するために、配線２による凹凸を埋め込む状態で絶縁膜３上へ平坦化膜４を形成した。絶縁膜３上への平坦化膜４の形成は、実施例２７の光硬化性組成物を基板上にスピン塗布し、ホットプレート上でプリベーク（９０℃／１２０秒）した後、マスク上から高圧水銀灯を用いてｉ線（３６５ｎｍ）を４５ｍＪ／ｃｍ2（エネルギー強度２０ｍＷ／ｃｍ2）照射した後、ホットプレ－ト上で１１０℃９０秒の加熱処理を行い、アルカリ水溶液にて現像してパターンを形成し、２３０℃／３０分間の加熱処理を行った。
　光硬化性組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。更に、配線２の平均段差は５００ｎｍ、作製した平坦化膜４の膜厚は２，０００ｎｍであった。 Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photocurable composition of Example 27 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, heat treatment is performed at 110 ° C. for 90 seconds on a hot plate, and the pattern is developed with an aqueous alkali solution. Then, heat treatment was performed at 230 ° C./30 minutes.
The applicability when applying the photocurable composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
　次に、得られた平坦化膜４上に、ボトムエミッション型の有機ＥＬ素子を形成した。まず、平坦化膜４上に、ＩＴＯからなる第一電極５を、コンタクトホール７を介して配線２に接続させて形成した。その後、レジストを塗布、プリベークし、所望のパターンのマスクを介して露光し、現像した。このレジストパターンをマスクとして、ＩＴＯエッチャント用いたウエットエッチングによりパターン加工を行った。その後、レジスト剥離液（リムーバ１００、ＡＺエレクトロニックマテリアルズ社製）を用いて上記レジストパターンを５０℃で剥離した。こうして得られた第一電極５は、有機ＥＬ素子の陽極に相当する。 Next, a bottom emission type organic EL element was formed on the obtained flattening film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.
　次に、第一電極５の周縁を覆う形状の絶縁膜８を形成した。絶縁膜８には、実施例１３の光硬化性組成物を用い、上記と同様の方法で絶縁膜８を形成した。この絶縁膜８を設けることによって、第一電極５とこの後の工程で形成する第二電極との間のショートを防止することができる。 Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photocurable composition of Example 13 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.
　更に、真空蒸着装置内で所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設けた。次いで、基板上方の全面にＡｌからなる第二電極を形成した。得られた上記基板を蒸着機から取り出し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止した。 Further, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
　以上のようにして、各有機ＥＬ素子にこれを駆動するためのＴＦＴ１が接続してなるアクティブマトリックス型の有機ＥＬ表示装置が得られた。駆動回路を介して電圧を印加したところ、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving it was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.
（実施例３９）
　以下に述べる方法により本発明の高屈折率の硬化性樹脂材料を用いてタッチパネル表示装置を作成した。
＜第一の透明電極パターンの形成＞
［透明電極層の形成］
　あらかじめマスク層が形成された強化処理ガラス（３００ｍｍ×４００ｍｍ×０．７ｍｍ）の前面板を、真空チャンバー内に導入し、ＳｎＯ2含有率が１０質量％のＩＴＯターゲット（インジウム：錫＝９５：５（モル比））を用いて、ＤＣマグネトロンスパッタリング（条件：基材の温度２５０℃、アルゴン圧０．１３Ｐａ、酸素圧０．０１Ｐａ）により、厚さ４０ｎｍのＩＴＯ薄膜を形成し、透明電極層を形成した前面板を得た。ＩＴＯ薄膜の表面抵抗は８０Ω／□であった。 (Example 39)
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 front plate of tempered glass (300 mm × 400 mm × 0.7 mm) with a mask layer formed in advance is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5) with a SnO 2 content of 10% by mass. (Molar ratio)) was used to form an ITO thin film having a thickness of 40 nm by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode layer was formed. A formed front plate was obtained. The surface resistance of the ITO thin film was 80Ω / □.
　次いで、市販のエッチングレジストをＩＴＯ上に塗布・乾燥し、エッチングレジスト層を形成した。露光マスク（透明電極パターンを有す石英露光マスク）面とエッチングレジスト層との間の距離を１００μｍに設定し、露光量５０ｍＪ／ｃｍ2（ｉ線）でパターン露光したのち、専用の現像液で現像を行い、更に１３０℃３０分間のポストベーク処理を行って、透明電極層とエッチング用光硬化性樹脂層パターンとを形成した前面板を得た。 Next, a commercially available etching resist was applied onto ITO and dried to form an etching resist layer. Set the distance between the exposure mask (quartz exposure mask with a transparent electrode pattern) surface and the etching resist layer to 100 μm, pattern exposure with an exposure amount of 50 mJ / cm 2 (i-line), and then use a dedicated developer. Development was performed, and a post-bake treatment at 130 ° C. for 30 minutes was further performed to obtain a front plate on which a transparent electrode layer and a photocurable resin layer pattern for etching were formed.
　透明電極層とエッチング用光硬化性樹脂層パターンとを形成した前面板を、ＩＴＯエッチャント（塩酸、塩化カリウム水溶液。液温３０℃）を入れたエッチング槽に浸漬し、１００秒処理し、エッチングレジスト層で覆われていない露出した領域の透明電極層を溶解除去し、エッチングレジスト層パターンのついた透明電極層パターン付の前面板を得た。
　次に、エッチングレジスト層パターンのついた透明電極層パターン付の前面板を、専用のレジスト剥離液に浸漬し、エッチング用光硬化性樹脂層を除去し、マスク層と第一の透明電極パターンとを形成した前面板を得た。 The front plate on which the transparent electrode layer and the 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. The exposed transparent electrode layer not covered with the layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern with an etching resist layer pattern.
Next, the 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.
［絶縁層の形成］
　マスク層と第一の透明電極パターンとを形成した前面板の上に、実施例１の光硬化性組成物を塗布・乾燥（膜厚１μｍ、９０℃１２０秒）し、光硬化性組成物層を得た。露光マスク（絶縁層用パターンを有す石英露光マスク）面と光硬化性組成物層との間の距離を３０μｍに設定し、露光量５０ｍＪ／ｃｍ2（ｉ線）でパターン露光した。
　次に、２．３８質量％のテトラメチルアンモニウムヒドロキシド水溶液により２３℃で１５秒間浸液盛り法にて現像し、更に超純水で１０秒間リンスした。続いて２２０℃４５分のポストベーク処理を行って、マスク層、第一の透明電極パターン、絶縁層パターンを形成した前面板を得た。 [Formation of insulating layer]
On the front plate on which the mask layer and the first transparent electrode pattern were formed, the photocurable composition of Example 1 was applied and dried (film thickness: 1 μm, 90 ° C., 120 seconds) to form a photocurable composition layer. Got. The distance between the exposure mask (quartz exposure mask having an insulating layer pattern) surface and the photocurable composition layer was set to 30 μm, and pattern exposure was performed at an exposure amount of 50 mJ / cm 2 (i-line).
Next, 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. Subsequently, 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.
＜第二の透明電極パターンの形成＞
［透明電極層の形成］
　上記第一の透明電極パターンの形成と同様にして、絶縁層パターンまで形成した前面板をＤＣマグネトロンスパッタリング処理し（条件：基材の温度５０℃、アルゴン圧０．１３Ｐａ、酸素圧０．０１Ｐａ）、厚さ８０ｎｍのＩＴＯ薄膜を形成し、透明電極層を形成した前面板を得た。ＩＴＯ薄膜の表面抵抗は１１０Ω／□であった。
　第一の透明電極パターンの形成の形成と同様にして、市販のエッチングレジストを用いて、第一の透明電極パターン、実施例１の光硬化性組成物を用いて形成した絶縁層パターン、透明電極層、エッチングレジストパターンを形成した前面板を得た（ポストベーク処理；１３０℃３０分間）。
　更に、第一の透明電極パターンの形成の形成と同様にして、エッチングし、エッチングレジスト層を除去することにより、マスク層、第一の透明電極パターン、実施例１の光硬化性組成物を用いて形成した絶縁層パターン、第二の透明電極パターンを形成した前面板を得た。 <Formation of second transparent electrode pattern>
[Formation of transparent electrode layer]
In the same manner as the formation of the first transparent electrode pattern, the front plate formed up to the insulating layer pattern was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa). An ITO thin film having a thickness of 80 nm was formed to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 110Ω / □.
In the same manner as in the formation of the first transparent electrode pattern, a commercially available etching resist is used, the first transparent electrode pattern, the insulating layer pattern formed using the photocurable composition of Example 1, and the transparent electrode A front plate on which a layer and an etching resist pattern were formed was obtained (post-bake treatment; 130 ° C. for 30 minutes).
Further, the mask layer, the first transparent electrode pattern, and the photocurable composition of Example 1 were used by etching and removing the etching resist layer in the same manner as the formation of the first transparent electrode pattern. A front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was obtained.
＜第一及び第二の透明電極パターンとは別の導電性要素の形成＞
　上記第一、及び、第二の透明電極パターンの形成と同様にして、第一の透明電極パターン、実施例１の光硬化性組成物を用いて形成した絶縁層パターン、第二の透明電極パターンを形成した前面板をＤＣマグネトロンスパッタリング処理し、厚さ２００ｎｍのアルミニウム（Ａｌ）薄膜を形成した前面板を得た。
　上記第一、及び、第二の透明電極パターンの形成と同様にして、市販のエッチングレジストを用いて、第一の透明電極パターン、実施例１の光硬化性組成物を用いて形成した絶縁層パターン、第二の透明電極パターン、エッチングレジストパターンを形成した前面板を得た。（ポストベーク処理；１３０℃３０分間）。
　更に、第一の透明電極パターンの形成の形成と同様にして、エッチング（３０℃５０秒間）し、エッチングレジスト層を除去（４５℃２００秒間）することにより、マスク層、第一の透明電極パターン、実施例１の光硬化性組成物を用いて形成した絶縁層パターン、第二の透明電極パターン、第一及び第二の透明電極パターンとは別の導電性要素を形成した前面板を得た。 <Formation of Conductive Element Different from First and Second Transparent Electrode Pattern>
Similar to the formation of the first and second transparent electrode patterns, the first transparent electrode pattern, the insulating layer pattern formed using the photocurable composition of Example 1, and the second transparent electrode pattern The front plate on which was formed was subjected to DC magnetron sputtering to obtain a front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed.
Insulating layer formed using the first transparent electrode pattern, the photocurable composition of Example 1, using a commercially available etching resist in the same manner as the formation of the first and second transparent electrode patterns. A front plate on which a pattern, a second transparent electrode pattern, and an etching resist pattern were formed was obtained. (Post-bake treatment; 130 ° C. for 30 minutes).
Further, in the same manner as in the formation of the first transparent electrode pattern, etching (30 ° C. for 50 seconds) is performed, and the etching resist layer is removed (45 ° C. for 200 seconds), whereby the mask layer and the first transparent electrode pattern are removed. In addition, an insulating layer pattern formed using the photocurable composition of Example 1, a second transparent electrode pattern, and a front plate on which conductive elements different from the first and second transparent electrode patterns were formed were obtained. .
＜透明保護層の形成＞
　絶縁層の形成と同様にして、上記第一及び第二の透明電極パターンとは別の導電性要素まで形成した前面板に、実施例１の光硬化性組成物を塗布・乾燥（膜厚１μｍ、９０℃１２０秒）し、光硬化性組成物膜を得た。更に、露光マスクを介さずに露光量５０ｍＪ／ｃｍ2（ｉ線）で前面露光し、現像、ポスト露光（１，０００ｍＪ／ｃｍ2）、ポストベーク処理を行って、マスク層、第一の透明電極パターン、実施例１の光硬化性組成物を用いて形成した絶縁層パターン、第二の透明電極パターン、第一及び第二の透明電極パターンとは別の導電性要素の全てを覆うように実施例１の光硬化性組成物を用いて形成した絶縁層（透明保護層）を積層した前面板を得た。 <Formation of transparent protective layer>
In the same manner as the formation of the insulating layer, the photocurable composition of Example 1 was applied and dried (film thickness: 1 μm) on the front plate formed up to the conductive element different from the first and second transparent electrode patterns. , 90 ° C. for 120 seconds) to obtain a photocurable composition film. Furthermore, 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 The electrode pattern, the insulating layer pattern formed using the photocurable composition of Example 1, the second transparent electrode pattern, and all the conductive elements different from the first and second transparent electrode patterns are covered. The front board which laminated | stacked the insulating layer (transparent protective layer) formed using the photocurable composition of Example 1 was obtained.
＜画像表示装置（タッチパネル）の作製＞
　特開２００９－４７９３６公報に記載の方法で製造した液晶表示素子に、先に製造した前面板を貼り合わせ、公知の方法で静電容量型入力装置を構成要素として備えた画像表示装置を作製した。 <Production of image display device (touch panel)>
The liquid crystal display device manufactured by the method described in Japanese Patent Application Laid-Open No. 2009-47936 was bonded to the previously manufactured front plate, and an image display device including a capacitive input device as a constituent element was manufactured by a known method. .
＜前面板、及び、画像表示装置の評価＞
　第一の透明電極パターン、第二の透明電極パターン、及び、これらとは別の導電性要素の、各々の導電性には問題がなく、一方で、第一の透明電極パターンと第二の透明電極パターンの間では絶縁性を有してあり、タッチパネルとして良好な表示特性が得られた。更に、第一及び第二の透明電極パターンは視認されにくく、表示特性に優れた画像表示装置が得られた。 <Evaluation of front plate and image display device>
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and other conductive elements, while the first transparent electrode pattern and the second transparent electrode pattern Between the electrode patterns, there was insulation, and good display characteristics as a touch panel were obtained. Furthermore, the first and second transparent electrode patterns were hardly visible and an image display device having excellent display characteristics was obtained.
（実施例４０）
－転写材料の作製－
　厚さ７５μｍのポリエチレンテレフタレートフィルム仮支持体の上に、スリット状ノズルを用いて、下記処方Ｈ１からなる熱可塑性樹脂層用塗布液を塗布、乾燥させた。次に、下記処方Ｐ１からなる中間層用塗布液を塗布、乾燥させた。更に、実施例４の光硬化性組成物を塗布、乾燥させ、仮支持体の上に乾燥膜厚が１４．６μｍの熱可塑性樹脂層と、乾燥膜厚が１．６μｍの中間層と、乾燥膜厚が１μｍの硬化性樹脂層を設け、保護フイルム（厚さ１２μｍポリプロピレンフィルム）を圧着した。
　こうして仮支持体と熱可塑性樹脂層と中間層（酸素遮断膜）と硬化性樹脂層とが一体となった転写材料Ｔ１を作製した。 (Example 40)
-Production of transfer material-
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, the photocurable composition of Example 4 was applied and dried, and a thermoplastic resin layer with a dry film thickness of 14.6 μm, an intermediate layer with a dry film thickness of 1.6 μm, A curable resin layer having a thickness of 1 μm was provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded.
Thus, a transfer material T1 in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the curable resin layer were integrated was produced.
＜熱可塑性樹脂層用塗布液：処方Ｈ１＞
　・メタノール：１１．１部
　・プロピレングリコールモノメチルエーテル：６．３６部
　・メチルエチルケトン：５２．４部
　・メチルメタクリレート／２－エチルヘキシルアクリレート／ベンジルメタクリレート／メタクリル酸共重合体（共重合組成比（モル比）＝５５／３０／１０／５、分子量＝１０万、Ｔｇ≒７０℃）：５．８３部
　・スチレン／アクリル酸共重合体（共重合組成比（モル比）＝６５／３５、分子量＝１万、Ｔｇ≒１００℃）：１３．６部
・ビスフェノールＡにペンタエチレングリコールモノメタクリートを２当量脱水縮合した化合物（新中村化学（株）製ＢＰＥ－５００）：９.１部
・フッ素系ポリマー（Ｃ6Ｆ13ＣＨ2ＣＨ2ＯＣＯＣＨ＝ＣＨ2 ４０部と、Ｈ（Ｏ（ＣＨ3）ＣＨＣＨ2）7ＯＣＯＣＨ＝ＣＨ2　５５部と、Ｈ（ＯＣＨＣＨ2）7ＯＣＯＣＨ＝ＣＨ2　５部との共重合体、分子量３万、メチルイソブチルケトン３０％溶液、ＤＩＣ（株）製、商品名：メガファックＦ７８０Ｆ）：０．５４部 <Coating liquid for thermoplastic resin layer: Formulation H1>
Methanol: 11.1 parts Propylene glycol monomethyl ether: 6.36 parts Methyl ethyl ketone: 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio)) = 55/30/10/5, molecular weight = 100,000, Tg≈70 ° C.): 5.83 parts Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 65/35, molecular weight = 10,000 , Tg≈100 ° C.): 13.6 parts Compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (BPE-500, Shin-Nakamura Chemical Co., Ltd.): 9.1 parts Fluoropolymer ( and C 6 F 13 CH 2 CH 2 OCOCH = CH 2 40 parts, H (O (CH 3) CHCH 2) and 7 OCOCH = CH 2 55 parts H (OCHCH 2) 7 copolymer of OCOCH = CH 2 5 parts, molecular weight 30,000, 30% methyl isobutyl ketone solution, DIC (trade name) manufactured by: Megafac F780F): 0.54 parts
＜中間層用塗布液：処方Ｐ１＞
　・ＰＶＡ２０５（ポリビニルアルコール、クラレ（株）製、鹸化度＝８８％、重合度５５０）：３２．２部
　・ポリビニルピロリドン（ＢＡＳＦ社製、Ｋ－３０）：１４．９部
　・蒸留水：５２４部
　・メタノール：４２９部 <Intermediate layer coating solution: Formulation P1>
PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, polymerization degree 550): 32.2 parts Polyvinylpyrrolidone (manufactured by BASF, K-30): 14.9 parts Distilled water: 524 parts・ Methanol: 429 parts
＜転写及び画像の形成＞
　無アルカリガラス基板を、２５℃に調整したガラス洗浄剤液をシャワーにより２０秒間吹き付けながらナイロン毛を有する回転ブラシで洗浄し、純水シャワー洗浄後、シランカップリング液（Ｎ－β（アミノエチル）γ－アミノプロピルトリメトキシシラン０．３％水溶液、商品名：ＫＢＭ６０３、信越化学工業（株）製）をシャワーにより２０秒間吹き付け、純水シャワー洗浄した。この基板を基板予備加熱装置で１００℃２分加熱して次のラミネーターに送った。
　上記転写材料Ｔ１の保護フイルムを剥離後、ラミネーター（（株）日立テクノエンジニアリング製）を用い、上記１００℃に加熱した基板に、ゴムローラー温度１３０℃、線圧１００Ｎ／ｃｍ、搬送速度２．２ｍ／分でラミネートした。
　仮支持体を剥離したところ、仮支持体と熱可塑性樹脂層の間できれいに剥離し、ガラスに硬化性樹脂層／中間層／熱可塑性樹脂層が転写したサンプルが得られた。 <Transfer and image formation>
A non-alkali glass substrate is washed with a rotating brush having nylon bristles while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering. After washing with pure water, silane coupling solution (N-β (aminoethyl) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water by shower. This substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device and sent to the next laminator.
After peeling off the protective film of the transfer material T1, a substrate heated to 100 ° C. using a laminator (manufactured by Hitachi Techno Engineering Co., Ltd.), rubber roller temperature 130 ° C., linear pressure 100 N / cm, conveyance speed 2.2 m Laminated at / min.
When the temporary support was peeled off, the sample was peeled cleanly between the temporary support and the thermoplastic resin layer, and a sample in which the curable resin layer / intermediate layer / thermoplastic resin layer was transferred to glass was obtained.
　この転写サンプルにつき、ｇｈｉ線高圧水銀灯露光機を用いて、エネルギー強度２０ｍＷ／ｃｍ2、２００ｍＪ／ｃｍ2にて、ラインアンドスペース１：１の１％～６０％グラデーション付きマスクを介して露光した。その後、１１０℃で９０秒の加熱処理を行った。
　次に、トリエタノールアミン系現像液（２．５％のトリエタノールアミン含有、ノニオン界面活性剤含有、ポリプロピレン系消泡剤含有、商品名：Ｔ－ＰＤ１、富士フイルム（株））にて３０℃５０秒、フラットノズル圧力０．０４ＭＰａでシャワー現像し熱可塑性樹脂層と酸素遮断膜を除去した。
　次に、２．３８質量％のテトラメチルアンモニウムヒドロキシド水溶液により２３℃で１５秒間浸液盛り法にて硬化性樹脂層を現像し、更に超純水で１０秒間リンスすることにより、上記マスクパタ－ンに対応したラインアンドスペースパタ－ンを得た。得られたパタ－ンの解像性は液材料として評価した実施例１と同等であり、本材料が転写材料としても有効であることが確認できた。 This transfer sample was exposed through a 1% to 60% gradation mask with a line-and-space ratio of 1: 1 with an energy intensity of 20 mW / cm 2 and 200 mJ / cm 2 using a ghi-line high-pressure mercury lamp exposure machine. Thereafter, heat treatment was performed at 110 ° C. for 90 seconds.
Next, 30 ° C. in a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, FUJIFILM Corporation) Shower development was carried out for 50 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier film.
Next, the curable resin layer was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds and rinsed with ultrapure water for 10 seconds. A line and space pattern corresponding to the pattern was obtained. The resolution of the obtained pattern was equivalent to that of Example 1 evaluated as a liquid material, and it was confirmed that this material was also effective as a transfer material.
　１：ＴＦＴ（薄膜トランジスター）、２：配線、３：絶縁膜、４：平坦化膜、５：第一電極、６：ガラス基板、７：コンタクトホール、８：絶縁膜、１０：液晶表示装置、１２：バックライトユニット、１４，１５：ガラス基板、１６：ＴＦＴ、１７：硬化膜、１８：コンタクトホール、１９：ＩＴＯ透明電極、２０：液晶、２２：カラーフィルター、３０：静電容量型入力装置、３１：前面板、３２：マスク層、３３：第一の透明電極パターン、３３ａ：パッド部分、３３ｂ：接続部分、３４：第二の透明電極パターン、３５：絶縁層、３６：導電性要素、３７：透明保護層、３８：開口部 1: 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

Claims (18)

  1. 　（成分Ａ）２つ以上の窒素原子を有する複素環化合物、
    　（成分Ｂ）金属酸化物粒子、
    　（成分Ｃ）溶剤、及び、
    　（成分Ｘ）硬化性成分を含有し、
    　成分Ａが、下記式（１）で表される化合物であることを特徴とする
    　光硬化性組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式（１）中、Ｒ1及びＲ2はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アリール基、又は、メルカプト基を表し、Ｒ1とＲ2とが結合して二価の有機基であってもよく、Ｒ3及びＲ4はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、又は、ヘテロ環基を表し、Ｌ1は５員環又は６員環を形成する二価の連結基を表し、Ｒ3又はＲ4とＬ1とが結合して環を形成していてもよく、また、点線の結合は、点線で記載した含窒素二重結合が存在する場合は、Ｒ2及びＲ4が存在しないことを表し、点線で記載した含窒素二重結合が存在しない場合は、Ｒ2及びＲ4が存在することを表す。）     (Component A) a heterocyclic compound having two or more nitrogen atoms,
    (Component B) metal oxide particles,
    (Component C) solvent, and
    (Component X) contains a curable component,
    Component A is a compound represented by following formula (1), The photocurable composition characterized by the above-mentioned.
    Figure JPOXMLDOC01-appb-C000001
     (In Formula (1), R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, or a mercapto group, and R 1 and R 2 are bonded to each other. R 3 and R 4 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and L 1 represents a 5-membered ring or It represents a divalent linking group that forms a 6-membered ring, and R 3 or R 4 and L 1 may be bonded to form a ring, and the dotted bond is the nitrogen-containing divalent bond described by the dotted line. When a double bond is present, R 2 and R 4 are not present, and when a nitrogen-containing double bond indicated by a dotted line is not present, R 2 and R 4 are present.)
  2. 　成分Ａの複素環の環員が、炭素原子及び窒素原子よりなる、請求項１に記載の光硬化性組成物。 The photocurable composition according to claim 1, wherein the ring member of the heterocycle of component A is composed of a carbon atom and a nitrogen atom.
  3. 　成分Ａが、メルカプト基又はチオキソ基を有する、請求項１又は２に記載の光硬化性組成物。 The photocurable composition according to claim 1 or 2, wherein Component A has a mercapto group or a thioxo group.
  4. 　成分Ａが、下記式（１－１）又は式（１－２）で表される化合物である、請求項１～３のいずれか１項に記載の光硬化性組成物。
    Figure JPOXMLDOC01-appb-C000002
     （式（１－１）及び式（１－２）中、Ｒ6～Ｒ8はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、又は、ヘテロ環基を表し、Ｌ2及びＬ3はそれぞれ独立に、５員環又は６員環を形成する二価の連結基を表し、Ｒ6とＬ2とが結合して環を形成していてもよく、Ｒ7又はＲ8とＬ3とが結合して環を形成していてもよい。）     The photocurable composition according to any one of claims 1 to 3, wherein component A is a compound represented by the following formula (1-1) or formula (1-2).
    Figure JPOXMLDOC01-appb-C000002
     (In Formula (1-1) and Formula (1-2), R 6 to R 8 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group; 2 and L 3 each independently represents a divalent linking group forming a 5-membered ring or a 6-membered ring, and R 6 and L 2 may be bonded to form a ring, and R 7 or R 3 8 and L 3 may be bonded to form a ring.)
  5. 　成分Ａの分子量が、１，０００以下である、請求項１～４のいずれか１項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 4, wherein the molecular weight of component A is 1,000 or less.
  6. 　成分Ｂの含有量が、組成物の全固形分に対し、３０質量％以上である、請求項１～５のいずれか１項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 5, wherein the content of component B is 30% by mass or more based on the total solid content of the composition.
  7. 　（成分Ｄ）分散剤を更に含む、請求項１～６のいずれか１項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 6, further comprising (Component D) a dispersant.
  8. 　成分Ｘとして、（成分Ｅ）重合性化合物、及び、（成分Ｆ）重合開始剤を含む、請求項１～７のいずれか１項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 7, comprising (Component E) a polymerizable compound and (Component F) a polymerization initiator as Component X.
  9. 　成分Ｘとして、（成分Ｍ）アルカリ可溶性樹脂、（成分Ｎ）架橋剤、及び、（成分Ｏ）酸発生剤を含む、請求項１～７のいずれか１項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 7, comprising (Component M) an alkali-soluble resin, (Component N) a crosslinking agent, and (Component O) an acid generator as Component X.
  10. 　支持体上に、請求項１～９のいずれか１項に記載の光硬化性組成物を少なくとも１層製膜させてなる、転写材料。 A transfer material comprising at least one layer of the photocurable composition according to any one of claims 1 to 9 formed on a support.
  11. 　少なくとも工程（ａ）～（ｃ）をこの順に含む硬化物の製造方法。
    　（ａ）請求項１～９のいずれか１項に記載の光硬化性組成物を基板上に塗布する塗布工程
    　（ｂ）塗布された組成物から溶剤を除去する溶剤除去工程
    　（ｃ）溶剤が除去された組成物に活性光線を照射する露光工程     A method for producing a cured product comprising at least steps (a) to (c) in this order.
    (A) an application step of applying the photocurable composition according to any one of claims 1 to 9 on a substrate; (b) a solvent removal step of removing the solvent from the applied composition; An exposure step of irradiating the removed composition with actinic rays
  12. 　少なくとも工程（１）～（４）をこの順に含む樹脂パターン製造方法。
    　（１）請求項１～９のいずれか１項に記載の光硬化性組成物を基板上に塗布する塗布工程
    　（２）塗布された組成物から溶剤を除去する溶剤除去工程
    　（３）溶剤が除去された組成物を活性光線によりパターン状に露光する露光工程
    　（４）未露光部の組成物を水性現像液により除去して現像する現像工程     A resin pattern manufacturing method comprising at least steps (1) to (4) in this order.
    (1) Application step of applying the photocurable composition according to any one of claims 1 to 9 on a substrate (2) Solvent removal step of removing the solvent from the applied composition (3) An exposure step in which the removed composition is exposed in a pattern with actinic rays (4) A development step in which the unexposed portion of the composition is removed with an aqueous developer and developed.
  13. 　請求項１１に記載の硬化物の製造方法、又は、請求項１２に記載の樹脂パターン製造方法により得られた硬化物。 The hardened | cured material obtained by the manufacturing method of the hardened | cured material of Claim 11, or the resin pattern manufacturing method of Claim 12.
  14. 　請求項１～９のいずれか１項に記載の光硬化性組成物を硬化してなる硬化膜。 A cured film obtained by curing the photocurable composition according to any one of claims 1 to 9.
  15. 　層間絶縁膜である、請求項１４に記載の硬化膜。 The cured film according to claim 14, which is an interlayer insulating film.
  16. 　請求項１４又は１５に記載の硬化膜を有する液晶表示装置。 A liquid crystal display device having the cured film according to claim 14 or 15.
  17. 　請求項１４又は１５に記載の硬化膜を有する有機ＥＬ表示装置。 An organic EL display device having the cured film according to claim 14 or 15.
  18. 　請求項１４又は１５に記載の硬化膜を有するタッチパネル表示装置。 A touch panel display device having the cured film according to claim 14 or 15.
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