WO2011155412A1 - Photosensitive resin composition, photosensitive element comprising the composition, method for formation of septum for image display device, process for production of image display device, and image display device - Google Patents
Photosensitive resin composition, photosensitive element comprising the composition, method for formation of septum for image display device, process for production of image display device, and image display device Download PDFInfo
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- WO2011155412A1 WO2011155412A1 PCT/JP2011/062831 JP2011062831W WO2011155412A1 WO 2011155412 A1 WO2011155412 A1 WO 2011155412A1 JP 2011062831 W JP2011062831 W JP 2011062831W WO 2011155412 A1 WO2011155412 A1 WO 2011155412A1
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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
- G03F7/027—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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/165—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
- G02F1/166—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 characterised by the electro-optical or magneto-optical effect
- G02F1/167—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 characterised by the electro-optical or magneto-optical effect by electrophoresis
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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
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/027—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
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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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
Definitions
- the present invention relates to a photosensitive resin composition, a photosensitive element using the same, 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 method 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 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.
- Non-Patent Document 2 Recently, there are also reports on realizing full color display by examining the flexibility of image display devices and combining color filters with white / black image display (for example, see Non-Patent Document 2).
- ITO Indium Tin Oxide
- ITO alternatives such as IZO (Indium Zinc Oxide), Ag wire ink, and organic conductive materials have been studied.
- IZO Indium Zinc Oxide
- Various degrees of flexibility have been studied, from those that can be flexed to those that can be rounded down and reduced in volume when carried.
- the radius of curvature in the case of small rounding is generally assumed to be about 15 to 20 mm, which is the limit of flexibility of the ITO electrode substrate, but about 5 to 15 mm for Ag wire ink, organic conductive material, and combinations thereof. The radius of curvature can be reduced up to.
- a color filter is used in combination with a white / black display image display device, so it is essential to improve the contrast between pixels. Therefore, a light shielding layer for shielding light between the pixels is required.
- a light shielding layer for shielding light between the pixels is required.
- monochrome display in order to increase the brightness of the image of the image display device without using a color filter, transparency rather than light shielding properties may be required.
- the partition wall of the image display device using the photolithography method is formed as follows. That is, a step of laminating a light shielding layer called a black matrix on a substrate by photolithography technology, and further forming a photosensitive resin composition layer by applying a photosensitive resin composition on the light shielding layer or laminating a photosensitive element. And a step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to photocure the exposed portion and a step of removing the unexposed portion to form a photocured product pattern. Note that a light shielding layer called a black matrix may be omitted. 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.
- IZO which has been studied as a flexible electrode substrate, contains amphoteric metal zinc, so that it has a problem of being dissolved in the step of attaching the electrode substrate.
- an electrode material having a high degree of flexibility and capable of handling a curvature radius of about 5 to 15 mm for example, an Ag wire ink, an organic conductive material, or a combination thereof is used as the electrode material, There was a problem of being damaged.
- the present invention has been made in view of the above problems, and a photosensitive resin composition capable of forming a partition wall that can suppress dissolution of an electrode and suppress breakage during bending, and a photosensitive resin using the same. It is an object to provide a conductive element, a method for forming a partition wall of an image display device, a method for manufacturing the image display device, and an image display device.
- the present invention provides a photosensitive resin composition for forming a partition separating pixels in a flexible image display device having a transparent electrode on at least a display surface
- the photosensitive resin composition comprises (A) component: binder polymer having a carboxyl group in the molecule, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: molecule.
- a sheet-like cured product having a width of 10 mm and a thickness of 45 ⁇ m, comprising a compound having an epoxy group therein, photocuring the photosensitive resin composition, and heating at 120 ° C. for 1 hour in air,
- a photosensitive resin composition having an elongation at 25 ° C. of 40% or more is provided.
- the photosensitive resin composition having the above-described configuration it is possible to form a partition wall that can suppress breakage during bending while suppressing dissolution of the electrode, which is a problem when forming the partition wall of the image display device. Moreover, according to the said photosensitive resin composition, the photocured material pattern excellent in the resolution and adhesiveness can be formed with a sufficient sensitivity. Although the detailed reason why dissolution of the electrode is suppressed by the photosensitive resin composition having the above configuration is not clear, the (D) component traps the carboxyl group remaining in the cured product of the photosensitive resin composition. It is thought that dissolution of the electrode is suppressed.
- the breakage of the partition walls at the time of bending is suppressed by reducing the crosslink density of the cured product of the photosensitive resin composition and adjusting the elongation rate to be in the above range, thereby bending the image display device. This is considered to be because it is possible to follow the elongation without breaking the partition wall.
- the photosensitive resin composition of the present invention even when the image display device is bent with a curvature radius of about 5 to 15 mm, it is possible to form a partition wall that can sufficiently suppress the occurrence of breakage.
- the photosensitive resin composition of the present invention may further contain (E) component: an inorganic black pigment. Moreover, it is preferable that the said (E) component contains titanium black.
- the conflicting characteristics of photosensitivity and light shielding property can be maintained in a well-balanced manner.
- a photosensitive resin composition for forming a partition wall containing no inorganic black pigment (component (E)) and a photosensitive element using the same are required. Therefore, what is necessary is just to add (E) component as needed.
- the present invention also provides a photosensitive element comprising a support and a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention formed on the support.
- a photosensitive element comprising a support and a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention formed on the support.
- the present invention is also a method for forming a partition wall of an image display device having flexibility, comprising at least a transparent electrode disposed on a display surface and a partition wall for separating pixels, on the substrate of the image display device, A lamination step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention, and an exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to photocure an exposed portion; And a developing step of forming a photocured product pattern by removing a portion other than the exposed portion of the photosensitive resin composition layer.
- the present invention further relates to a method for manufacturing a flexible image display device comprising at least a transparent electrode disposed on a display surface and a partition wall for separating pixels, and the partition wall of the image display device according to the present invention is formed.
- a method for manufacturing an image display device comprising the step of forming the partition wall by a method.
- the partition wall is formed by the above-described photosensitive resin composition of the present invention, dissolution of the electrode when forming the partition wall is suppressed.
- a partition wall that can suppress breakage during bending can be formed.
- the transparent electrode is preferably made of a material formed by applying a solution containing at least one type of metal conductive fiber.
- the electrode material include Ag wire and ink.
- the photosensitive resin composition of the present invention is a photosensitive resin composition for forming a partition for separating pixels in a flexible image display device having a transparent electrode on at least a display surface, wherein (A) Component: Contains a binder polymer having a carboxyl group in the molecule, (B) component: a photopolymerizable compound, (C) component: a photopolymerization initiator, and (D) component: a compound having an epoxy group in the molecule. And after photocuring the said photosensitive resin composition, the elongation rate in 25 degreeC of the sheet-like hardened
- binder polymers examples include two or more types of binder polymers composed of different copolymer components, two or more types of binder polymers having different weight average molecular weights, two or more types of binder polymers having different degrees of dispersion, and the like. Can be mentioned.
- a polymer having a multimode molecular weight distribution described in JP-A-11-327137 can also be used.
- the binder polymer may have a photosensitive group as necessary.
- an acrylic copolymer containing methacrylic acid, methyl methacrylate, and butyl methacrylate is preferable in terms of excellent developability and resolution.
- the acid value can be measured as follows. That is, first, about 1 g of a resin solution whose acid value is to be measured is precisely weighed, and then 30 g of acetone is added to this resin solution to dissolve it uniformly. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. And an acid value is computed by following Formula.
- the content of the component (A) in the photosensitive resin composition is 40 parts by mass in terms of excellent coating properties of the photosensitive resin composition with respect to 100 parts by mass of the total amount of the components (A) and (B).
- the above is preferable, and 45 parts by mass or more is more preferable.
- 70 mass parts or less are preferable with respect to 100 mass parts of total amounts of (A) component and (B) component, and 60 mass parts or less are more preferable.
- (B) Component Photopolymerizable Compound
- the component (B) that can be used in the present invention is not particularly limited as long as it can be photocrosslinked.
- the component (B1) ethylenically unsaturated in the molecule Compound having group and urethane bond
- Component (B2) Compound obtained by reacting polyalcohol and / or glycidyl group-containing compound with ⁇ , ⁇ -unsaturated carboxylic acid
- Component (B3) ethylenic in the molecule A compound having one unsaturated bond may be mentioned.
- 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. .
- 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 an integer of 1 to 15.
- m is an integer of 1-15.
- R 2 represents a hydrogen atom or a methyl group
- n represents an integer of 1 to 9
- m represents an integer of 1 to 15.
- 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 an integer of 1 to 6 in terms of excellent chemical resistance.
- m is preferably an integer of 3 to 6 from the viewpoint 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.
- Examples of the EO-modified urethane di (meth) acrylate include product name UA-11 manufactured by Shin-Nakamura Chemical Co., Ltd.
- Examples of the EO, PO-modified urethane di (meth) acrylate include product name UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd.
- 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
- 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 repeating structural units composed of oxyethylene groups
- n 1 , n 2 , n 3 and n 4 represent the number of repeating structural units composed of oxypropylene groups.
- the total number of repeating oxyethylene groups m 1 + m 2 , m 3 and m 4 each independently represents an integer of 1 to 30, and the total number of repeating oxypropylene groups n 1 , n 2 + n 3 and n 4 are independent Represents an integer of 1 to 30.
- the total number of repeating oxyethylene groups m 1 + m 2 , m 3 and m 4 are each independently an integer of 1 to 30, It is preferably an integer of 1 to 10, more preferably an integer of 4 to 9, and still more preferably an integer of 5 to 8. In terms of excellent resolution and adhesion, the total number of repetitions is preferably 10 or less, more preferably 9 or less, and even more preferably 8 or less.
- the total number of repeating oxypropylene groups n 1 , n 2 + n 3 and n 4 is each independently an integer of 1 to 30, preferably an integer of 5 to 20, and preferably an integer of 8 to 16. Is more preferable, and an integer of 10 to 14 is more preferable. In terms of excellent resolution improvement and sludge reduction, the total number of repetitions is preferably 20 or less, more preferably 16 or less, and even more preferably 14 or less.
- 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 an integer of 0 to 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 component (B) can be used alone or in combination of two or more.
- the crosslink density of the cured product of the photosensitive resin composition can be adjusted mainly by a combination of the above-described components (A) and (B).
- the elongation rate at 25 ° C. of the sheet-like cured product having a width of 10 mm and a thickness of 45 ⁇ m heated at 120 ° C. for 1 hour in air is 40%.
- the photosensitive resin composition of the present invention even when the image display device is bent with a curvature radius of about 5 to 15 mm, it is possible to form a partition wall that can sufficiently suppress the occurrence of breakage.
- 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
- 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. In addition, with respect to 100 parts by mass of the total amount of the component (A) and the component (B), it is preferably 20 parts by mass or less, and preferably 10 parts by mass or less in terms of excellent photocurability inside the photosensitive resin composition. It is more preferable that
- the content thereof is 100 parts by mass in total of the components (A) and (B).
- 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.
- it is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.
- Component (D) Compound having an epoxy group in the molecule
- Examples of the component (D) that can be used in the present invention include compounds having an epoxy group (oxirane ring) in the molecule.
- 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.
- 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. Moreover, 10 mass parts or less are preferable at the point which is excellent in adhesiveness and resolution, and 5 mass parts or less are more preferable.
- 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.
- Plasticizers such as, pigments other than black, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc.
- Each component (A) and component (B) can be contained in an amount of about 0.01 to 20 parts by mass per 100 parts by mass in total. These can be used alone or in combination of two or more.
- the photosensitive resin composition of the present invention 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 resin composition 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 used as a liquid resist on the substrate.
- a method of applying and drying can be used.
- a protective film can be coat
- the protective film used as a liquid resist and coated with a protective film after coating include polymer films such as polyethylene and polypropylene.
- the cured product is formed into a sheet having a width of 10 mm and a thickness of 45 ⁇ m, and the cured product is obtained at a constant speed of 25 ° C., a distance between chucks of 50 mm, and a speed of 2 cm / min.
- the method of obtaining the elongation percentage (%) when pulled until it breaks by the following formula is used.
- Elongation rate (%) ⁇ (length at break-initial length) / initial length ⁇ ⁇ 100
- the photosensitive resin composition is formed by forming a photosensitive resin composition layer composed of the photosensitive resin composition on a transparent electrode, photocuring the photosensitive resin composition layer, and then at 120 ° C. in air. It is preferable that the wire is not disconnected when a direct voltage of 80 V is applied to the transparent electrode for 100 hours under conditions of 60 ° C. and 90% RH after heating for 1 hour.
- the photo-curing of the photosensitive resin composition layer is performed by exposing with a necessary energy amount when forming the partition using the photosensitive resin composition layer, and developing as necessary.
- the amount of energy is preferably an amount of energy at which the number of remaining step stages after development of the 41-step step tablet is 29.0.
- the resistance value of the anode is measured with a tester, and those that can be measured are determined not to be broken by melting, and those that are not measurable are determined to be broken due to melting. For those that can be measured, the rate of increase from the initial resistance value can also be obtained.
- 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 invention includes a support 1, a photosensitive resin composition layer 2 made of the photosensitive resin composition formed thereon, and a photosensitive resin composition layer.
- 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.
- 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 support body 1 is transparent, when exposing to the photosensitive resin composition layer 2, since exposure can be performed through the support body 1, it is preferable.
- the formation method of the photosensitive resin composition layer 2 on the support 1 is not particularly limited, it can be preferably carried out by applying and drying a solution of the photosensitive resin composition.
- the thickness of the photosensitive resin composition layer to be applied varies depending on the required properties, but the thickness after drying is preferably about 10 to 100 ⁇ m, more preferably 20 to 100 ⁇ m, and more preferably 30 to 100 ⁇ m. It is more preferable that the thickness is 40 to 100 ⁇ 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, for example, at 70 to 150 ° C. for about 2 to 30 minutes. Moreover, it is preferable that the amount of the residual organic solvent in the photosensitive resin composition layer 2 shall be 2 mass% or less from the point which prevents the spreading
- a protective film 3 may be laminated on the photosensitive resin composition layer 2 formed on the support 1 to cover the surface of the photosensitive resin composition layer 2.
- the protective film 3 has a smaller adhesive force between the photosensitive resin composition layer 2 and the protective film 3 than the adhesive force between the photosensitive resin composition layer 2 and the support 1.
- an olefin film such as polyethylene or polypropylene or a polyester film typified by polyethylene terephthalate is used.
- a polyester film is used as the support 1 and the same kind of polyester film is used for the protective film 3, it is preferable to use a protective film 3 whose surface is in contact with the photosensitive resin composition layer.
- the protective film 3 is preferably a low fish eye film.
- fish eye means that foreign materials, undissolved materials, oxidatively deteriorated materials, etc. of the material are contained in the film when the material is melted by heat, kneaded, extruded, biaxially stretched, casting method, etc. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.
- the photosensitive element 10 has 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 resin composition layer 2, the support 1 and the optional protective film 3. You may do it.
- 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 resin composition layer 2, the support 1 and the optional protective film 3. You may do it.
- the manufactured photosensitive element 10 is usually stored by being wound around a cylindrical winding core. At this time, it is preferable that the support 1 is wound up so as to be on the outside.
- 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.
- edge fusion refers to a phenomenon in which the photosensitive resin composition layer 2 oozes out from the end face, which is also called cold flow. When this phenomenon occurs, it becomes a foreign matter generation source when forming the partition wall, which is an undesirable phenomenon.
- the material of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer).
- 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 resin composition 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 for laminating the photosensitive resin composition 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 it. It can also be used.
- the photosensitive element 10 when the protective film 3 is present on the photosensitive resin composition layer 2, the photosensitive element 10 is laminated on the electrode substrate 30 while removing the protective film 3.
- the lamination condition for example, the photosensitive resin composition layer 2 is heated to about 70 to 130 ° C. and pressed onto the electrode substrate 30 at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm 2 ).
- the method of laminating by doing, etc. are mentioned, It is also possible to laminate
- the surface of the electrode substrate 30 is usually formed with an electrode pattern, but may be flat or uneven as needed.
- the photosensitive resin composition layer 2 After lamination of the photosensitive resin composition layer 2, as shown in FIG. 2 (b), the photosensitive resin composition layer 2 is irradiated with an actinic ray 8 in the form of an image, and the exposed portion is photocured (exposure process). .
- a mask pattern 7 As a method of irradiating the actinic light 8 in an image form, as shown in FIG. 2B, a mask pattern 7 is placed on the photosensitive resin composition layer 2 and the actinic ray 8 is irradiated in an image form for exposure. There is a method of photocuring a part of the photosensitive resin composition layer 2.
- 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 photosensitive resin composition layer 2 in the unexposed area is selectively removed by development to be photocured on the substrate for the image display device (electrode substrate 30).
- An object pattern 20 is formed (development process). In 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.
- an alkaline aqueous solution examples include a dilute solution of 0.1 to 5% by mass sodium carbonate, a dilute solution of 0.1 to 5% by mass potassium carbonate, a dilute solution of 0.1 to 5% by mass potassium hydroxide, and the like.
- 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 resin composition layer.
- Examples of 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.
- 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.
- a transparent electrode substrate is used at least for the electrode substrate on the display surface side of the image display device.
- 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 cope with 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.
- Examples 1 to 4 and Comparative Examples 1 to 5 After blending the (A) component, (B) component, (C) component, (E) component, and other components shown in Table 1, the (D) component shown in Table 1 was added and dissolved therein. Photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were obtained. The amount of each component (unit: g) is as shown in Table 1.
- Photopolymerizable compound * 3 a photopolymerizable compound obtained by reacting a hydroxyl group-terminated polycarbonate compound, organic isocyanate and 2-hydroxyethyl acrylate (weight average molecular weight 4000, Hitachi Chemical Co., Ltd.) (Product name: HT-9082-95) * 4; UA-21EB (made by Shin-Nakamura Chemical Co., Ltd., trade name) * 5; FA-023M (trade name, manufactured by Hitachi Chemical Co., Ltd.) * 6: FA-024M (trade name, manufactured by Hitachi Chemical Co., Ltd.) * 7; ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl-o-phthalate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-MECH)
- (E) component inorganic black pigment * 19; titanium black dispersion (manufactured by Gemco, trade name: BT-1HCA)
- pigment dispersant manufactured by Kyoeisha Chemical Co., Ltd., trade name: Floren DOPA-17HF
- Methacryloyloxypropyltrimethoxysilane made by Toray Dow Corning Co., Ltd., trade name: SZ-6030
- the obtained photosensitive resin composition solution was uniformly applied onto a 16 ⁇ m-thick polyethylene terephthalate film (manufactured by Teijin DuPont Films, trade name: HTR-02), and hot air convection drying at 90 ° C.
- the photosensitive resin composition layer was formed by drying with a machine for 10 minutes.
- the photosensitive resin composition layer 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, manufactured by Tamapoly Co., Ltd., trade name: NF-15).
- a photosensitive element was obtained.
- the film thickness after drying of the photosensitive resin composition layer was 45 ⁇ m.
- the above photosensitive element is placed on the ITO surface of a PET substrate with ITO (trade name: R-300, manufactured by Toyobo Co., Ltd.) so that the photosensitive resin composition layer is in contact with the surface of the PET substrate with ITO.
- the film was laminated through a laminating roll heated to 110 ° C. while peeling off the protective film. From the bottom, the structure of the obtained laminate is a PET substrate with ITO, a photosensitive resin composition layer, and a polyethylene terephthalate film.
- the obtained laminate was evaluated for sensitivity, adhesion, resolution, and goby folding.
- Adhesion is represented by the width ( ⁇ m) of the smallest line that remains without being peeled off by the developer. The smaller the value, the tighter the line is, without peeling from the glass substrate. Is high. Table 2 shows the evaluation results.
- a parallel light exposure machine EXM-1201 manufactured by Oak Manufacturing Co., Ltd.
- the exposure was performed with an energy amount of 29.0 after the development of the 41-step tablet.
- the polyethylene terephthalate film was peeled off, and a 1% by mass sodium carbonate aqueous solution was sprayed at 30 ° C.
- the resolution is represented by the smallest space width ( ⁇ m) in which the unexposed portion is removed favorably by the development processing, and the smaller the numerical value, the better the resolution.
- Table 2 shows the evaluation results.
- the evaluation sheet thus obtained is folded, and the cured product of the photosensitive resin composition layer is not peeled off from the PET substrate with ITO, and no damage is seen, and the peeling is seen from the PET substrate with ITO, Alternatively, B was determined to be damaged.
- the photosensitive element On the IZO and ITO surfaces of an IZO-TEG (Test Element Group) substrate and an ITO-TEG (Test Element Group) substrate, the photosensitive element is composed of an IZO-TEG substrate and an ITO-TEG substrate, respectively.
- the film was laminated through a laminating roll heated to 110 ° C. while peeling off the polyethylene protective film so as to be in contact with the surface.
- the structure of the obtained laminate is a TEG substrate, a photosensitive resin composition layer, and a polyethylene terephthalate film from the bottom.
- 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. Exposure was performed with an energy amount of 29.0. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds to remove the unexposed portion of the photosensitive resin composition layer. Thereby, the evaluation board
- the obtained evaluation substrate was allowed to stand for 1 hour in a box-type dryer (manufactured by Mitsubishi Electric Corporation, model number: NV50-CA) heated to 120 ° C. Thereafter, under the conditions of 60 ° C. and 90% RH, a DC voltage of 80 V was applied to the electrode of the evaluation substrate, and the resistance value of the anode after 100 hours was measured with a tester.
- Table 2 shows the evaluation results. In the table, A indicates that the resistance value can be measured and it is determined that there is no disconnection due to dissolution, and B indicates that it is impossible to measure and it is determined that there is disconnection due to dissolution.
- a value obtained by dividing the resistance value of the anode after 100 hours by the initial resistance value and multiplying by 100 is indicated as a rate of increase in resistance (%). It can be evaluated that dissolution of the electrode is suppressed as the resistance increase rate is smaller.
- the photosensitive element is placed on a polytetrafluoroethylene sheet (manufactured by Nitto Denko Corporation, product name: Nitoflon Film No. 900U), so that the photosensitive resin composition layer is in contact with the surface of the polytetrafluoroethylene sheet.
- the film was laminated through a laminating roll heated to 110 ° C. while peeling off the polyethylene protective film.
- the structure of the obtained laminate is in the order of a polytetrafluoroethylene sheet, a photosensitive resin composition 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 was cut into a width of 10 mm, the distance between chucks was set to 50 mm, and the cured product of the photosensitive resin composition layer was pulled at a constant speed of 2 cm / min until the cured product of the photosensitive resin composition was broken. Elongation rate (%) was determined. Table 2 shows the evaluation results.
- a photosensitive film capable of forming a partition for an image display device capable of suppressing breakage during bending while suppressing dissolution of an electrode when a voltage is applied under high temperature and high humidity.
- a photosensitive resin composition, a photosensitive element using the same, a method for forming partition walls of an image display device, a method for manufacturing an image display device, and an image display device can be provided.
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Abstract
Description
本発明の感光性樹脂組成物は、少なくとも表示面に透明電極を備えた屈曲性を有する画像表示装置における、画素を分離する隔壁を形成するための感光性樹脂組成物であって、(A)成分:分子内にカルボキシル基を有するバインダーポリマー、(B)成分:光重合性化合物、(C)成分:光重合開始剤、及び、(D)成分:分子内にエポキシ基を有する化合物、を含有し、上記感光性樹脂組成物を光硬化させた後、空気下120℃で1時間加熱してなる幅10mm、厚さ45μmのシート状の硬化物の、25℃における伸び率が40%以上であることを特徴とするものである。 (Photosensitive resin composition)
The photosensitive resin composition of the present invention is a photosensitive resin composition for forming a partition for separating pixels in a flexible image display device having a transparent electrode on at least a display surface, wherein (A) Component: Contains a binder polymer having a carboxyl group in the molecule, (B) component: a photopolymerizable compound, (C) component: a photopolymerization initiator, and (D) component: a compound having an epoxy group in the molecule. And after photocuring the said photosensitive resin composition, the elongation rate in 25 degreeC of the sheet-like hardened | cured material of width 10mm and thickness 45micrometer formed by heating at 120 degreeC in air for 1 hour is 40% or more. It is characterized by being.
本発明に用いることのできる(A)成分としては、分子内にカルボキシル基を有し、フィルム性を付与できるものであれば特に制限なく、例えば、アクリル系樹脂、スチレン系樹脂、エポキシ系樹脂、アミド系樹脂、アミドエポキシ系樹脂、アルキド系樹脂、フェノール系樹脂、ウレタン系樹脂が挙げられる。中でも、アクリル系樹脂が、アルカリ現像性の観点からは好ましい。これらは単独で、又は二種類以上を組み合わせて用いることができる。二種類以上のバインダーポリマーの組み合わせの例としては、異なる共重合成分からなる二種類以上のバインダーポリマー、異なる重量平均分子量の二種類以上のバインダーポリマー、異なる分散度の二種類以上のバインダーポリマー等が挙げられる。また、特開平11-327137号公報記載のマルチモード分子量分布を有するポリマーを用いることもできる。なお、必要に応じて、バインダーポリマーは感光性基を有していてもよい。 (A) component: binder polymer having a carboxyl group in the molecule (A) component that can be used in the present invention is not particularly limited as long as it has a carboxyl group in the molecule and can impart film properties. Examples thereof include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, and urethane resins. Among these, acrylic resins are preferable from the viewpoint of alkali developability. These can be used alone or in combination of two or more. Examples of combinations of two or more types of binder polymers include two or more types of binder polymers composed of different copolymer components, two or more types of binder polymers having different weight average molecular weights, two or more types of binder polymers having different degrees of dispersion, and the like. Can be mentioned. In addition, a polymer having a multimode molecular weight distribution described in JP-A-11-327137 can also be used. In addition, the binder polymer may have a photosensitive group as necessary.
式中、Aは酸価(mgKOH/g)を示し、Vfは0.1NのKOH水溶液の滴定量(mL)を示し、Wpは測定した樹脂溶液の質量(g)を示し、Iは測定した樹脂溶液中の不揮発分の割合(質量%)を示す。 A = 10 × Vf × 56.1 / (Wp × I)
In the formula, A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of a 0.1N KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I was measured. The ratio (mass%) of the non volatile matter in a resin solution is shown.
ポンプ:日立 L-6000型(株式会社日立製作所製)
カラム:Gelpack GL-R420 + Gelpack GL-R430 +
Gelpack GL-R440(計3本)(以上、日立化成工業株式会社製、商品名)溶離液:テトラヒドロフラン
測定温度:25℃
流量:2.05mL/分
検出器:日立 L-3300型RI(株式会社日立製作所製) [GPC measurement conditions]
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.)
Column: Gelpack GL-R420 + Gelpack GL-R430 +
Gelpack GL-R440 (three in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.) Eluent: Tetrahydrofuran Measurement temperature: 25 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)
本発明に用いることのできる(B)成分としては、光架橋が可能であれば特に制限はないが、例えば、(B1)成分:分子内にエチレン性不飽和基及びウレタン結合を有する化合物、(B2)成分:多価アルコール及び/又はグリシジル基含有化合物にα,β-不飽和カルボン酸を反応させて得られる化合物、(B3)成分:分子内にエチレン性不飽和結合を1つ有する化合物が挙げられる。 (B) Component: Photopolymerizable Compound The component (B) that can be used in the present invention is not particularly limited as long as it can be photocrosslinked. For example, the component (B1): ethylenically unsaturated in the molecule Compound having group and urethane bond, Component (B2): Compound obtained by reacting polyalcohol and / or glycidyl group-containing compound with α, β-unsaturated carboxylic acid, Component (B3): ethylenic in the molecule A compound having one unsaturated bond may be mentioned.
硬化物の伸びを向上させることができ、フレキシブル基板への密着性に優れる点では、(B1)成分を含むことが好ましい。 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. .
(B2)成分としては、例えば、ポリエチレングリコールジ(メタ)アクリレート(エチレン基の数が2~14のもの)、ポリプロピレングリコールジ(メタ)アクリレート(プロピレン基の数が2~14のもの)等のポリアルキレングリコールジ(メタ)アクリレート;トリメチロールプロパンジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパンエトキシトリ(メタ)アクリレート、トリメチロールプロパンプロポキシトリ(メタ)アクリレート等のトリメチロールプロパン(メタ)アクリレート化合物;テトラメチロールメタントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート等のテトラメチロールメタン(メタ)アクリレート化合物;ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等のジペンタエリスリトール(メタ)アクリレート化合物;ビスフェノールAジオキシエチレンジ(メタ)アクリレート、ビスフェノールAトリオキシエチレンジ(メタ)アクリレート、ビスフェノールAデカオキシエチレンジ(メタ)アクリレート等のビスフェノールAジオキシエチレンジ(メタ)アクリレート;トリメチロールプロパントリグリシジルエーテルトリアクリレート及びビスフェノールAジグリシジルエーテルアクリレートが挙げられる。 Component (B2): Compound obtained by reacting polyhydric alcohol and / or glycidyl group-containing compound with α, β-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) acrylate; dipentaerythritol (meth) acrylate compounds such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; bisphenol A di Bisphenol A dioxyethylene di (meth) acrylate such as oxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate; trimethylolpropane triglycidyl ether triacrylate And bisphenol A diglycidyl ether acrylate.
(B3)成分としては、特に制限はないが、解像度に優れる点では、下記一般式(8)で表される化合物を含むことが好ましい。 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.
本発明に用いることのできる(C)成分としては、使用する露光機の光波長にあわせたものであれば特に制限はなく、具体的には例えば、ベンゾフェノン、N,N’-テトラメチル-4,4’-ジアミノベンゾフェノン(ミヒラーケトン)、N,N’-テトラエチル-4,4’-ジアミノベンゾフェノン、4-メトキシ-4’-ジメチルアミノベンゾフェノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノ-プロパノン-1等の芳香族ケトン;2-エチルアントラキノン、フェナントレンキノン、2-tert-ブチルアントラキノン、オクタメチルアントラキノン、1,2-ベンズアントラキノン、2,3-ベンズアントラキノン、2-フェニルアントラキノン、2,3-ジフェニルアントラキノン、1-クロロアントラキノン、2-メチルアントラキノン、1,4-ナフトキノン、9,10-フェナンタラキノン、2-メチル-1,4-ナフトキノン、2,3-ジメチルアントラキノン等のキノン類;ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインフェニルエーテル等のベンゾインエーテル化合物;ベンゾイン、メチルベンゾイン、エチルベンゾイン等のベンゾイン化合物;1-(4-メトキシフェニル)-2,2-ジメトキシ-2-フェニルエタン-1-オン、1-(4-メトキシフェニル)-2-メトキシ-2-エトキシ-2-フェニルエタン-1-オン、1-(4-メトキシフェニル)-2-メトキシ-2-プロポキシ-2-フェニルエタン-1-オン、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(通称ベンジルジメチルケタール)等のベンジルケタール等のベンジル誘導体;9-フェニルアクリジン、1,7-ビス(9,9’-アクリジニル)ヘプタン等のアクリジン誘導体;N-フェニルグリシン、N-フェニルグリシン誘導体;クマリン系化合物;2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-クロロフェニル)-4,5-ジ(メトキシフェニル)イミダゾール二量体、2-(o-フルオロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体、2-(p-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体等のイミダゾール二量体;が挙げられる。また、2,4,5-トリアリールイミダゾール二量体における2つの2,4,5-トリアリールイミダゾールのアリール基の置換基は、同一で対称な化合物を与えてもよいし、相違して非対称な化合物を与えてもよい。また、ジエチルチオキサントンとジメチルアミノ安息香酸の組み合わせのように、チオキサントン系化合物と3級アミン化合物とを組み合わせてもよい。これらは、単独で、又は二種類以上を組み合わせて用いることができる。 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. Specifically, for example, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2 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-benzanthraquinone, 2, -Benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, Quinones such as 2,3-dimethylanthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; 1- (4-methoxyphenyl) -2 , 2-Dimethoxy-2-phenylethane-1-one, 1- (4-methoxyphenyl) -2-methoxy-2-ethoxy-2-phenylethane-1-one, 1- (4-methoxyphenyl) -2 -Methoxy-2-pro Benzyl derivatives such as benzyl ketal such as xyl-2-phenylethane-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one (commonly called benzyldimethyl ketal); 9-phenylacridine, 1,7 -Acridine derivatives such as bis (9,9'-acridinyl) heptane; N-phenylglycine, N-phenylglycine derivatives; coumarin compounds; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2 -(O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4 , 5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Imidazole dimer and the like; and the like. In addition, the 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. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. These can be used alone or in combination of two or more.
本発明で用いることのできる(D)成分としては、分子内にエポキシ基(オキシラン環)を有する化合物が挙げられる。 Component (D): Compound having an epoxy group in the molecule Examples of the component (D) that can be used in the present invention include compounds having an epoxy group (oxirane ring) in the molecule.
本発明で用いることのできる(E)成分としては、例えば、チタンブラック、カーボンブラック、コバルトブラックが挙げられ、波長360nm及び405nmの光の透過性が良好である点で、チタンブラックが好ましい。 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.
伸び率(%)={(破断時の長さ-初期の長さ)/初期の長さ}×100 As a specific method for measuring the elongation rate of the cured product, the cured product is formed into a sheet having a width of 10 mm and a thickness of 45 μm, and the cured product is obtained at a constant speed of 25 ° C., a distance between chucks of 50 mm, and a speed of 2 cm / min. The method of obtaining the elongation percentage (%) when pulled until it breaks by the following formula is used.
Elongation rate (%) = {(length at break-initial length) / initial length} × 100
図1は、本発明の感光性エレメントの好適な一実施形態を示す模式断面図である。図1に示すように、本発明の感光性エレメント10は、支持体1と、その上に形成された上記感光性樹脂組成物からなる感光性樹脂組成物層2と、感光性樹脂組成物層2上に形成された保護フィルム3と、を備える。なお、保護フィルム3は、必要に応じて設けられる。 (Photosensitive element)
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. As shown in FIG. 1, the
次に、本発明の感光性樹脂組成物又は感光性エレメントを用いた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について説明する。 (Method for forming partition of image display device, method for manufacturing image display device, and image display device)
Next, a method for forming a partition of an image display device using the photosensitive resin composition or photosensitive element of the present invention, a method for manufacturing the image display device, and an image display device will be described.
表1に示す(A)成分、(B)成分、(C)成分、(E)成分、及びその他の成分を配合した後、そこへ表1に示す(D)成分を加えて溶解させ、実施例1~4及び比較例1~5の感光性樹脂組成物を得た。各成分の配合量(単位:g)は表1に示す通りである。 (Examples 1 to 4 and Comparative Examples 1 to 5)
After blending the (A) component, (B) component, (C) component, (E) component, and other components shown in Table 1, the (D) component shown in Table 1 was added and dissolved therein. Photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were obtained. The amount of each component (unit: g) is as shown in Table 1.
(A)成分:バインダーポリマー
*1;メタクリル酸/メタクリル酸メチル/メタクリル酸ブチル共重合体(樹脂A、質量比30/35/35、重量平均分子量50000、酸価196)の48質量%メチルセロソルブ/トルエン(質量比6/4)溶液93.75g(固形分45g)
*2;メタクリル酸/メタクリル酸メチル/ベンジルメタクリレート/スチレン共重合体(樹脂B、質量比30/5/25/40、重量平均分子量56000、酸価196)の48質量%メチルセロソルブ/トルエン(質量比6/4)溶液93.75g(固形分45g) The details of each component in Table 1 are as follows. In addition, about (A) component, although the following quantity was mix | blended as a resin solution, in Table 1, the quantity of solid content was shown.
(A) Component: Binder polymer * 1; 48% by mass methyl cellosolve of methacrylic acid / methyl methacrylate / butyl methacrylate copolymer (resin A,
* 2: 48% by mass of methyl cellosolve / toluene (mass) of methacrylic acid / methyl methacrylate / benzyl methacrylate / styrene copolymer (resin B,
*3;末端にヒドロキシル基を有するポリカーボネート化合物、有機イソシアネート及び2-ヒドロキシエチルアクリレートを反応させて得られた光重合性化合物(重量平均分子量4000、日立化成工業株式会社製、商品名:HT-9082-95)
*4;UA-21EB(新中村化学工業株式会社製、商品名)
*5;FA-023M(日立化成工業株式会社製、商品名)
*6;FA-024M(日立化成工業株式会社製、商品名)
*7;γ-クロロ-β-ヒドロキシプロピル-β’-メタクリロイルオキシエチル-o-フタレート(日立化成工業株式会社製、商品名:FA-MECH) Component (B): Photopolymerizable compound * 3; a photopolymerizable compound obtained by reacting a hydroxyl group-terminated polycarbonate compound, organic isocyanate and 2-hydroxyethyl acrylate (weight average molecular weight 4000, Hitachi Chemical Co., Ltd.) (Product name: HT-9082-95)
* 4; UA-21EB (made by Shin-Nakamura Chemical Co., Ltd., trade name)
* 5; FA-023M (trade name, manufactured by Hitachi Chemical Co., Ltd.)
* 6: FA-024M (trade name, manufactured by Hitachi Chemical Co., Ltd.)
* 7; γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-MECH)
*8;N,N’-テトラエチル-4,4’-ジアミノベンゾフェノン(保土ヶ谷化学工業株式会社製、商品名:EAB)
*9;トリブロモメチルフェニルスルホン(住友精化株式会社製、製品名:TPS)
*10;1,7-ビス(9-アクリジニル)ヘプタン(株式会社ADEKA社製、商品名:N-1717)
*11;ベンジルジメチルケタール(チバスペシャリティーケミカル株式会社製、商品名:I-651) Component (C): Photopolymerization initiator * 8; N, N′-tetraethyl-4,4′-diaminobenzophenone (manufactured by Hodogaya Chemical Co., Ltd., trade name: EAB)
* 9; Tribromomethylphenylsulfone (manufactured by Sumitomo Seika Co., Ltd., product name: TPS)
* 10; 1,7-bis (9-acridinyl) heptane (trade name: N-1717, manufactured by ADEKA Corporation)
* 11: Benzyldimethyl ketal (Ciba Specialty Chemicals, trade name: I-651)
*12;クレゾールノボラック型エポキシ樹脂(DIC株式会社製、商品名:EPICLON N-670-EXP-S)
*13;ジシクロペンタジエン型エポキシ樹脂(DIC株式会社製、商品名:EPICLON HP-7200L)
*14;ビスフェノールA型エポキシ樹脂(DIC株式会社製、商品名:EPICLON1055)
*15;クレゾールノボラック型エポキシ樹脂(DIC株式会社製、商品名:EPICLON N-665-EXP) Component (D): Compound having an epoxy group in the molecule * 12; Cresol novolak type epoxy resin (manufactured by DIC Corporation, trade name: EPICLON N-670-EXP-S)
* 13: Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, trade name: EPICLON HP-7200L)
* 14: Bisphenol A type epoxy resin (manufactured by DIC Corporation, trade name: EPICLON 1055)
* 15: Cresol novolac type epoxy resin (manufactured by DIC Corporation, trade name: EPICLON N-665-EXP)
*16;ブロックイソシアネート(住友バイエルウレタン株式会社製、商品名:スミジュールBL3175)
*17;ブロックイソシアネート(住友バイエルウレタン株式会社製、商品名:デスモジュールBL3475)
*18;ブロックイソシアネート(住友バイエルウレタン株式会社製、商品名:デスモジュールVPLS2253) Block isocyanate compound * 16; Block isocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name: Sumidur BL3175)
* 17: Block isocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name: Death Module BL3475)
* 18: Block isocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name: Death Module VPLS2253)
*19;チタンブラック分散液(ジェムコ社製、商品名:BT-1HCA) (E) component: inorganic black pigment * 19; titanium black dispersion (manufactured by Gemco, trade name: BT-1HCA)
*20;顔料分散剤(共栄社化学社製、商品名:フローレンDOPA-17HF)
*21;メタクリロイルオキシプロピルトリメトキシシラン(東レ・ダウコーニング株式会社製、商品名:SZ-6030) Other components * 20; pigment dispersant (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Floren DOPA-17HF)
* 21; Methacryloyloxypropyltrimethoxysilane (made by Toray Dow Corning Co., Ltd., trade name: SZ-6030)
高圧水銀灯ランプを有する平行光露光機EXM-1201(オーク製作所株式会社製)を用いて、41段ステップタブレットを有するフォトツールを積層物のポリエチレンテレフタレートフィルム上に密着させ、露光を行った。露光後、ポリエチレンテレフタレートフィルムを剥離し、1質量%炭酸ナトリウム水溶液を30℃で20秒間スプレーすることにより、感光性樹脂組成物層の未露光部分を除去した。41段ステップタブレットの現像後の残存ステップ段数が29.0となるエネルギー量(露光量)を感度(mJ/cm2)とした。このエネルギー量の数値が小さい程、感度が高いことを示す。表2に評価結果を示す。また、上記エネルギー量で露光を行った際の、実際の残存ステップ段数を表2に示す。 <Evaluation of sensitivity>
Using a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp, a phototool having a 41-step tablet was brought into close contact with the laminated polyethylene terephthalate film for exposure. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds to remove the unexposed portion of the photosensitive resin composition layer. The energy amount (exposure amount) at which the number of remaining step steps after development of the 41-step tablet was 29.0 was defined as sensitivity (mJ / cm 2 ). It shows that a sensitivity is so high that the numerical value of this energy amount is small. Table 2 shows the evaluation results. Table 2 shows the actual number of remaining steps when exposure is performed with the above energy amount.
高圧水銀灯ランプを有する平行光露光機EXM-1201(オーク製作所株式会社製)を用いて、密着性評価用ネガとしてライン幅/スペース幅が10/300~80/300(単位:μm、スペース幅一定)の配線パターンを有するフォトツールと、41段ステップタブレットを有するフォトツールとを積層物のポリエチレンテレフタレートフィルム上に密着させ、41段ステップタブレットの現像後の残存ステップ段数が29.0となるエネルギー量で露光を行った。露光後、ポリエチレンテレフタレートフィルムを剥離し、1質量%炭酸ナトリウム水溶液を30℃で20秒間スプレーすることにより、感光性樹脂組成物層の未露光部分を除去して密着性を評価した。密着性は、現像液により剥離されずに残った最も小さいラインの幅(μm)で表され、この数値が小さい程、細いラインでもガラス基板から剥離せずに密着していることから、密着性が高いことを示す。表2に評価結果を示す。 <Evaluation of adhesion>
Using a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp, the line width / space width is 10/300 to 80/300 (unit: μm, constant space width) as a negative for adhesion evaluation ) And a photo tool having a 41-step tablet are closely attached to the polyethylene terephthalate film of the laminate, and the amount of remaining energy after developing the 41-step tablet is 29.0. The exposure was performed. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds to remove the unexposed portion of the photosensitive resin composition layer and evaluate the adhesion. Adhesion is represented by the width (μm) of the smallest line that remains without being peeled off by the developer. The smaller the value, the tighter the line is, without peeling from the glass substrate. Is high. Table 2 shows the evaluation results.
41段ステップタブレットを有するフォトツールと、解像度評価用ネガとしてライン幅/スペース幅が30/30~200/200(単位:μm)の配線パターンを有するフォトツールとを積層物のポリエチレンテレフタレートフィルム上に密着させ、高圧水銀灯ランプを有する平行光露光機EXM-1201(オーク製作所株式会社製)を用いて、41段ステップタブレットの現像後の残存ステップ段数が29.0となるエネルギー量で露光を行った。露光後、ポリエチレンテレフタレートフィルムを剥離し、1質量%炭酸ナトリウム水溶液を30℃で20秒間スプレーすることにより、感光性樹脂組成物層の未露光部分を除去して解像度を評価した。解像度は、現像処理によって未露光部が良好に除去された最も小さいスペース幅(μm)で表され、この数値が小さいほど解像度は良好である。
表2に評価結果を示す。 <Evaluation of resolution>
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: μm) as a resolution evaluation negative on a polyethylene terephthalate film of a laminate Using a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp lamp, the exposure was performed with an energy amount of 29.0 after the development of the 41-step tablet. . After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass sodium carbonate aqueous solution was sprayed at 30 ° C. for 20 seconds to remove the unexposed portion of the photosensitive resin composition layer and evaluate the resolution. The resolution is represented by the smallest space width (μm) in which the unexposed portion is removed favorably by the development processing, and the smaller the numerical value, the better the resolution.
Table 2 shows the evaluation results.
高圧水銀灯ランプを有する平行光露光機EXM-1201(オーク製作所株式会社製)を用いて、41段ステップタブレットの現像後の残存ステップ段数が29.0となるエネルギー量で露光を行った。露光後、ポリエチレンテレフタレートフィルムを剥離し、1質量%炭酸ナトリウム水溶液を30℃で20秒間スプレーし、感光性樹脂組成物層の未露光部分を除去した。次いで、120℃に加熱した箱型乾燥機(三菱電機株式会社製、型番:NV50-CA、空気雰囲気)内に1時間静置した。得られた評価シートをハゼ折りし、ITO付PET基材から感光性樹脂組成物層の硬化物が剥がれず破損が見られないものをA、ITO付PET基材から剥がれが見られたもの、又は、破損が見られたものをBとした。 <Goat folding test>
Using a parallel light exposure machine EXM-1201 (manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp, exposure was performed with an energy amount such that the number of remaining step steps after development of the 41-step step tablet was 29.0. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds to remove the unexposed portion of the photosensitive resin composition layer. Subsequently, it was left still for 1 hour in a box-type dryer (Mitsubishi Electric Corporation, model number: NV50-CA, air atmosphere) heated to 120 ° C. The evaluation sheet thus obtained is folded, and the cured product of the photosensitive resin composition layer is not peeled off from the PET substrate with ITO, and no damage is seen, and the peeling is seen from the PET substrate with ITO, Alternatively, B was determined to be damaged.
IZO-TEG(Test Element Group)基板、ITO-TEG(Test Element Group)基板のIZO、ITO面上に、上記感光性エレメントを、各々感光性樹脂組成物層がIZO-TEG基板、ITO-TEG基板の表面に接するように、ポリエチレン製保護フィルムを剥離しながら110℃に加熱したラミネートロールを通してラミネートした。得られた積層物の構成は、下からTEG基板、感光性樹脂組成物層、ポリエチレンテレフタレートフィルムとなる。41段ステップタブレットを有するフォトツールを積層物のポリエチレンテレフタレートフィルム上に密着させ、高圧水銀灯ランプを有する平行光露光機EXM-1201(オーク製作所株式会社製)を用いて、現像後の残存ステップ段数が29.0となるエネルギー量で露光を行った。露光後、ポリエチレンテレフタレートフィルムを剥離し、1質量%炭酸ナトリウム水溶液を30℃で20秒間スプレーすることにより、感光性樹脂組成物層の未露光部分を除去した。これにより、感光性樹脂組成物層の光硬化物がTEG基板上に形成された評価基板を得た。次いで、得られた評価基板を、120℃に加熱した箱型乾燥機(三菱電機株式会社製、型番:NV50-CA)内に1時間静置した。その後、60℃、90%RHの条件下で、80Vの直流電圧を評価基板の電極に印加し、100時間後の陽極の抵抗値をテスターで測定した。表2に評価結果を示す。表中、Aは抵抗値の測定が可能であり、溶解による断線なしと判断したものを示し、Bは、測定不能であり溶解による断線ありと判断したものを示す。また、Aについては、100時間後の陽極の抵抗値を初期抵抗値で割って100倍した値を抵抗上昇率(%)として記載した。抵抗上昇率の値が小さいほど、電極の溶解が抑制されていると評価できる。 <Solubility of electrode>
On the IZO and ITO surfaces of an IZO-TEG (Test Element Group) substrate and an ITO-TEG (Test Element Group) substrate, the photosensitive element is composed of an IZO-TEG substrate and an ITO-TEG substrate, respectively. The film was laminated through a laminating roll heated to 110 ° C. while peeling off the polyethylene protective film so as to be in contact with the surface. The structure of the obtained laminate is a TEG substrate, a photosensitive resin composition layer, and a polyethylene terephthalate film from the bottom. 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. Exposure was performed with an energy amount of 29.0. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds to remove the unexposed portion of the photosensitive resin composition layer. Thereby, the evaluation board | substrate with which the photocured material of the photosensitive resin composition layer was formed on the TEG board | substrate was obtained. Next, the obtained evaluation substrate was allowed to stand for 1 hour in a box-type dryer (manufactured by Mitsubishi Electric Corporation, model number: NV50-CA) heated to 120 ° C. Thereafter, under the conditions of 60 ° C. and 90% RH, a DC voltage of 80 V was applied to the electrode of the evaluation substrate, and the resistance value of the anode after 100 hours was measured with a tester. Table 2 shows the evaluation results. In the table, A indicates that the resistance value can be measured and it is determined that there is no disconnection due to dissolution, and B indicates that it is impossible to measure and it is determined that there is disconnection due to dissolution. As for A, a value obtained by dividing the resistance value of the anode after 100 hours by the initial resistance value and multiplying by 100 is indicated as a rate of increase in resistance (%). It can be evaluated that dissolution of the electrode is suppressed as the resistance increase rate is smaller.
ポリ四フッ化エチレンシート(日東電工株式会社製、製品名:ニトフロンフィルムNo.900U)上に上記感光性エレメントを、感光性樹脂組成物層がポリ四フッ化エチレンシート表面に接するように、ポリエチレン製保護フィルムを剥離しながら110℃に加熱したラミネートロールを通してラミネートした。得られた積層物の構成は、ポリ四フッ化エチレンシート、感光性樹脂組成物層、ポリエチレンテレフタレートフィルムの順となる。上記積層物のポリエチレンテレフタレートフィルム上から平行光露光機EXM-1201(株式会社オーク製作所製)を用いて、露光した。なお、積層物の露光にあたっては、41段ステップタブレットの現像後の残存ステップ段数が29.0となるエネルギー量とした。露光後、ポリエチレンテレフタレートフィルムを剥離し、1質量%炭酸ナトリウム水溶液を30℃で30秒間スプレーすることにより、感光性樹脂組成物層の未露光部分を除去した。これにより、感光性樹脂組成物層の光硬化物がポリ四フッ化エチレンシート上に形成された評価シートを得た。次いで、得られた評価シートを、120℃に加熱した箱型乾燥機(三菱電機株式会社製、型番:NV50-CA、空気雰囲気)内に1時間静置した。加熱処理後の評価シートを10mm幅に切り出し、チャック間距離を50mmとし、速度2cm/minの一定速度で、感光性樹脂組成物層の硬化物が破断するまで引っ張り、25℃での硬化物の伸び率(%)を求めた。表2に評価結果を示す。 <Elongation of cured product>
The photosensitive element is placed on a polytetrafluoroethylene sheet (manufactured by Nitto Denko Corporation, product name: Nitoflon Film No. 900U), so that the photosensitive resin composition layer is in contact with the surface of the polytetrafluoroethylene sheet. The film was laminated through a laminating roll heated to 110 ° C. while peeling off the polyethylene protective film. The structure of the obtained laminate is in the order of a polytetrafluoroethylene sheet, a photosensitive resin composition layer, and a polyethylene terephthalate film. It exposed using the parallel light exposure machine EXM-1201 (made by Oak Manufacturing Co., Ltd.) on the polyethylene terephthalate film of the said laminated body. In the exposure of the laminate, the energy amount was such that the number of remaining step steps after development of the 41-step tablet was 29.0. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 30 seconds to remove the unexposed portion of the photosensitive resin composition layer. Thereby, the evaluation sheet | seat in which the photocured material of the photosensitive resin composition layer was formed on the polytetrafluoroethylene sheet was obtained. Next, 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 was cut into a width of 10 mm, the distance between chucks was set to 50 mm, and the cured product of the photosensitive resin composition layer was pulled at a constant speed of 2 cm / min until the cured product of the photosensitive resin composition was broken. Elongation rate (%) was determined. Table 2 shows the evaluation results.
Claims (9)
- 少なくとも表示面に透明電極を備えた屈曲性を有する画像表示装置における、画素を分離する隔壁を形成するための感光性樹脂組成物であって、
前記感光性樹脂組成物は、
(A)成分:分子内にカルボキシル基を有するバインダーポリマー、
(B)成分:光重合性化合物、
(C)成分:光重合開始剤、及び、
(D)成分:分子内にエポキシ基を有する化合物、
を含有し、
前記感光性樹脂組成物を光硬化させた後、空気下120℃で1時間加熱してなる幅10mm、厚さ45μmのシート状の硬化物の、25℃における伸び率が40%以上である、感光性樹脂組成物。 A photosensitive resin composition for forming a partition separating pixels in a flexible image display device having a transparent electrode on at least a display surface,
The photosensitive resin composition is
(A) component: a binder polymer having a carboxyl group in the molecule;
(B) component: a photopolymerizable compound,
Component (C): a photopolymerization initiator, and
(D) component: a compound having an epoxy group in the molecule,
Containing
The photosensitive resin composition is photocured and then heated at 120 ° C. for 1 hour in air, and the sheet-like cured product having a width of 10 mm and a thickness of 45 μm has an elongation at 40 ° C. of 40% or more. Photosensitive resin composition. - 更に(E)成分:無機系黒色顔料を含有する、請求項1記載の感光性樹脂組成物。 Furthermore, (E) component: The photosensitive resin composition of Claim 1 containing an inorganic type black pigment.
- 前記(E)成分が、チタンブラックを含む、請求項2記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 2, wherein the component (E) contains titanium black.
- 支持体と、該支持体上に形成された請求項1~3のいずれか一項に記載の感光性樹脂組成物からなる感光性樹脂組成物層と、を備える感光性エレメント。 A photosensitive element comprising: a support; and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 3 formed on the support.
- 少なくとも表示面に配置された透明電極と、画素を分離する隔壁とを備える、屈曲性を有する画像表示装置の隔壁の形成方法であって、
前記画像表示装置の基板上に、請求項1~3のいずれか一項に記載の感光性樹脂組成物からなる感光性樹脂組成物層を積層する積層工程と、
前記感光性樹脂組成物層の所定部分に活性光線を照射して露光部を光硬化せしめる露光工程と、
前記感光性樹脂組成物層の前記露光部以外の部分を除去して光硬化物パターンを形成する現像工程と、
を有する、画像表示装置の隔壁の形成方法。 A method for forming a partition wall of an image display device having flexibility, comprising at least a transparent electrode disposed on a display surface and a partition wall for separating pixels.
A laminating step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 3 on a substrate of the image display device;
An exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to photocure an exposed portion; and
A development step of removing a portion other than the exposed portion of the photosensitive resin composition layer to form a photocured product pattern;
A method for forming a partition wall of an image display device. - 少なくとも表示面に配置された透明電極と、画素を分離する隔壁とを備える、屈曲性を有する画像表示装置の製造方法であって、
請求項5記載の方法により前記隔壁を形成する工程を有する、画像表示装置の製造方法。 A method of manufacturing an image display device having flexibility, comprising at least a transparent electrode disposed on a display surface and a partition wall for separating pixels,
A method for manufacturing an image display device, comprising the step of forming the partition wall by the method according to claim 5. - 前記透明電極は、少なくとも1種類の金属導電性繊維を含む溶液を塗布して形成された材料で構成されたものである、請求項6記載の画像表示装置の製造方法。 The method for manufacturing an image display device according to claim 6, wherein the transparent electrode is made of a material formed by applying a solution containing at least one metal conductive fiber.
- 前記隔壁内に表示媒体を充填する工程と、
一方の基板に対向するように隔壁の反対側に基板を貼り付ける工程と、
を更に含む、請求項6又は7記載の画像表示装置の製造方法。 Filling the partition with a display medium;
A step of attaching the substrate to the opposite side of the partition so as to face one of the substrates;
The manufacturing method of the image display apparatus of Claim 6 or 7 further including these. - 請求項6~8のいずれか一項に記載の製造方法により製造される、画像表示装置。 An image display device manufactured by the manufacturing method according to any one of claims 6 to 8.
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KR1020127033751A KR101486641B1 (en) | 2010-06-07 | 2011-06-03 | Photosensitive resin composition, photosensitive element comprising the composition, method for formation of septum for image display device, process for production of image display device, and image display device |
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