WO2013065693A1 - 感光性樹脂組成物、これを用いた感光性エレメント、硬化物、画像表示装置の隔壁の形成方法、画像表示装置の製造方法及び画像表示装置 - Google Patents

感光性樹脂組成物、これを用いた感光性エレメント、硬化物、画像表示装置の隔壁の形成方法、画像表示装置の製造方法及び画像表示装置 Download PDF

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WO2013065693A1
WO2013065693A1 PCT/JP2012/078061 JP2012078061W WO2013065693A1 WO 2013065693 A1 WO2013065693 A1 WO 2013065693A1 JP 2012078061 W JP2012078061 W JP 2012078061W WO 2013065693 A1 WO2013065693 A1 WO 2013065693A1
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Prior art keywords
image display
meth
component
display device
resin composition
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PCT/JP2012/078061
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English (en)
French (fr)
Japanese (ja)
Inventor
真弓 佐藤
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日立化成株式会社
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Priority to JP2013541788A priority Critical patent/JP5920357B2/ja
Publication of WO2013065693A1 publication Critical patent/WO2013065693A1/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
    • G02F1/1675—Constructional details
    • G02F1/1679—Gaskets; Spacers; Sealing of cells; Filling or closing of cells
    • G02F1/1681—Gaskets; Spacers; Sealing of cells; Filling or closing of cells having two or more microcells partitioned by walls, e.g. of microcup type

Definitions

  • the present invention relates to a photosensitive resin composition, a photosensitive element using the same, a cured product, a method for forming partition walls of an image display device, a method for manufacturing an image display device, and an image display device.
  • an image display device (PLD: Paper Like Display) that is as thin as paper, can be freely carried, and can display characters and images has attracted attention.
  • PLD Paper Like Display
  • Such an image display device has visibility and portability, which are the advantages of paper as a normal printed matter, and is capable of electrically rewriting information, so that it can be used as a substitute for paper from the viewpoint of environment and cost. Practical application is being attempted.
  • Non-Patent Document 1 As the display technology of the image display device, various types such as a type in which particles are moved by electrophoresis, a liquid crystal type, and an electrochemical type have been devised (for example, see Non-Patent Document 1).
  • a type for moving particles methods such as a microcapsule electrophoresis method, a microcup electrophoresis method, an electronic powder fluid method, and a toner display have been studied.
  • white and black particles as a display medium are sealed between transparent electrodes, an electric field is applied, and these particles are electrically moved to form and display a white / black image.
  • active driving and passive driving as driving methods of the image display device, and a back technology (panel circuit) for the image display device has been studied.
  • a partition wall (a partition wall for separating pixels) for enclosing white / black particles as described above is required.
  • a method for forming such partition walls a mold transfer method, a screen printing method, a sand blast method, a photolithography method, an additive method, and the like have been proposed (for example, see Patent Document 1).
  • a photolithographic method that can form a high-definition pattern efficiently by irradiation with actinic rays using a photosensitive resin composition has attracted attention.
  • the partition of an image display device using a photolithographic method is a process of laminating a light shielding layer called a black matrix on a substrate by a photolithographic technique, applying a photosensitive resin composition on the light shielding layer, or laminating a photosensitive film. Is formed through a step of forming a photosensitive layer, a step of irradiating a predetermined portion of the photosensitive layer with actinic rays to form a photocured portion, and a step of removing an unexposed portion to form a photocured product pattern. . Therefore, in general, the photosensitive resin composition for forming the partition walls of the image display device is required to have sensitivity, resolution, and adhesion to the substrate.
  • the substrate to be used has shifted from a rigid substrate such as a glass substrate to a flexible substrate such as a PET substrate and an FPC substrate on which ITO is sputtered.
  • a voltage is applied under high temperature and high humidity.
  • Patent Documents 2 to 4 listed below are disclosed as photosensitive resin compositions for forming partition walls of an image display device.
  • JP 2007-178881 A JP 2010-066666 A JP 2010-169934 A JP 2010-256775 A
  • the present invention has been made in view of the above problems, and can reduce dissolution of an electrode substrate, and can form a partition wall for an image display device having a low elastic modulus and a high resolution and high adhesion.
  • An object of the present invention is to provide a photosensitive resin composition that can be used, a photosensitive element using the same, and a cured product.
  • Another object of the present invention is to provide a method for forming partition walls of an image display device, a method for manufacturing the image display device, and an image display device using the photosensitive resin composition, the photosensitive element, or the cured product. .
  • the present invention provides a photosensitive resin composition for forming partition walls of an image display device,
  • the photosensitive resin composition is (A) component: binder polymer, (B) component: a photopolymerizable compound, Component (C): photopolymerization initiator, (D) component: containing a compound having an epoxy group in the molecule,
  • the photosensitive resin composition of the present invention it is possible to reduce dissolution of the electrode substrate, the cured film (partition wall) has a low elastic modulus, and has high resolution and high adhesion.
  • a partition wall can be formed.
  • the said photosensitive resin composition can form a partition simply with sufficient workability
  • the photosensitive resin composition of the present invention preferably further contains an inorganic black pigment as the component (E). Thereby, the light-shielding property of the photosensitive resin composition improves.
  • the present invention also provides a photosensitive element comprising a support and a photosensitive layer containing the photosensitive resin composition formed on the support.
  • the thickness of the photosensitive layer is preferably 10 to 80 ⁇ m.
  • the photosensitive element can be easily used as a partition wall of an image display device.
  • this invention provides the hardened
  • cured material can be obtained by hardening the photosensitive resin composition of this invention with light and / or a heat
  • the present invention provides a lamination step of providing a photosensitive layer containing the photosensitive resin composition on a substrate, an exposure step of irradiating a predetermined portion of the photosensitive layer with an actinic ray to form a photocured portion, And a developing step of forming a photocured product pattern by removing portions other than the photocured portion.
  • this formation method it is possible to reduce dissolution of the electrode substrate, and it is possible to form a partition wall for an image display device having a low elastic modulus of the cured film and high resolution and high adhesion. .
  • the substrate preferably has flexibility.
  • the image display device on which the partition walls are formed becomes more flexible.
  • the method for forming the partition wall of the image display device of the present invention preferably further includes a heating step in which the photocured product pattern formed in the development step is heat-treated by heat treatment at 60 to 250 ° C.
  • the partition of the image display apparatus formed by this formation method hardens more.
  • the present invention also provides a method for manufacturing an image display device, comprising: a step of filling a display medium in the partition wall; and a step of attaching a substrate to the opposite side of the partition wall so as to face one substrate. To do.
  • the present invention provides an image display device manufactured by the above manufacturing method.
  • the present invention it is possible to reduce dissolution of the electrode substrate, and it is possible to easily and easily form a partition wall for an image display device having a low elastic modulus, a high resolution, and a high adhesion of the cured film.
  • a photosensitive resin composition and a photosensitive element using the same can be provided.
  • the formation method of the partition of an image display apparatus using the said photosensitive resin composition or photosensitive element, the manufacturing method of an image display apparatus, and an image display apparatus can be provided.
  • FIG. 3 is a schematic cross-sectional view showing a state where the image display device of FIG. 2 (e) is bent with a radius of curvature of about 5 to 15 mm.
  • (meth) acrylic acid means acrylic acid and methacrylic acid
  • (meth) acrylate means acrylate and the corresponding methacrylate
  • (meth) acryloyl means acryloyl and methacryloyl.
  • the photosensitive resin composition of the present embodiment comprises (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: epoxy group in the molecule.
  • the photosensitive resin composition of the present embodiment has the above-described configuration, so that the dissolution of the electrode substrate can be reduced, the elastic modulus of the cured film is low, and the image display has high resolution and high adhesion.
  • a partition for the device can be formed.
  • this inventor has guessed as follows. That is, a hydroxyl group in a copolymer having a structural unit based on a (meth) acrylic acid alkyl ester containing a hydroxyl group reacts with an isocyanate group in a (meth) acrylic acid alkyl ester containing an isocyanate group.
  • the binder polymer is a structural unit based on (meth) acrylic acid, a structural unit based on (meth) acrylic acid alkyl ester, a structural unit based on (meth) acrylic acid alkyl ester containing a hydroxyl group, and the urethane.
  • Binder Polymer (A) Component is a structural unit based on (meth) acrylic acid, a structural unit based on (meth) acrylic acid alkyl ester, and a structure based on (meth) acrylic acid alkyl ester containing a hydroxyl group
  • the binder polymer obtained by making the copolymer which has a unit and the (meth) acrylic-acid alkylester containing an isocyanate group react is included.
  • a copolymer having a structural unit based on (meth) acrylic acid, a structural unit based on (meth) acrylic acid alkyl ester, and a structural unit based on (meth) acrylic acid alkyl ester containing a hydroxyl group is (meth) acrylic acid.
  • (meth) acrylic acid alkyl ester and (meth) acrylic acid alkyl ester containing a hydroxyl group can be produced by radical polymerization.
  • the (meth) acrylic acid alkyl ester containing the hydroxyl group is not particularly limited as long as it reacts with the later-described isocyanate group-containing (meth) acrylic acid alkyl ester.
  • the content of the (meth) acrylic acid alkyl ester containing a hydroxyl group contained in the copolymer is preferably 1 to 40% by mass, based on the total mass of the copolymer, and 2 to 39% by mass. More preferably, it is 3 to 35% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 30% by mass.
  • Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and structural isomers thereof.
  • the (meth) acrylic acid alkyl ester containing the isocyanate group can be used without particular limitation as long as it reacts with the copolymer.
  • 2-isocyanate methyl (meth) acrylate, 2-isocyanate ethyl (meth) acrylate, 2-isocyanate propyl (meth) acrylate and 2-isocyanate octyl (meth) acrylate can be used.
  • 2-isocyanate ethyl (meth) acrylate and 2-isocyanate methyl (meth) acrylate are preferable.
  • the binder polymer may be prepared by reacting the above copolymer with an (meth) acrylic acid alkyl ester containing an isocyanate group under normal reaction conditions.
  • an (meth) acrylic acid alkyl ester containing an isocyanate group under normal reaction conditions.
  • the hydroxyl group of the (meth) acrylic acid alkyl ester containing a hydroxyl group and the isocyanate group in the (meth) acrylic acid alkyl ester containing an isocyanate group are 100. % Reaction is preferred.
  • the “alkyl” in the “(meth) acrylic acid alkyl ester” in the binder polymer is preferably a linear or branched alkyl group as in the exemplified compound described above, and the binder polymer has a cyclic structure. It is preferable that the structural unit is not included. For example, when a structural unit having a cyclic structure such as a cycloalkyl group is included, when the image display device is driven, the chargeability of the display medium is affected and the contrast tends to be adversely affected. Such a problem does not occur unless a structural unit having a structure is included. For the same reason, the binder polymer preferably does not contain a structural unit having a cyclic structure such as a structural unit based on styrene or a structural unit based on benzyl (meth) acrylate.
  • the weight average molecular weight of component (A) is excellent in developing solution resistance and is sufficient in functioning as a partition wall. Greater than 5,000, more preferably greater than 25,000, even more preferably greater than 30,000, particularly preferably greater than 35,000, and most preferably greater than 40,000. From the viewpoint of shortening the development time, it is preferably 300,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less.
  • the weight average molecular weight of the binder polymer is measured by gel permeation chromatography and converted using a standard polystyrene calibration curve. The measurement conditions for gel permeation chromatography (GPC) are the same as in the examples.
  • the content of the structural unit based on (meth) acrylic acid in the component (A) is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, based on the total mass of the molecule, More preferably, it is 25 mass%. In terms of excellent resolution, the content is preferably 5% by mass or more, and preferably 35% by mass or less from the viewpoint of electrode dissolution.
  • the content of the structural unit based on (A) component (meth) acrylic acid alkyl ester is preferably 5 to 80% by mass, more preferably 10 to 70% by mass based on the total mass of the molecule. More preferably, it is 20 to 60% by mass. In terms of excellent resolution, the content is preferably 5% by mass or more, and preferably 80% by mass or less from the viewpoint of electrode dissolution.
  • the content of the structural unit based on the (meth) acrylic acid alkyl ester containing a hydroxyl group in the component (A) is 5 to 30% by mass based on the total mass of the molecule from the viewpoint of reducing the elasticity of the cured film. It is preferably 10 to 30% by mass, more preferably 15 to 25% by mass.
  • the content of the structural unit based on the (meth) acrylic acid alkyl ester containing an isocyanate group is 5 to 35% by mass based on the total mass of the molecule from the viewpoint of electrode dissolution and low elasticity of the cured film. It is preferably 11 to 35% by mass, more preferably 17 to 29% by mass.
  • the content of the component (A) in the photosensitive resin composition is preferably 50 parts by mass or more in terms of excellent film formability with respect to 100 parts by mass of the total amount of the components (A) and (B), and 60 masses. Part or more is more preferable, and 65 parts by mass or more is still more preferable.
  • the content of the component (A) is preferably 90 parts by mass or less, and 80 parts by mass or less with respect to 100 parts by mass of the total amount of the components (A) and (B). Is more preferable, and 70 mass parts or less is still more preferable.
  • Component (B) Photopolymerizable compound
  • the component (B) that can be used in the present embodiment is not particularly limited as long as photocrosslinking is possible.
  • the component (B1) ethylenically Compound having saturated group and urethane bond
  • component (B2) Compound obtained by reacting polyhydric alcohol and / or glycidyl group-containing compound with ⁇ , ⁇ -unsaturated carboxylic acid
  • component (B3) ethylene in the molecule A compound having one ionic unsaturated bond.
  • Component (B1) Compound having an ethylenically unsaturated group and a urethane bond in the molecule It is preferable that component (B1) is included in that the elongation of the cured product can be improved and the adhesiveness to the flexible substrate is excellent. .
  • (B1) component which can be used in this embodiment, It is preferable to contain the compound which has an isocyanuric ring structure.
  • the compound which has an isocyanuric ring structure the compound represented by following General formula (1) is mentioned, for example.
  • each R 1 is independently a group represented by the following general formula (2), a group represented by the following general formula (3), or a group represented by the following general formula (4). And at least one of R 1 is a group represented by the following general formula (4). ]
  • R 2 represents a hydrogen atom or a methyl group, and m represents 1 to 15.
  • R 2 represents a hydrogen atom or a methyl group
  • n represents 1 to 9
  • m represents 1 to 15.
  • N and m represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the number of structural units is defined in the same manner.
  • At least two of R 1 in the general formula (1) are more preferably groups represented by the general formula (4), and all of R 1 are represented by the general formula.
  • a group represented by (4) is more preferable.
  • m is preferably 1 to 6 in terms of excellent chemical resistance.
  • m is preferably 3 to 6 in terms of excellent mechanical strength.
  • Examples of commercially available compounds represented by the above general formula (1) include, for example, NK Oligo UA-21EB (Shin Nakamura Chemical Co., Ltd., trade name, general formula (1), wherein R 1 is all represented by the general formula Compound (4)).
  • These compounds may be those synthesized by conventional methods, or commercially available ones may be used.
  • Examples of commercially available products include UF-8003M, UF-TCB-50, UF-TC4-55 (trade names, manufactured by Kyoeisha Chemical Co., Ltd.) and HT9082-95 (trade names, manufactured by Hitachi Chemical Co., Ltd.). Can be mentioned.
  • component (B1) other than the above for example, a (meth) acryl monomer having a hydroxyl group at the ⁇ -position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexa Addition reaction products with diisocyanate compounds such as methylene diisocyanate; EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate.
  • the EO-modified urethane di (meth) acrylate include UA-11 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).
  • Examples of EO and PO-modified urethane di (meth) acrylates include UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).
  • Content of the said (B1) component in the photosensitive resin composition is 100 mass of total amounts of (A) component and (B) component in the point which is excellent in film formation, the improvement of elongation of hardened
  • the amount is preferably 1 to 25 parts by weight, more preferably 5 to 25 parts by weight, and still more preferably 5 to 20 parts by weight.
  • Component (B2) Component obtained by reacting polyhydric alcohol and / or glycidyl group-containing compound with ⁇ , ⁇ -unsaturated carboxylic acid (B2)
  • Component includes, for example, polyethylene glycol di (meth) acrylate (ethylene group) Polyalkylene glycol di (meth) acrylates such as polypropylene glycol di (meth) acrylate (having 2 to 14 propylene groups); trimethylolpropane di (meth) acrylate, Trimethylolpropane (meth) acrylate compounds such as methylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane propoxytri (meth) acrylate; tetramethylolmethane tri (meth) acrylate, Tetramethylolmethane (meth) acrylate compounds such as lamethylolmethane tetra (meth) acryl
  • polyalkylene glycol di (meth) acrylate as (B2) component in the point which is excellent in the resolution and adhesiveness, maintaining the low elasticity of a cured film, and the following general formula (5), (6 It is more preferable that the compound represented by (7) or (7) is included.
  • R shows a hydrogen atom or a methyl group each independently
  • EO shows an oxyethylene group
  • PO shows an oxypropylene group.
  • m 1 , m 2 , m 3 and m 4 represent the number of structural units composed of oxyethylene groups
  • n 1 , n 2 , n 3 and n 4 represent the number of structural units composed of oxypropylene groups.
  • the total number of structural units m 1 + m 2 , m 3 and m 4 of the oxyethylene group independently represents 1 to 30, and the total number of structural units n 1 , n 2 + n 3 and n 4 of the oxypropylene group is Each independently represents 1 to 30.
  • the total number of structural units m 1 + m 2 , m 3 and m 4 of the oxyethylene group is each independently 1 to 30, Is preferably 10 to 10, more preferably 4 to 9, and still more preferably 5 to 8.
  • the total number of structural units is preferably 10 or less, more preferably 9 or less, and even more preferably 8 or less.
  • the total number of structural units n 1 , n 2 + n 3 and n 4 of the oxypropylene group is independently 1 to 30, preferably 5 to 20, more preferably 8 to 16, more preferably 10 More preferably, it is -14. In terms of excellent resolution improvement and sludge reduction, the total number of structural units is preferably 20 or less, more preferably 16 or less, and even more preferably 14 or less.
  • the content of the component (B2) in the photosensitive resin composition is 100 parts by mass of the total amount of the component (A) and the component (B) in terms of excellent resolution and adhesion while maintaining low elasticity of the cured film.
  • the amount is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 1 to 10 parts by mass.
  • Component (B3) Compound having one ethylenically unsaturated bond in the molecule (B3) Component is not particularly limited, but includes a compound represented by the following general formula (8) in terms of excellent resolution. It is preferable.
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents a hydrogen atom, a methyl group or a halogenated methyl group
  • R 5 represents an alkyl group having 1 to 6 carbon atoms
  • halogen It represents either an atom or a hydroxyl group
  • p represents 0-4.
  • Examples of the compound represented by the general formula (8) include ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ ′-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ ′-(meth).
  • Examples include acryloyloxyethyl-o-phthalate and ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, among which ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyl Oxyethyl-o-phthalate is preferred.
  • ⁇ -Chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (product name, manufactured by Hitachi Chemical Co., Ltd.).
  • the content of the component (B3) in the photosensitive resin composition is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) in terms of excellent resolution.
  • the amount is more preferably 1 to 10 parts by mass, and further preferably 1 to 7 parts by mass.
  • the component (B) can be used alone or in combination of two or more.
  • the content of the component (B) in the photosensitive resin composition is 15 to 45 masses with respect to 100 parts by mass of the total amount of the components (A) and (B), from the viewpoints of resolution, adhesion, and film formability.
  • the range is preferably in the range of 20 parts to 45 parts by weight.
  • Component (C) Photopolymerization initiator
  • the component (C) that can be used in the present invention is not particularly limited as long as it matches the light wavelength of the exposure machine to be used.
  • An aromatic ketone such as dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 2-ethylanthraquinone, Phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinon
  • substituents of the aryl groups of two 2,4,5-triarylimidazoles in the 2,4,5-triarylimidazole dimer may give the same and symmetrical compounds, or differently asymmetric Such compounds may be provided.
  • the component (C) preferably contains a benzyl derivative such as benzyl ketal in terms of excellent curability at the bottom of the resist after curing of the photosensitive resin composition.
  • a benzyl derivative such as benzyl ketal
  • an acridine derivative is included in the point which is excellent in sclerosis
  • both benzyl derivatives such as benzyl ketal and acridine derivatives are included in terms of excellent curability of the upper base.
  • the thickness of the layer containing the photosensitive resin composition increases, it is necessary to adjust the curability at the bottom of the resist and the curability at the top of the resist in a balanced manner.
  • the component (C) preferably contains an acridine derivative and a benzyl derivative, particularly 1,7-bis (9,9′-acridinyl) from the viewpoint of improving resolution and suppressing tailing of the resist after curing.
  • acridine derivative preferably contains 1,7-bis (9,9′-acridinyl) from the viewpoint of improving resolution and suppressing tailing of the resist after curing.
  • heptane and 2,2-dimethoxy-1,2-diphenylethane-1-one are included.
  • the content of the component (C) in the photosensitive resin composition is 0.1 parts by mass or more in terms of excellent photosensitivity with respect to 100 parts by mass of the total amount of the components (A) and (B). Preferably, it is 0.2 parts by mass or more. Moreover, content of (C) component is 20 mass parts or less in the point which is excellent in photocurability inside the photosensitive resin composition with respect to 100 mass parts of total amounts of (A) component and (B) component. It is preferable that it is 10 parts by mass or less.
  • the content thereof is 100 parts by mass with respect to the total amount of the components (A) and (B). From the viewpoint of excellent photosensitivity, it is preferably 0.05 to 1 part by mass, and more preferably 0.1 to 0.5 part by mass.
  • 2,2-dimethoxy-1,2-diphenylethane-1-one when included as the component (C), the content thereof is 100 parts by mass in total of the components (A) and (B). On the other hand, 1 mass part or more is preferable and 2 mass parts or more is more preferable in the point which is excellent in a photosensitivity and adhesiveness.
  • the content of 2,2-dimethoxy-1,2-diphenylethane-1-one is preferably 10 parts by mass or less, more preferably 5 parts by mass or less from the viewpoint of suppressing outgassing in the heat treatment step. preferable.
  • Component (D) Compound having an epoxy group in the molecule
  • Examples of the component (D) that can be used in this embodiment include compounds having an epoxy group (oxirane ring) in the molecule.
  • Examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F type epoxy resins such as bisphenol F diglycidyl ether, and bisphenol S type epoxy such as bisphenol S diglycidyl ether.
  • Resin biphenol type epoxy resin such as biphenol diglycidyl ether, bixylenol type epoxy resin such as bixylenol diglycidyl ether, hydrogenated bisphenol A type epoxy resin such as hydrogenated bisphenol A glycidyl ether, dicyclopentadiene type epoxy resin, cresol Examples thereof include novolak type epoxy resins and dibasic acid-modified diglycidyl ether type epoxy resins.
  • Examples of bisphenol F diglycidyl ether include Epicoat 807 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.).
  • Examples of bisphenol S diglycidyl ether include EBPS-200 (trade name, manufactured by Nippon Kayaku Co., Ltd.). , Epicron EXA-1514 (manufactured by DIC Corporation, trade name) and the like.
  • biphenol diglycidyl ether examples include YL-6121 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.).
  • bixylenol diglycidyl ether examples include YX-4000 (product manufactured by Japan Epoxy Resin Co., Ltd., product). Name).
  • examples of the hydrogenated bisphenol A glycidyl ether include ST-2004 and ST-2007 (both manufactured by Tohto Kasei Co., Ltd., trade names) and the like.
  • examples of the dicyclopentadiene type epoxy resin Epicron HP-7200L (Product name) manufactured by DIC Corporation, and the like.
  • cresol novolac type epoxy resins include Epicron N-665-EXP, Epicron N-670-EXP-S (Product name, manufactured by DIC Corporation) and the like. Can be mentioned.
  • Examples of the dibasic acid-modified diglycidyl ether type epoxy resin include ST-5100 and ST-5080 (both manufactured by Tohto Kasei Co., Ltd.).
  • dicyclopentadiene type epoxy resin and cresol novolac type epoxy resin are preferable, and cresol novolak type epoxy resin is more preferable in terms of suppressing dissolution of the electrode.
  • the said (D) component can be used individually or in combination of 2 or more types.
  • the content of the component (D) in the photosensitive resin composition is preferably 5 parts by mass or more in terms of suppressing dissolution of the electrode with respect to 100 parts by mass of the total amount of the components (A) and (B). More than mass part is more preferable.
  • the content of the component (D) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less, from the viewpoint that the photosensitive resin composition is excellent in film formability.
  • Component (E) Inorganic black pigment
  • examples of the component (E) that can be used in the present invention include titanium black, carbon black, and cobalt black, which have good light transmittance at wavelengths of 360 nm and 405 nm. In this respect, titanium black is preferable.
  • the content of the component (E) in the photosensitive resin composition is preferably 0.1 parts by mass or more in terms of excellent light shielding properties with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferably 2 parts by mass or more.
  • the content of the component (E) is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less in terms of excellent adhesion and resolution.
  • the photosensitive resin composition of the present embodiment exhibits excellent rust prevention effects, residual film prevention effects, and film adhesion effects without corroding copper and copper alloys such as metal wirings and metal layers, ITO, IZO and the like. It is preferable that the component (F) includes a heterocyclic compound.
  • the component (F) refers to a cyclic compound in which a ring is composed of two or more element atoms (in addition to carbon, nitrogen, oxygen, sulfur, etc.).
  • Heterocyclic compounds include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring , Pyrazine ring, piperidine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, compounds having a triazine ring, salts of these compounds, and the like.
  • compounds having a triazole ring, a pyrrole ring, a pyrazole ring, a thiazole ring, an imidazole ring and a tetrazole ring containing a carbon atom and a nitrogen atom, and salts of these compounds are preferred, and compounds having a triazole ring or a tetrazole ring and these It is more preferable to include a salt of the compound, and it is further preferable to include a compound having a triazole ring and a salt of these compounds.
  • heterocyclic compound (F) examples include 1,2,4-triazole, 1,2,3-triazole, 1,2,5-triazole, 4-amino-3,5- Dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2,4-triazole, 3-amino-5-isopropyl-1,2,4-triazole, 3- Amino-5-methyl-4H-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-amino-3,5-dimethyl-1,2,4-triazole, 3,5- Diamino-1H-1,2,4-triazole, benzotriazole, 5-methyl-1H-benzotriazole, 5,6-dimethylbenzotriazole, 5-amino-1H-benzotriazole, benzotrizol-4 Sulfonic acid, 1H-tetrazole, 5-methyl-1H-tetrazole, 5- (methylthio) -1H-tetrazol
  • heterocyclic compound of the component (F) is a tetrazole ring, it is preferably at least one selected from the group consisting of 1H-tetrazole, 5 substituted-1H-tetrazole, 1-substituted-1H-tetrazole and derivatives thereof. .
  • heterocyclic compound of component (F) is a triazole ring, 1,2,3-triazole, 1,2,4-triazole and its derivatives, 1,2,3-benzotriazole, 5-substituted-1H-benzo It is preferably selected from the group consisting of triazole, 6-substituted-1H-benzotriazole, 5,6-substituted-1H-benzotriazole and derivatives thereof. Among them, it is preferable to contain an amine salt of 4-methyl-1H benzotriazolone or an amine salt of 5-methyl-1H benzotriazolone (ANTAGE TDP (phenothiazine, trade name, manufactured by Kawaguchi Chemical Co., Ltd.)).
  • ANTAGE TDP phenothiazine, trade name, manufactured by Kawaguchi Chemical Co., Ltd.
  • the blending amount of the component (F) in the photosensitive resin composition is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferably, it is ⁇ 5 parts by mass.
  • the photosensitive resin composition of the present embodiment preferably contains a compound represented by the following general formula (9).
  • R 11 , R 12 , R 13 and R 14 each independently represent a hydrogen atom or a monovalent group represented by the following General Formula (10). ]
  • R 15 represents a hydrocarbon group having 4 to 30 carbon atoms.
  • R 11 to R 14 are a hydrogen atom or a monovalent group represented by the general formula (10).
  • R 11 to R 14 are distributed over R 11 to R 14.
  • the proportion of the monovalent group represented by the general formula (10) is preferably 10 to 80%, more preferably 20 to 50% in the general formula (9). If the distribution ratio of the group represented by the general formula (10) is within 80%, the resolution and the adhesion tend to be excellent, and if it is 10% or more, the antistatic effect tends to be excellent.
  • the total number of moles M OH of the hydroxyl groups of the compound represented by the general formula (9) contained an ester group (R 11 ⁇ R 14 is the general formula (10
  • the ratio [M OH / M ESTER ] to the total number of moles M ESTER of the monovalent group represented by) is preferably in the range of 0.1 to 4, preferably 0.25 to 1 It is more preferable to be within the range.
  • R 15 in the general formula (10) is a fatty acid having 4 to 30 carbon atoms.
  • An example of such a compound is diglycerin oleate. Oleic acid diglycerin is commercially available, for example, “Electro Stripper ME-1” and “Sunsulzer W-4120A” (trade name, manufactured by Kao Corporation).
  • the photosensitive resin composition of the present embodiment is represented by the general formula (9), and R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom or —CO—C 17 H 33 . It is preferable to contain a compound mixture in which the distribution ratio of —CO—C 17 H 33 in R 11 , R 12 , R 13 and R 14 is 10 to 80%. If the distribution ratio of —CO—C 17 H 33 is within 80%, the resolution and adhesion tend to be excellent, and if it is 10% or more, the antistatic effect tends to be excellent.
  • Examples of such a mixture include “Electro Stripper ME-1” (trade name, —CO—C 17 H 33 distribution ratio: 40%, manufactured by Kao Corporation) and “Sunsulzer W-4120A” (above (Trade name, distribution ratio of —CO—C 17 H 33 : 30%) manufactured by Kao Corporation is commercially available.
  • the compounding amount of the compound represented by the general formula (9) in the photosensitive resin composition is 100 parts by mass of the total amount of the component (A) and the component (B) in terms of further improving the antistatic effect and adhesion.
  • the amount is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 5 parts by mass.
  • the photosensitive resin composition containing the above components may further comprise a dye such as malachite green, a photochromic agent such as tribromophenyl sulfone or leuco crystal violet, a thermal color developing inhibitor, p-toluenesulfonamide.
  • a dye such as malachite green
  • a photochromic agent such as tribromophenyl sulfone or leuco crystal violet
  • a thermal color developing inhibitor p-toluenesulfonamide.
  • plasticizers pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc.
  • Each component and component (B) can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass in total.
  • the photosensitive resin composition of the present embodiment containing the above components can be obtained, for example, by uniformly kneading and mixing the contained components with a roll mill, a bead mill or the like. If necessary, it can be dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof to obtain a solid content of 30 It can be used as a solution of about ⁇ 60% by mass.
  • a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof to obtain a solid content of 30 It can be used as
  • a method for forming a photosensitive layer on a substrate for an image display device using the obtained photosensitive resin composition is not particularly limited, but the photosensitive resin composition is applied as a liquid resist on the substrate and dried. Can be formed. Moreover, a protective film can be coat
  • the thickness of the photosensitive layer to be applied varies depending on the use, but the thickness after drying is preferably about 1 to 100 ⁇ m.
  • Examples of the protective film in the case where the protective film is used after being coated as a liquid resist include polymer films such as polyethylene and polypropylene.
  • FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention.
  • the photosensitive element 10 of the present embodiment includes a support 1, a photosensitive layer 2 made of the photosensitive resin composition formed thereon, and a protection formed on the photosensitive layer 2.
  • the protective film 3 is provided as needed.
  • a polymer film of polyethylene terephthalate, polypropylene, polyethylene, polyester, or the like can be preferably used as the support 1, for example, a polymer film of polyethylene terephthalate, polypropylene, polyethylene, polyester, or the like can be preferably used.
  • the thickness of the polymer film is preferably about 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, and still more preferably 10 to 30 ⁇ m.
  • the formation method of the photosensitive layer 2 on the support 1 is not particularly limited, but can be preferably carried out by applying and drying a solution of the photosensitive resin composition.
  • the thickness of the photosensitive layer 2 to be applied varies depending on the application, but is preferably about 1 to 100 ⁇ m after drying. When used as a partition wall of an image display device, the thickness of the photosensitive layer 2 is more preferably 10 to 90 ⁇ m after drying, and further preferably 10 to 80 ⁇ m.
  • Application can be performed by a known method such as a roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater, or the like. Drying can be performed at 70 to 150 ° C. for about 5 to 30 minutes. Further, the amount of the remaining organic solvent in the photosensitive layer 2 is preferably 2% by mass or less from the viewpoint of preventing the organic solvent from diffusing in the subsequent step.
  • the surface of the photosensitive layer 2 may be coated using the polymer film used as the support 1 as the protective film 3.
  • the protective film 3 preferably has a smaller adhesive strength between the photosensitive layer 2 and the protective film 3 than the adhesive strength between the photosensitive layer 2 and the support 1, and is preferably a low fisheye film. “Low fish eye” means that there are few foreign materials such as foreign materials, undissolved materials, oxidized degradation products, and the like in the film.
  • the photosensitive element 10 may have an intermediate layer and a protective layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer in addition to the photosensitive layer 2, the support 1 and the optional protective film 3. Good.
  • a protective layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer in addition to the photosensitive layer 2, the support 1 and the optional protective film 3. Good.
  • the manufactured photosensitive element 10 is usually stored by being wound around a cylindrical winding core. In addition, it is preferable to wind up so that the support body 1 may become an outer side at this time.
  • An end face separator is preferably installed on the end face of the roll-shaped photosensitive element roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance.
  • the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene polymer).
  • an electrode substrate 30 comprising an electrode 4 and a substrate 5 is prepared.
  • the above-described photosensitive element 10 is formed on the electrode substrate 30.
  • the photosensitive layer 2 and the support 1 are laminated (lamination step).
  • the substrate 5 constituting the electrode substrate 30 is not particularly limited as long as it is a flexible substrate, and examples thereof include an insulating substrate such as a polymer film substrate and a semiconductor substrate such as a silicon substrate.
  • Examples of the electrode substrate 30 include a substrate 5 on which a flexible electrode 4 such as ITO, IZO, and Ag wire ink is formed.
  • Examples of the method of forming the electrode 4 include a method of patterning an electrode material laminated by a method such as vapor deposition and sputtering using a photolithography method, a method of patterning a photosensitive electrode material, and the like. There are no particular restrictions on the method of forming this electrode 4.
  • a method of laminating the photosensitive layer 2 on the electrode substrate 30 in addition to the method using the photosensitive element 10 described above, a method of applying a solution of the photosensitive resin composition onto the electrode substrate 30 and drying can also be used. .
  • the photosensitive element 10 when the protective film 3 exists on the photosensitive layer 2, the photosensitive element 10 is laminated on the electrode substrate 30 while removing the protective film 3.
  • the photosensitive layer 2 is laminated to the electrode substrate 30 by being pressure-bonded onto the electrode substrate 30 at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm 2 ) while being heated to about 70 to 130 ° C. It is also possible to perform lamination under reduced pressure.
  • the surface of the electrode substrate 30 is usually formed with an electrode pattern, but may be flat or uneven as needed.
  • the photosensitive layer 2 is irradiated with an actinic ray 8 in an image shape to photocur the exposed portion (exposure process).
  • an actinic ray 8 in an image form As a method of irradiating actinic rays 8 in an image form, as shown in FIG. 2 (b), a mask pattern 7 is placed on the photosensitive layer 2 to irradiate actinic rays 8 in an image form, and a photosensitive layer in an exposed portion.
  • the mask pattern 7 may be a negative type or a positive type, and those generally used can be used.
  • a known light source for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used.
  • a direct drawing exposure method in which a pattern is directly drawn with a laser without using the mask pattern 7 can also be used.
  • the photocured material pattern 20 is formed on the substrate (electrode substrate 30) for the image display device by selectively removing the unexposed portion of the photosensitive layer 2 by development. It is formed (development process).
  • 3 and 4 show an example of the pattern of the photocured product.
  • FIG. 3 is a schematic plan view showing an example in which the partition walls in FIG. 2C are formed in a lattice shape
  • FIG. 4 is a schematic plan view showing an example in which the partition walls in FIG. 2C are formed in a hexagonal shape.
  • the substrate 5 is disposed under the electrode 4 and the photocured material pattern 20 as shown in FIG. 2C.
  • the electrode 4 may be an ITO electrode
  • the substrate 5 is a PET substrate. But you can.
  • the development step when the support 1 is present, the support 1 is removed prior to development.
  • Development is performed by removing unexposed portions by wet development, dry development, or the like using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent.
  • a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent.
  • the alkaline aqueous solution include 0.1 to 5% by mass sodium carbonate solution, 0.1 to 5% by mass potassium carbonate solution, and 0.1 to 5% by mass potassium hydroxide solution.
  • the pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive layer. Moreover, you may mix surfactant, an antifoamer, an organic solvent, etc. in alkaline aqueous solution.
  • the development method include a dip method, a spray method, brushing, and slapping. The spray method is preferable for improving the resolution.
  • the formed photocured product pattern 20 is further cured by a heat treatment at about 60 to 250 ° C. as necessary.
  • the curing temperature is preferably about 80 to 200 ° C., more preferably about 100 to 150 ° C.
  • the curing time is not particularly limited, but is preferably 10 minutes to 3 hours, and more preferably 30 minutes to 2 hours.
  • a display medium 50 such as particles is filled in the photocured product pattern 20 formed in the above development step.
  • a display medium An electronic powder body, pigment ink, a white fine particle, etc. are mentioned.
  • the space in the photocured material pattern 20 other than those is filled with air, an olefin solvent, silicone oil, or the like.
  • the step of attaching another electrode substrate 30 to the photocured material pattern 20 can be performed as follows. That is, in the above process, the adhesive 40 is laminated on the photocured material pattern 20 as shown in FIG. 2D, and the electrode substrate 30 and the photocured material are cured by the adhesive 40 as shown in FIG. This is done by adhering the object pattern 20.
  • the electrode substrate 30 may be directly bonded to the photocured material pattern 20 without using the adhesive 40.
  • a transparent electrode substrate is used at least for the electrode substrate on the display surface side of the image display device 100.
  • a preferable embodiment of the image display device 100 includes an embodiment in which a transparent glass substrate is used as the substrate 5 and a transparent ITO electrode is used as the electrode 4.
  • the image display device formed through the above-described steps includes an electrode substrate 30 having flexibility and a partition made of a photocured material pattern 20 having high elongation, and achieves excellent flexibility. Can do.
  • an image display device having a high degree of flexibility that can handle a curvature radius of about 5 to 15 mm can be obtained.
  • the partition formed using the photosensitive resin composition of the present invention can sufficiently suppress the occurrence of breakage even when the image display device is bent with a curvature radius of about 5 to 15 mm (see FIG. 5). ).
  • Example 1 to 3 and Comparative Examples 1 to 4 After blending the (B) component, (C) component, (D) component, (E) component, and other components shown in Table 1, the (A) component shown in Table 1 was added and dissolved therein. Photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 6 were obtained. The amount of each component (unit: g) is as shown in Table 1.
  • Binder polymer resin A A copolymer obtained by reacting 20 g of methacrylic acid, 30 g of methyl methacrylate, 30 g of butyl methacrylate and 20 g of 2-hydroxyethyl methacrylate is added to 2-isocyanate.
  • Binder polymer synthesis example 1 To a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 100 g of propylene glycol monomethyl ether acetate was added, stirred while blowing nitrogen gas, and heated to 100 ° C.
  • a solution prepared by dissolving 0.25 g of azobisisobutyronitrile in 12 g of propylene glycol monomethyl ether acetate was dropped into the flask over 5 minutes.
  • the solution after dropping was kept warm at 100 ° C. for 0.5 hours while stirring, then heated to 140 ° C. over 0.5 hours, and kept warm for 2 hours while stirring. Furthermore, it is cooled to 70 ° C. over 0.5 hours, stirred while switching from nitrogen gas to dry air, and mixed with 0.2 g of methoquinone, 0.02 g of dibutyltin laurate, and 25 g of propylene glycol monomethyl ether acetate. The mixture was kept at 70 ° C. for 0.5 hours with stirring.
  • binder polymer (resin A) was obtained.
  • the obtained binder polymer had a weight average molecular weight of 50,000.
  • the weight average molecular weight of the binder polymer was measured by gel permeation chromatography, and was derived by conversion using a standard polystyrene calibration curve.
  • the measurement conditions of gel permeation chromatography (GPC) are shown below.
  • solution b a solution in which 20 g of methacrylic acid, 45 g of methyl methacrylate, 35 g of butyl methacrylate and 3.5 g of azobisisobutyronitrile were mixed was prepared, and the solution b was added to the solution a for 4 hours. Then, the mixture was kept warm at 80 ° C. for 2 hours with stirring. Further, a solution prepared by dissolving 0.15 g of azobisisobutyronitrile in 6 g of ethylene glycol and 4 g of toluene was dropped into the flask over 40 minutes.
  • binder polymer (resin D).
  • the obtained binder polymer had a weight average molecular weight of 50,000.
  • Photopolymerizable compound HT-9082-95 (a photopolymerizable compound obtained by reacting a hydroxyl group-terminated polycarbonate compound, organic isocyanate and 2-hydroxyethyl acrylate: weight average molecular weight 4000, Hitachi Kasei Kogyo Co., Ltd., trade name) UA-21EB (Shin Nakamura Chemical Co., Ltd., trade name, compound in which R 1 is all represented by the general formula (4) in the above general formula (1))) FA-023M (trade name, manufactured by Hitachi Chemical Co., Ltd.) FA-024M (trade name, manufactured by Hitachi Chemical Co., Ltd.) FA-MECH (trade name, manufactured by Hitachi Chemical Co., Ltd.)
  • Component (D) Compound having an epoxy group in its molecule, Epicron N-670-EXP-S (cresol novolac type epoxy resin, DIC Corporation, trade name)
  • Nonen KY-TB ⁇ , ⁇ , ⁇ -tribromomethylphenylsulfone, Maruhishi Oil Chemical Co., Ltd., trade name
  • ANTAGE TDP phenothiazine, Kawaguchi Chemical Co., Ltd., trade name
  • Electro stripper ME-1 Specific surfactant, Kao Corporation, trade name
  • Florene DOPA-17HF disersant, Kyoeisha Chemical Co., Ltd., trade name
  • SH-193 leveling agent, Toray Dow Corning Co., Ltd., trade name
  • this photosensitive resin composition solution was uniformly applied onto a 16 ⁇ m thick polyethylene terephthalate film (trade name: FB-40, manufactured by Toray Industries, Inc.) and then dried for 10 minutes with a hot air convection dryer at 90 ° C.
  • the film was protected with a polyethylene protective film (tensile strength in the film longitudinal direction: 16 Mpa, tensile strength in the film width direction: 12 Mpa, trade name: NF-15, manufactured by Tamapoly Co., Ltd.) to obtain a photosensitive element.
  • the film thickness after drying of the photosensitive layer was 45 ⁇ m.
  • a phototool having a 41-step tablet and a phototool having a wiring pattern with a line width / space width of 30/30 to 200/200 (unit: ⁇ m) as a negative for resolution evaluation are adhered to the polyethylene terephthalate film of the laminate. Then, using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd.) EXM-1201 having a high-pressure mercury lamp, exposure was performed with an energy amount such that the number of remaining step stages after development of the 41-step step tablet was 29.0.
  • the polyethylene terephthalate film After exposure, the polyethylene terephthalate film is peeled off, and an unexposed portion is removed by spraying a 0.3% by mass sodium carbonate aqueous solution and 0.2% by mass nonal 912A (Toho Chemical Industries, trade name) at 26 ° C. for 90 seconds. And evaluated the resolution.
  • the resolution is represented by the smallest space width ( ⁇ m) in which the unexposed portion is well removed by the development process, and the smaller this value, the better the resolution. Table 2 shows the evaluation results.
  • the photosensitive element is placed on the ITO surface of an ITO-TEG (Test Element Group) substrate through a laminating roll heated to 110 ° C. while peeling the protective film made of polyethylene so that the photosensitive layer is in contact with the ITO-TEG substrate surface. Laminated. From the bottom, the structure of the obtained laminate was an ITO-TEG substrate, a photosensitive layer, and a polyethylene terephthalate film. A phototool having a 41-step tablet is closely attached to the laminated polyethylene terephthalate film, and the number of remaining steps after development is measured using a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp.
  • EXM-1201 manufactured by Oak Manufacturing Co., Ltd.
  • Exposure was performed with an energy amount of 29.0. After the exposure, the polyethylene terephthalate film was peeled off, and a 0.3 mass (usually 1 mass%) sodium carbonate aqueous solution and 0.2 mass% nonal 912A (Toho Chemical Industries, trade name) were placed at 26 ° C. for 90 seconds (previous 30 ° C. For 20 seconds) to remove the unexposed areas. Thereby, the evaluation board
  • a box-type dryer manufactured by Mitsubishi Electric Corporation, model number: NV50-CA
  • Table 2 shows the evaluation results.
  • A indicates that the resistance value can be measured and it is determined that there is no disconnection due to dissolution
  • B indicates that it is impossible to measure and it is determined that there is disconnection due to dissolution.
  • ultraviolet irradiation (ultraviolet irradiation degree: 2 J / cm 2 ) was performed using an ultraviolet irradiation device (Toshiba Electric Materials Co., Ltd., rated voltage 200 V, rated power consumption 7.2 kW).
  • the polyethylene terephthalate film was peeled off and allowed to stand in a box-type dryer (Mitsubishi Electric Corporation, model number: NV50-CA) heated to 120 ° C. for 60 minutes.
  • the photosensitive element after heat treatment was cut into a width of 10 mm, the distance between chucks was 50 mm, and the tensile elastic modulus (N / m 2 ) was determined at a constant speed of 2 cm / min. Table 2 shows the evaluation results.
  • the above-mentioned photosensitive element is placed on a polytetrafluoroethylene sheet (manufactured by Nitto Denko Corporation, product name: Nitoflon film No. 900U), and a protective film made of polyethylene so that the photosensitive layer is in contact with the surface of the polytetrafluoroethylene sheet.
  • a laminating roll heated to 110 ° C.
  • the composition of the obtained laminate was in the order of a polytetrafluoroethylene sheet, a photosensitive layer, and a polyethylene terephthalate film.
  • the obtained evaluation sheet was allowed to stand for 1 hour in a box-type dryer (Mitsubishi Electric Corporation, model number: NV50-CA, air atmosphere) heated to 120 ° C.
  • the evaluation sheet after the heat treatment is cut out to a width of 10 mm, the distance between chucks is set to 50 mm, and the cured product of the photosensitive layer is pulled at a constant speed of 2 cm / min until the cured product breaks. )
  • Table 2 shows the evaluation results.
  • Examples 1 to 3 had no electrode dissolution, low elasticity, good elongation, and excellent sensitivity, resolution, and adhesion.
  • Comparative Examples 1 to 6 were inferior in at least one of electrode solubility, elastic modulus, elongation, sensitivity, resolution, and adhesion.
  • the present invention it is possible to reduce dissolution of the electrode substrate, and it is possible to easily and easily form a partition wall for an image display device having a low elastic modulus, a high resolution, and a high adhesion of the cured film.
  • a photosensitive resin composition, a photosensitive element using the same, and a cured product can be provided.
  • cured material, the manufacturing method of an image display apparatus, and an image display apparatus can be provided. .

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PCT/JP2012/078061 2011-11-01 2012-10-30 感光性樹脂組成物、これを用いた感光性エレメント、硬化物、画像表示装置の隔壁の形成方法、画像表示装置の製造方法及び画像表示装置 WO2013065693A1 (ja)

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