WO2013084873A1 - タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント、並びに、タッチパネルの製造方法 - Google Patents
タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント、並びに、タッチパネルの製造方法 Download PDFInfo
- Publication number
- WO2013084873A1 WO2013084873A1 PCT/JP2012/081362 JP2012081362W WO2013084873A1 WO 2013084873 A1 WO2013084873 A1 WO 2013084873A1 JP 2012081362 W JP2012081362 W JP 2012081362W WO 2013084873 A1 WO2013084873 A1 WO 2013084873A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- protective film
- touch panel
- resin composition
- photosensitive
- Prior art date
Links
Images
Classifications
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- 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
- 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
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04102—Flexible digitiser, i.e. constructional details for allowing the whole digitising part of a device to be flexed or rolled like a sheet of paper
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
Definitions
- the present invention relates to a method for forming a protective film for an electrode for a touch panel, and in particular, a method for forming a protective film suitable for protecting an electrode of a capacitive touch panel, a photosensitive resin composition and a photosensitive element used therefor, and a touch panel It relates to the manufacturing method.
- Liquid crystal display elements and touch panels are used in large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, and display devices such as OA / FA devices.
- These liquid crystal display elements and touch panels are provided with electrodes made of a transparent conductive electrode material.
- ITO Indium-Tin-Oxide
- indium oxide and tin oxide are known, and these materials exhibit high visible light transmittance, so that they can be used as electrode materials for substrates for liquid crystal display elements. It has become mainstream.
- capacitive touch panel when a fingertip that is a conductor contacts the touch input surface, the fingertip and the conductive film are capacitively coupled to form a capacitor. For this reason, the capacitive touch panel detects the coordinates by capturing the change in charge at the contact position of the fingertip.
- the projected capacitive touch panel can detect multiple fingertips, so it has a good operability to give complex instructions.
- a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes.
- ITO Indium-Tin-Oxide
- the frame area of the touch panel is an area where the touch position cannot be detected, reducing the area of the frame area is an important factor for improving the product value.
- metal wiring is required to transmit a touch position detection signal, but in order to reduce the frame area, it is necessary to reduce the width of the metal wiring.
- copper is used for metal wiring.
- a capacitive projection type touch panel in which an insulating layer is formed on metal is disclosed (for example, Patent Document 1).
- a silicon dioxide layer is formed on a metal by a plasma chemical vapor deposition method (plasma CVD method) to prevent corrosion of the metal.
- plasma CVD method plasma chemical vapor deposition method
- this method uses a plasma CVD method, there is a problem that a high temperature treatment is required, a base material is limited, and a manufacturing cost is increased.
- JP 2011-28594 A JP-A-7-253666 JP 2005-99647 A Japanese Patent Laid-Open No. 11-133617
- a protective film with a photosensitive resin composition can be expected to reduce costs compared to the plasma CVD method.
- the protective film is formed on the electrode for the touch panel, if the thickness of the protective film is large, a step may be conspicuous between a place where the film is present and a place where the film is not present. Therefore, it is necessary to make the protective film as thin as possible.
- the rust preventive property of the film formed from the photosensitive resin composition has been studied at a thickness of 10 ⁇ m or less.
- the present invention provides a method for forming a protective film for a touch panel electrode that can form a protective film having sufficient rust prevention properties on a predetermined touch panel electrode, and can form such a protective film. It aims at providing the manufacturing method of the photosensitive resin composition, the photosensitive element, and a touch panel.
- the photosensitive resin composition containing a specific binder polymer, a specific photopolymerizable compound, and a photopolymerization initiator has sufficient developability.
- the inventors have found that even when the film formed by photocuring has a thickness of 10 ⁇ m or less, the film exhibits sufficient rust prevention properties and can sufficiently prevent corrosion of metals such as copper, and the present invention has been completed.
- a photosensitive layer made of a photosensitive resin composition containing a photopolymerizable compound having a saturated group and a photopolymerization initiator is provided, and a predetermined portion of the photosensitive layer is cured by irradiation with actinic rays and then other than the predetermined portion.
- a protective film made of a cured product of the predetermined portion of the photosensitive layer that covers a part or all of the electrode is formed.
- a thickness of 10 ⁇ m or less is sufficient while ensuring developability and adhesion to a substrate.
- a protective film having rust prevention properties can be formed. According to the present invention, it is possible to form a protective film having both good aesthetics and rust prevention properties using a photosensitive resin composition, and thus it is possible to reduce the manufacturing cost in the production of touch panels.
- the photopolymerizable compound is a (meth) acrylate compound having a skeleton derived from pentaerythritol, a (meth) acrylate compound having a skeleton derived from dipentaerythritol, or a skeleton derived from trimethylolpropane. It is preferable to include at least one compound selected from the group consisting of a (meth) acrylate compound having a glycerin and a (meth) acrylate compound having a glycerin-derived skeleton.
- the photosensitive layer preferably has a minimum visible light transmittance of 90% or more at 400 to 700 nm. In this case, it is suitable for forming a protective film that covers the electrodes in the sensing region.
- the photosensitive layer preferably has a b * in the CIELAB color system of ⁇ 0.2 to 1.0. In this case, it is suitable for forming a protective film that covers the electrodes in the sensing region.
- the photosensitive resin composition further contains at least one compound selected from the group consisting of triazole compounds, thiadiazole compounds, and tetrazole compounds from the viewpoint of achieving both developability and rust prevention properties.
- the photosensitive resin composition further contains at least one compound selected from the group consisting of triazole compounds, thiadiazole compounds, and tetrazole compounds from the viewpoint of achieving both developability and rust prevention properties.
- both developability and rust resistance can be achieved, and a protective film having rust resistance can be formed with a good pattern.
- the photopolymerization initiator contains an oxime ester compound and / or a phosphine oxide compound.
- an oxime ester compound and / or a phosphine oxide compound as a photoinitiator, a pattern can be formed with sufficient resolution even when the photosensitive layer is thin.
- the present inventors have found that when patterning a thin photosensitive layer having high transparency, the resolution tends to decrease. The present inventors consider that the reason is that when the thickness of the photosensitive layer is reduced, it is easily affected by light scattering from the base material and halation occurs.
- the photopolymerization initiator contains an oxime ester compound and / or a phosphine oxide compound, whereby a pattern can be formed with sufficient resolution.
- the reason why the above effect can be obtained is that the oxime moiety contained in the oxime ester compound or the phosphine oxide moiety contained in the phosphine oxide compound has a relatively high photolysis efficiency but does not decompose with slight light leakage.
- the present inventors infer that the influence of leakage light is suppressed because of having a large threshold.
- a photosensitive element comprising a support film and a photosensitive layer made of the photosensitive resin composition provided on the support film is prepared, and the photosensitive element is prepared.
- the photosensitive layer of the photosensitive element can be transferred onto the substrate to provide the photosensitive layer.
- a roll-to-roll process can be easily realized, and the solvent drying process can be shortened, which can greatly contribute to shortening of the manufacturing process and cost reduction.
- the present invention also includes a binder polymer having a carboxyl group and an acid value of 30 to 120 mgKOH / g, a photopolymerizable compound having at least three ethylenically unsaturated groups, and a photopolymerization initiator.
- the photosensitive resin composition used for the protective film formation of the electrode for touchscreens is provided.
- a protective film having sufficient antirust property can be formed on a predetermined touch panel electrode even if it is a thin film.
- the photosensitive resin composition of the present invention preferably has a minimum visible light transmittance of 90% or more when a protective film is formed.
- the photosensitive resin composition of the present invention has a b * in the CIELAB color system when a protective film is formed of -0.2 to 1.0. Is preferred.
- the photosensitive resin composition of the present invention further contains at least one compound selected from the group consisting of triazole compounds, thiadiazole compounds, and tetrazole compounds from the viewpoint of achieving both developability and rust prevention properties. Is preferred.
- the photopolymerization initiator preferably contains an oxime ester compound and / or a phosphine oxide compound. In this case, it is possible to form a thin protective film having a high resolution and a pattern having sufficient resolution.
- the present invention also provides a photosensitive element comprising a support film and a photosensitive layer comprising the photosensitive resin composition according to the present invention provided on the support film.
- a protective film having sufficient antirust property can be formed on a predetermined touch panel electrode even if it is a thin film.
- the thickness of the photosensitive layer can be 10 ⁇ m or less.
- the present invention also provides a method for manufacturing a touch panel comprising a step of forming a protective film covering a part or all of the electrodes by a method for forming a protective film according to the present invention on a substrate having a touch panel electrode. To do.
- a method for forming a protective film for a touch panel electrode that can form a protective film having sufficient rust prevention properties even on a thin film on a predetermined touch panel electrode, and such a protective film are provided.
- the photosensitive resin composition and photosensitive element which can be formed, and the manufacturing method of a touch panel can be provided.
- the metal electrode of the capacitive touch panel can be protected. Furthermore, according to the present invention, it is possible to protect the electrodes in the frame region of the touch panel in which a metal layer such as copper, which is easily rusted by moisture or salt, is formed to improve conductivity.
- the photosensitive resin composition of the present invention is excellent in transparency and rust prevention properties, it is not affected by changes in the configuration of the touch panel as long as it is intended to protect the electrode forming part of the touch panel (touch sensor). It can be used suitably. Specifically, the purpose of protecting the electrode forming part of the touch panel (touch sensor) even when the configuration of the touch panel is changed from the cover glass, the touch panel, and the liquid crystal panel to the cover glass integrated type and the on-cell type. If it is, it can use suitably.
- the electrode for the touch panel includes not only the electrode in the sensing area of the touch panel but also the metal wiring in the frame area. Either or both of the electrodes provided with the protective film may be provided.
- excellent in transparency means that visible light of 400 to 700 nm is transmitted by 90% or more, and even if light is scattered to some extent, it is included in the concept of transparency.
- (meth) acrylic acid means acrylic acid or methacrylic acid
- (meth) acrylate means acrylate or the corresponding methacrylate
- (meth) acryloyl group means acryloyl.
- the (poly) oxyethylene chain means an oxyethylene group or a polyoxyethylene group
- the (poly) oxypropylene chain means an oxypropylene group or a polyoxypropylene group.
- (EO) modified” means a compound having a (poly) oxyethylene chain
- (PO) modified” means a compound having a (poly) oxypropylene chain.
- (EO) ⁇ (PO) modified” means a compound having both a (poly) oxyethylene chain and a (poly) oxypropylene chain.
- process is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included.
- a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive element of the present invention.
- the photosensitive element 1 shown in FIG. 1 is opposite to the support film 10, the photosensitive layer 20 made of the photosensitive resin composition according to the present invention provided on the support film 10, and the support film 10 of the photosensitive layer 20. And a protective film 30 provided on the side.
- the photosensitive element 1 of the present embodiment can be suitably used for forming a protective film for a touch panel electrode.
- a polymer film can be used as the support film 10.
- the polymer film include films made of polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, and the like.
- the thickness of the support film 10 is preferably 5 to 100 ⁇ m from the viewpoint of ensuring coverage and suppressing a decrease in resolution when irradiated with actinic rays through the support film 10. More preferably, it is more preferably 15 to 40 ⁇ m, and particularly preferably 20 to 35 ⁇ m.
- the photosensitive resin composition according to the present invention constituting the photosensitive layer 20 includes a binder polymer having a carboxyl group and an acid value of 30 to 120 mgKOH / g (hereinafter also referred to as component (A)), and at least three A photopolymerizable compound having an ethylenically unsaturated group (hereinafter also referred to as (B) component) and a photopolymerization initiator (hereinafter also referred to as (C) component) are contained.
- component (A) a binder polymer having a carboxyl group and an acid value of 30 to 120 mgKOH / g
- B ethylenically unsaturated group
- C photopolymerization initiator
- a protective film having a sufficient antirust property can be formed with a thickness of 10 ⁇ m or less. Therefore, according to the photosensitive resin composition which concerns on this embodiment, the protective film which can make aesthetics and rust prevention property compatible can be formed.
- the photosensitive layer is usually formed with a thickness exceeding 10 ⁇ m, and the acid value of the binder polymer contained in the photosensitive resin composition used for ensuring the developability at this time is adjusted.
- the acid value is set to a value of about 140 to 250 mgKOH / g.
- the component (A) having an appropriate acid value
- the component (B) that can further improve rust prevention, it is considered that rust prevention and developability could be achieved at a high level.
- the acid value of the binder polymer as the component (A) can be measured as follows. That is, first, 1 g of the binder polymer that is the object of acid value measurement is precisely weighed. 30 g of acetone is added to the precisely weighed binder polymer and dissolved 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.
- Acid value 0.1 ⁇ Vf ⁇ 56.1 / (Wp ⁇ I)
- Vf represents the titration amount (mL) of the aqueous KOH solution
- Wp represents the weight (g) of the solution containing the measured binder polymer
- I represents the ratio of the nonvolatile content in the solution containing the measured binder polymer. (Mass%) is shown.
- the binder polymer as the component (A) is preferably a copolymer containing structural units derived from (a) (meth) acrylic acid and (b) (meth) acrylic acid alkyl ester. .
- (b) (meth) acrylic acid alkyl esters examples include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and Examples include (meth) acrylic acid hydroxyl ethyl ester.
- the copolymer may further contain other monomer that can be copolymerized with the component (a) and / or the component (b) as a constituent unit.
- Examples of the other monomer that can be copolymerized with the component (a) and / or the component (b) include (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, and (meth) acrylic.
- Acid diethylaminoethyl ester (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate , (Meth) acrylamide, (meth) acrylonitrile, diacetone (meth) acrylamide, styrene, and vinyltoluene.
- the above monomers may be used alone or in combination of two or more.
- the molecular weight of the binder polymer as component (A) is not particularly limited, but from the viewpoints of coatability, coating film strength, and developability, the weight average molecular weight is usually preferably 10,000 to 200,000. More preferably, it is 30,000 to 150,000, and very preferably 50,000 to 100,000.
- the measurement conditions of a weight average molecular weight shall be the same measurement conditions as the Example of this-application specification.
- the acid value of the binder polymer as the component (A) can be developed with various known developing solutions in the step of selectively removing the photosensitive resin composition layer in the development step, From the viewpoint of improving resistance to corrosive components such as moisture and salt when functioning as a protective film, the range is from 30 to 120 mgKOH / g.
- the acid value of the binder polymer by setting the acid value of the binder polymer to 30 to 120 mg KOH / g, development can be performed using an alkaline aqueous solution containing water, an alkali metal salt, and a surfactant.
- the acid value of the binder polymer is 30 mgKOH / g or more, sufficient developability can be obtained, and when it is 120 mgKOH / g or less, resistance to corrosive components such as moisture and salt can be improved. .
- the acid value of the component (A) is 50 to 120 mgKOH / g.
- the acid value of the component (A) is in such a range, for example, sufficient development is possible even when developing using an aqueous alkali solution such as sodium carbonate, potassium carbonate, tetramethylammonium hydroxide, triethanolamine and the like. Sex can be obtained.
- it is preferably 50 mgKOH / g or more, more preferably 60 mgKOH / g or more, and still more preferably 70 mgKOH / g or more.
- the electrode for touch panels when protecting the electrode for touch panels, from a viewpoint of protecting an electrode from corrosive components, such as a water
- Examples of the photopolymerizable compound having at least three ethylenically unsaturated groups as the component (B) include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meta )
- Examples thereof include compounds obtained by adding an ⁇ , ⁇ -unsaturated carboxylic acid to a glycidyl group-containing compound such as acrylate.
- the photopolymerizable compound having at least three ethylenically unsaturated groups preferably has an acid value of 5 mgKOH / g or less from the viewpoint of excellent rust prevention.
- a (meth) acrylate compound having a skeleton derived from pentaerythritol and a (meth) acrylate having a skeleton derived from dipentaerythritol from the viewpoint of electrode corrosion inhibition power and ease of development.
- It preferably contains at least one selected from a compound, a (meth) acrylate compound having a skeleton derived from trimethylolpropane, and a (meth) acrylate compound having a glycerin-derived skeleton, and has a skeleton derived from dipentaerythritol ( It is more preferable to include at least one selected from a (meth) acrylate compound and a (meth) acrylate compound having a skeleton derived from trimethylolpropane.
- (meth) acrylate having a skeleton derived from dipentaerythritol means an esterified product of dipentaerythritol and (meth) acrylic acid, and the esterified product is a compound modified with an alkyleneoxy group.
- the above esterified product preferably has 6 ester bonds in one molecule, but a compound having 1 to 5 ester bonds may be mixed.
- the (meth) acrylate compound having a skeleton derived from trimethylolpropane means an esterified product of trimethylolpropane and (meth) acrylic acid, and the esterified product is modified with an alkyleneoxy group. Also included are compounds. In the above esterified product, the number of ester bonds in one molecule is preferably 3, but a compound having 1 to 2 ester bonds may be mixed.
- an alkylene oxide-modified trimethylolpropane (meth) acrylate compound an alkylene oxide-modified tetra is preferable from the viewpoint of further improving the ability to suppress electrode corrosion and ease of development.
- Methylolmethane (meth) acrylate compound alkylene oxide modified pentaerythritol (meth) acrylate compound, alkylene oxide modified dipentaerythritol (meth) acrylate compound, alkylene oxide modified glycerin (meth) acrylate compound, and alkylene oxide modified trimethylolpropane triglycidyl
- it contains at least one compound selected from ether (meth) acrylates, and alkylene oxide-modified dipen
- alkylene oxide-modified tetramethylolmethane (meth) acrylate compound for example, EO-modified pentaerythritol tetraacrylate can be used.
- EO-modified pentaerythritol tetraacrylate is available as RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).
- the above compounds can be used alone or in combination of two or more.
- the content of the component (A) and the component (B) in the photosensitive resin composition of the present embodiment is such that the component (A) is 40 to 40 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 80 parts by mass, component (B) is preferably 20-60 parts by mass, component (A) is preferably 50-70 parts by mass, and component (B) is more preferably 30-50 parts by mass, More preferably, the component is 55 to 65 parts by mass and the component (B) is 35 to 45 parts by mass.
- the photosensitive resin composition of the present embodiment can contain a photopolymerizable compound other than the component (B).
- a photopolymerizable compound for example, the component (B) can be used in combination with one or more of a monofunctional monomer and a bifunctional monomer.
- Examples of the monofunctional monomer include (meth) acrylic acid, (meth) acrylic acid alkyl ester, and monomers copolymerizable therewith exemplified as suitable monomers used for the synthesis of the binder polymer of component (A). It is done.
- bifunctional vinyl monomer examples include polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A polyoxyethylene polyoxypropylene di (meth) acrylate (ie, 2,2-bis (4-acryloxypolyethoxypolypropoxyphenyl) propane), bisphenol A diglycidyl ether di (meth) acrylate, etc .; polyvalent carboxylic acid (phthalic anhydride, etc.), hydroxyl group and ethylenically unsaturated group Examples thereof include esterified products with a substance ( ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, etc.).
- the mixing ratio of these monomers is not particularly limited.
- the proportion of the photopolymerizable compound as the component (B) is preferably 30 parts by mass or more with respect to 100 parts by mass of the total amount of the photopolymerizable compound contained in the photosensitive resin composition.
- the amount is more preferably 50 parts by mass or more, and further preferably 75 parts by mass or more.
- Examples of the photopolymerization initiator (C) include benzophenone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N, N ′, N ′.
- Oxime ester compounds such as benzyl dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane; N-phenylglycine derivatives such as N-phenylglycine; Compounds; oxazole compounds; phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- an oxime ester compound and / or a phosphine oxide compound are preferable from the transparency of the protective film formed and the pattern forming ability when the film thickness is 10 ⁇ m or less.
- the transparency of the protective film is higher.
- the present inventors have found that when patterning a thin photosensitive layer having high transparency, the resolution tends to decrease. The present inventors consider that this is because when the thickness of the photosensitive layer is reduced, the photosensitive layer is easily affected by light scattering from the substrate and halation occurs.
- an oxime ester compound and / or a phosphine oxide compound as the component (C)
- pattern formation with sufficient resolution becomes possible.
- the reason why the above effect can be obtained is that the oxime moiety contained in the oxime ester compound or the phosphine oxide moiety contained in the phosphine oxide compound has a relatively high photolysis efficiency but does not decompose with slight light leakage.
- the present inventors infer that the influence of leakage light is suppressed because of having a large threshold.
- Examples of the oxime ester compound include compounds represented by the following general formula (C-1) and general formula (C-2). From the viewpoint of fast curability and transparency, the following general formula (C-1) The compound represented by these is preferable.
- R 1 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.
- the aromatic ring in the general formula (C-1) may have a substituent.
- R 1 is preferably an alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 4 to 15 carbon atoms, and an alkyl group having 4 to 8 carbon atoms, or carbon A cycloalkyl group having a number of 4 to 10 is more preferable.
- R 2 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms
- R 3 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl having 3 to 20 carbon atoms
- R 4 represents an alkyl group having 1 to 12 carbon atoms
- R 5 represents an alkyl group or aryl group having 1 to 20 carbon atoms
- p1 represents an integer of 0 to 3. When p1 is 2 or more, a plurality of R 4 may be the same or different. Note that carbazole may have a substituent as long as the effects of the present invention are not impaired.
- R 2 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably an ethyl group. .
- R 3 is preferably an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 4 to 15 carbon atoms, and an alkyl group having 1 to 4 carbon atoms or a carbon number More preferably, it is a 4-10 cycloalkyl group.
- Examples of the compound represented by the general formula (C-1) include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like.
- Examples of the compound represented by the general formula (C-2) include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl). Oxime) and the like.
- 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] is available as IRGACURE OXE 01 (trade name, manufactured by BASF Corp.).
- Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is IRGACURE OXE 02 (manufactured by BASF Corporation) (Commercial name) is commercially available. These are used alone or in combination of two or more.
- Examples of the phosphine oxide compound include compounds represented by the following general formula (C-3) and general formula (C-4). From the viewpoint of fast curability and transparency, a compound represented by the following general formula (C-3) is preferred.
- R 6 , R 7 and R 8 each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms.
- R 9 , R 10 and R 11 each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms.
- R 6 , R 7 or R 8 in the general formula (C-3) is an alkyl group having 1 to 20 carbon atoms
- R 9 , R 10 or R 11 in the general formula (C-4) are In the case of an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear, branched, or cyclic. Further, the alkyl group preferably has 5 to 10 carbon atoms.
- R 6 , R 7 or R 8 in the general formula (C-3) is an aryl group
- R 9 , R 10 or R 11 in the general formula (C-4) is an aryl group
- the aryl The group may have a substituent.
- the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
- R 6 , R 7 , and R 8 in the general formula (C-3) are preferably aryl groups.
- R 9 , R 10 and R 11 are preferably aryl groups.
- 2,4,6-trimethylbenzoyl-diphenyl- is used because of the transparency of the protective film to be formed and the pattern forming ability when the film thickness is 10 ⁇ m or less.
- Phosphine oxide is preferred.
- 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide is commercially available, for example, as LUCIRIN TPO (trade name, manufactured by BASF Corporation).
- the content of the photopolymerization initiator as component (C) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B), and 1 to 10 parts by mass. More preferably, the amount is 2 to 5 parts by mass.
- the photosensitivity becomes sufficient, and the absorption on the surface of the composition increases when irradiated with actinic rays, and the internal photocuring is insufficient. It is possible to suppress problems such as becoming visible and decreasing the visible light transmittance.
- the photosensitive resin composition of this embodiment is at least one compound selected from the group consisting of a triazole compound, a thiadiazole compound, and a tetrazole compound (hereinafter referred to as (D)) from the viewpoint of achieving both rust prevention and developability. It is preferable to further contain a component).
- triazole compound examples include triazole containing a mercapto group such as benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, and 3-mercaptotriazole. And triazole compounds containing an amino group such as 3-amino-5-mercaptotriazole.
- thiadiazole compound examples include 2-amino-5-mercapto-1,3,4-thiadiazole, 2,1,3-benzothiadiazole and the like.
- Examples of the tetrazole compound include compounds represented by the following general formula (D-1).
- R 11 and R 12 in the general formula (D-1) each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an amino group, a mercapto group, or a carboxymethyl group.
- alkyl group examples include a methyl group, an ethyl group, and a propyl group.
- tetrazole compound represented by the general formula (D-1) include, for example, 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 1-methyl-5-ethyl- Examples include tetrazole, 1-methyl-5-mercapto-tetrazole, and 1-carboxymethyl-5-mercapto-tetrazole.
- a water-soluble salt of a tetrazole compound represented by the above general formula (D-1) can be used.
- Specific examples include alkali metal salts of 1-carboxymethyl-5-mercapto-tetrazole such as sodium, potassium and lithium.
- the component (D) includes 1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-, from the viewpoint of electrode corrosion inhibition, adhesion to metal electrodes, easy development, and transparency. 5-mercapto-1H-tetrazole is particularly preferred.
- tetrazole compounds and water-soluble salts thereof may be used singly or in combination of two or more.
- the photosensitive resin composition is a tetrazole compound having an amino group among the above compounds It is preferable to further contain. In this case, development residues can be reduced, and it becomes easy to form a protective film with a good pattern. The reason for this may be that the balance between the solubility in the developer and the adhesion between the metal and the metal is improved by blending the tetrazole compound having an amino group.
- the photosensitive resin composition and the photosensitive element according to the present embodiment form a metal layer such as copper to improve conductivity. It is suitable for forming a protective film for protecting the electrode in the frame region of the touch panel.
- the content of the component (D) in the photosensitive resin composition of the present embodiment is 0.05 to 10.0 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B).
- the content is 0.1 to 2.0 parts by mass, and more preferably 0.2 to 1.0 part by mass.
- an adhesion imparting agent such as a silane coupling agent, a leveling agent, a plasticizer, a filler, an antifoaming agent, a flame retardant, a stabilizer, an oxidation agent.
- An inhibitor, a fragrance, a thermal crosslinking agent, a polymerization inhibitor and the like can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). These can be used alone or in combination of two or more.
- the minimum value of the visible light transmittance at 400 to 700 nm is preferably 90% or more, more preferably 92% or more, and further preferably 95% or more. preferable.
- the visible light transmittance of the photosensitive resin composition is determined as follows. First, the coating liquid containing the photosensitive resin composition is applied onto the support film so that the thickness after drying is 10 ⁇ m or less, and dried to form a photosensitive resin composition layer. Next, it laminates on a glass substrate using a laminator so that the photosensitive resin composition layer contacts. Thus, a measurement sample in which the photosensitive resin composition layer and the support film are laminated on the glass substrate is obtained. Next, after the photosensitive resin composition layer is photocured by irradiating the obtained measurement sample with ultraviolet rays, the transmittance in a measurement wavelength region of 400 to 700 nm is measured using an ultraviolet-visible spectrophotometer.
- the transmittance in the wavelength range of 400 to 700 nm which is a light ray in the general visible light wavelength range, is 90% or more, for example, when protecting the transparent electrode in the sensing area of the touch panel (touch sensor) or touch panel (touch When the protective layer is visible from the edge of the sensing area when the metal layer (for example, a layer in which a copper layer is formed on the ITO electrode) is protected, the image display quality and hue in the sensing area It is possible to sufficiently suppress a decrease in luminance.
- b * in the CIELAB color system is preferably ⁇ 0.2 to 1.0, and 0.0 It is more preferably from 0.7 to 0.7, still more preferably from 0.1 to 0.5.
- b * may be ⁇ 0.2 to 1.0 from the viewpoint of image display quality in the sensing area and prevention of deterioration in hue. preferable.
- the measurement of b * in the CIELAB color system is performed using, for example, a spectrophotometer “CM-5” manufactured by Konica Minolta, and a photosensitive resin composition having a thickness of 10 ⁇ m or less on a glass substrate having a thickness of 0.7 mm. It is obtained by forming a layer and irradiating with ultraviolet rays to photo-cure the photosensitive resin composition layer, and then measuring with a D65 light source set at a viewing angle of 2 °.
- CM-5 spectrophotometer
- the photosensitive resin composition of the present invention can be used for forming a photosensitive layer on a substrate having a touch panel electrode.
- a coating solution that can be obtained by uniformly dissolving or dispersing the photosensitive resin composition in a solvent is prepared, and a coating film is formed by coating on a substrate, and then the solvent is removed by drying.
- a layer can be formed.
- Solvents include ketones, aromatic hydrocarbons, alcohols, glycol ethers, glycol alkyl ethers, glycol alkyl ether acetates, esters, diethylene glycol, chloroform, and chloride from the standpoints of solubility of each component and ease of film formation. Methylene and the like can be used. These solvents may be used alone or as a mixed solvent composed of two or more solvents.
- ethylene glycol monobutyl ether acetate diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or the like.
- the photosensitive resin composition of the present embodiment is preferably used by forming a film on a photosensitive film like the photosensitive element 1 of the present embodiment.
- Laminating the photosensitive film on the base material 100 having the tapping panel electrode makes it possible to easily realize a roll-to-roll process and shorten the solvent drying process, thereby greatly contributing to shortening of the manufacturing process and cost reduction. Can do.
- the photosensitive layer 20 of the photosensitive element 1 can be formed by preparing a coating solution containing the photosensitive resin composition of the present embodiment, and applying and drying the coating solution on the support film 10.
- the coating solution can be obtained by uniformly dissolving or dispersing each component constituting the photosensitive resin composition of the present embodiment described above in a solvent.
- the solvent is not particularly limited and known ones can be used.
- Examples include ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, chloroform and methylene chloride.
- These solvents may be used alone or as a mixed solvent composed of two or more solvents.
- Application methods include, for example, doctor blade coating method, Meyer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, die coating Examples thereof include a coating method.
- the drying conditions are not particularly limited, but the drying temperature is preferably 60 to 130 ° C., and the drying time is preferably 30 seconds to 30 minutes.
- the thickness of the photosensitive layer 20 is a thickness after drying so that the step on the surface of the touch panel (touch sensor) generated by the formation of a partial electrode protective film can be minimized as much as possible to protect the electrode such as rust prevention. It is preferably 1 ⁇ m or more and 10 ⁇ m or less, more preferably 1 ⁇ m or more and 9 ⁇ m or less, further preferably 1 ⁇ m or more and 8 ⁇ m or less, further preferably 2 ⁇ m or more and 8 ⁇ m or less, and 3 ⁇ m or more and 8 ⁇ m or less. Is particularly preferred.
- the photosensitive layer 20 preferably has a minimum visible light transmittance of 90% or more, more preferably 92% or more, and still more preferably 95% or more.
- the photosensitive layer 20 is preferably adjusted so that b * in the CIELAB color system is ⁇ 0.2 to 1.0.
- the viscosity of the photosensitive layer 20 prevents the photosensitive resin composition from exuding from the end face of the photosensitive element 1 for more than one month. From the point of preventing exposure failure and residual development when irradiated with actinic rays caused by the photosensitive resin composition fragments adhering to the substrate, it is preferably 15 to 100 mPa ⁇ s at 30 ° C., It is more preferably 20 to 90 mPa ⁇ s, and further preferably 25 to 80 mPa ⁇ s.
- the viscosity is 1.96 ⁇ at 30 ° C. and 80 ° C. in the thickness direction of this sample using a circular film of 7 mm in diameter and 2 mm in thickness formed from the photosensitive resin composition as a measurement sample. This is a value obtained by measuring the rate of change of thickness when a load of 10 ⁇ 2 N is applied, and converting it to viscosity from the rate of change assuming a Newtonian fluid.
- Examples of the protective film 30 include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, and a film made of a laminated film of polyethylene-vinyl acetate copolymer and polyethylene.
- the thickness of the protective film 30 is preferably about 5 to 100 ⁇ m, but it is preferably 70 ⁇ m or less, more preferably 60 ⁇ m or less, and further preferably 50 ⁇ m or less from the viewpoint of being wound and stored in a roll shape. It is preferably 40 ⁇ m or less.
- Photosensitive element 1 can be stored in a roll or stored.
- the above-mentioned photosensitive resin composition of the present embodiment and a coating solution containing a solvent are applied onto a substrate having a touch panel electrode, dried, and then a photosensitive layer comprising the photosensitive resin composition. 20 may be provided.
- the photosensitive layer preferably satisfies the above-mentioned conditions of film thickness, visible light transmittance, and b * in the CIELAB color system.
- FIG. 2 is a schematic cross-sectional view for explaining an embodiment of a method for forming a protective film for an electrode for a touch panel according to the present invention.
- the method for forming the protective film 22 for the touch panel electrode according to the present embodiment is a method in which the photosensitive layer 20 made of the photosensitive resin composition according to the present embodiment is provided on the base material 100 having the touch panel electrodes 110 and 120. 1 step, a second step in which a predetermined portion of the photosensitive layer 20 is cured by irradiation with actinic light, and a portion other than the predetermined portion of the photosensitive layer 20 after irradiation with actinic light (a portion of the photosensitive layer that is not irradiated with actinic light) is removed And a third step of forming a protective film 22 made of a cured product of a predetermined portion of the photosensitive layer covering a part or all of the electrode. In this way, the touch panel 200 with the protective film 22 which is a touch input sheet is obtained.
- Examples of the base material 100 used in the present embodiment include substrates such as glass plates, plastic plates, and ceramic plates that are generally used for touch panels (touch sensors). On this substrate, a touch panel electrode to be a target for forming a protective film is provided. Examples of the electrode include electrodes such as ITO, Cu, Al, and Mo, and TFT. An insulating layer may be provided over the substrate between the substrate and the electrode.
- the substrate 100 having the touch panel electrodes 110 and 120 shown in FIG. 2 can be obtained, for example, by the following procedure. After forming a metal film by sputtering in the order of ITO and Cu on a substrate 100 such as a PET film, an etching photosensitive film is pasted on the metal film to form a desired resist pattern, and unnecessary Cu is chlorinated. After removing with an etching solution such as an iron aqueous solution, the resist pattern is peeled off.
- an etching solution such as an iron aqueous solution
- the touch panel electrodes 110 and 120 of the substrate 100 are provided while the photosensitive element 1 is heated.
- the photosensitive layer 20 is transferred onto the surface by pressure bonding and laminated (see FIG. 2A).
- Crimping means includes a crimping roll.
- the pressure roll may be provided with a heating means so that it can be heat-pressure bonded.
- the heating temperature for thermocompression bonding is such that the constituent components of the photosensitive layer 20 are sufficient to ensure the adhesion between the photosensitive layer 20 and the substrate 100 and the adhesion between the photosensitive layer 20 and the touch panel electrodes 110 and 120.
- the temperature is preferably 10 to 180 ° C., more preferably 20 to 160 ° C., and still more preferably 30 to 150 ° C. so that it is not easily cured or thermally decomposed.
- the pressure at the time of thermocompression bonding is 50 to 1 ⁇ 10 5 N / m in terms of linear pressure from the viewpoint of suppressing deformation of the substrate 100 while ensuring sufficient adhesion between the photosensitive layer 20 and the substrate 100.
- it is 2.5 ⁇ 10 2 to 5 ⁇ 10 4 N / m, more preferably 5 ⁇ 10 2 to 4 ⁇ 10 4 N / m.
- the preheating temperature at this time is preferably 30 to 180 ° C.
- the coating liquid containing the photosensitive resin composition and the solvent of the present embodiment is prepared, and the touch panel electrodes 110 and 120 of the substrate 100 are provided.
- the photosensitive layer 20 can be formed by coating on the surface and drying.
- the photosensitive layer 20 preferably satisfies the above-described conditions of film thickness, visible light transmittance, and b * in the CIELAB color system.
- a predetermined portion of the photosensitive layer 20 is irradiated with an actinic ray L in a pattern via a photomask 130 (see FIG. 2B).
- the actinic light When irradiating actinic light, if the support film 10 on the photosensitive layer 20 is transparent, the actinic light can be irradiated as it is, and if it is opaque, the actinic light is irradiated after removal. From the viewpoint of protecting the photosensitive layer 20, it is preferable to use a transparent polymer film as the support film 10 and to irradiate actinic rays through the polymer film with the polymer film remaining.
- a known actinic light source can be used, and examples thereof include a carbon arc lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, and a xenon lamp. Not limited.
- the irradiation amount of the actinic ray L is usually 1 ⁇ 10 2 to 1 ⁇ 10 4 J / m 2 , and heating can be accompanied at the time of irradiation. If the irradiation amount of actinic rays is less than 1 ⁇ 10 2 J / m 2 , the effect of photocuring tends to be insufficient, and if it exceeds 1 ⁇ 10 4 J / m 2 , the photosensitive layer 20 tends to discolor. There is.
- the photosensitive layer 20 after irradiation with actinic rays is developed with a developer to remove portions that are not irradiated with actinic rays (that is, other than predetermined portions of the photosensitive layer),
- a protective film 22 made of a cured product of a predetermined portion of the photosensitive layer of this embodiment that covers a part or the whole is formed (see FIG. 2C).
- the formed protective film 22 can have a predetermined pattern.
- the support film 10 is laminated on the photosensitive layer 20 after irradiation with actinic rays, the support film 10 is removed, and then development is performed to remove a portion not irradiated with actinic rays by the developer.
- a developing method using a known developer such as an alkaline aqueous solution, an aqueous developer, an organic solvent, etc., development is performed by a known method such as spraying, showering, rocking immersion, brushing, scraping, etc., and unnecessary portions are removed. Among them, it is preferable to use an alkaline aqueous solution from the viewpoint of environment and safety.
- a known developer such as an alkaline aqueous solution, an aqueous developer, an organic solvent, etc.
- an aqueous solution of sodium carbonate is preferable.
- a dilute solution of sodium carbonate 0.5 to 5% by mass aqueous solution at 20 to 50 ° C. is preferably used.
- the development temperature and time can be adjusted according to the developability of the photosensitive resin composition of the present embodiment.
- a surfactant an antifoaming agent, a small amount of an organic solvent for promoting development, and the like can be mixed in the alkaline aqueous solution.
- the base of the alkaline aqueous solution remaining in the photosensitive layer 20 after development and photocuring is used by known methods such as spraying, rocking immersion, brushing, and scraping using an organic acid, an inorganic acid, or an acid aqueous solution thereof.
- Acid treatment neutralization treatment
- the cured product may be further cured by irradiation with actinic rays (for example, 5 ⁇ 10 3 to 2 ⁇ 10 4 J / m 2 ) as necessary.
- actinic rays for example, 5 ⁇ 10 3 to 2 ⁇ 10 4 J / m 2
- the photosensitive resin composition of the present embodiment exhibits excellent adhesion to a metal without a heating step after development, but if necessary, instead of irradiation with actinic light after development or an active A heat treatment (80 to 250 ° C.) may be performed in combination with the irradiation of light.
- the photosensitive resin composition and the photosensitive element of this embodiment are suitable for use in forming a protective film for a touch panel electrode.
- a protective film can be formed using the coating liquid mixed with the solvent.
- this invention can provide the formation material of the protective film of the electrode for touchscreens containing the photosensitive resin composition which concerns on this invention.
- the protective film forming material for the electrode for a touch panel can include the above-described photosensitive resin composition of the present embodiment, and is preferably a coating solution containing the above-described solvent.
- FIG. 3 is a schematic top view illustrating an example of a capacitive touch panel.
- the touch panel shown in FIG. 3 has a touch screen 102 for detecting touch position coordinates on one surface of the transparent substrate 101, and the transparent electrode 103 and the transparent electrode 104 for detecting a change in capacitance in this region are the substrate 101. It is provided above.
- the transparent electrode 103 and the transparent electrode 104 detect the X position coordinate and the Y position coordinate of the touch position, respectively.
- a lead-out wiring 105 for transmitting a touch position detection signal from the transparent electrode 103 and the transparent electrode 104 to an external circuit.
- the lead-out wiring 105 is connected to the transparent electrode 103 and the transparent electrode 104 by a connection electrode 106 provided on the transparent electrode 103 and the transparent electrode 104.
- a connection terminal 107 for connecting to an external circuit is provided at the end of the lead-out wiring 105 opposite to the connection portion between the transparent electrode 103 and the transparent electrode 104.
- the photosensitive resin composition of this embodiment can be suitably used for forming the protective film 122 for the lead wiring 105, the connection electrode 106, and the connection terminal 107. At this time, the electrodes in the sensing area (touch screen 102) can be protected at the same time.
- the lead-out wiring 105, the connection electrode 106, a part of the sensing region electrode, and a part of the connection terminal 107 are protected by the protective film 122.
- a protective film 123 may be provided so as to protect the entire touch screen 102.
- FIG. 5 is a partial cross-sectional view taken along the line VV of the portion C shown in FIG. 3 and is a view for explaining a connection portion between the transparent electrode 104 and the lead-out wiring 105.
- the transparent electrode 104 and the lead wiring 105 are electrically connected via the connection electrode 106.
- a part of the transparent electrode 104 and all of the lead-out wiring 105 and the connection electrode 106 are covered with a protective film 122.
- the transparent electrode 103 and the lead wiring 105 are electrically connected via the connection electrode 106.
- the transparent electrode 104 and the lead-out wiring 105 may be directly electrically connected.
- the photosensitive resin composition and photosensitive element of this embodiment are suitable for use for forming a protective film for the above-mentioned structural portion.
- the transparent electrode (X position coordinate) 103 is formed on the transparent electrode 101 provided on the substrate 100.
- a transparent electrode (Y position coordinate) 104 is formed.
- the transparent electrode 103 and the transparent electrode 104 can be formed by a method of etching the transparent electrode layer formed on the transparent substrate 100.
- a lead-out wiring 105 for connecting to an external circuit and a connection electrode 106 for connecting the lead-out wiring with the transparent electrode 103 and the transparent electrode 104 are formed.
- the lead-out wiring 105 and the connection electrode 106 may be formed after the formation of the transparent electrode 103 and the transparent electrode 104, or may be formed simultaneously with the formation of each transparent electrode.
- the extraction wiring 105 and the connection electrode 106 can be formed by etching after metal sputtering.
- the lead-out wiring 105 can be formed at the same time as the connection electrode 106 is formed by screen printing using a conductive paste material containing flaky silver, for example.
- a connection terminal 107 for connecting the lead wiring 105 and an external circuit is formed.
- the photosensitive element 1 is pressure-bonded so as to cover the transparent electrode 103 and the transparent electrode 104, the lead-out wiring 105, the connection electrode 106, and the connection terminal 107 formed by the above-described process, and the photosensitive element 1 is exposed on the electrode.
- Layer 20 is provided.
- the actinic ray L is irradiated to the transferred photosensitive layer 20 in a desired shape through a photomask.
- development is performed to remove portions other than the predetermined portion of the photosensitive layer 20, thereby forming a protective film 122 made of a cured product of the predetermined portion of the photosensitive layer 20. In this manner, a touch panel including the protective film 122 can be manufactured.
- binder polymer solution (A1) A flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer was charged with (1) shown in Table 1, heated to 80 ° C. in a nitrogen gas atmosphere, and the reaction temperature was 80 ° C. ⁇ 2 While maintaining the temperature, (2) shown in Table 1 was added dropwise uniformly over 4 hours. After the dropwise addition of (2), stirring was continued at 80 ° C. ⁇ 2 ° C. for 6 hours, and a binder polymer solution (solid content 45% by mass) (A1) having a weight average molecular weight of about 65,000 and an acid value of 78 mgKOH / g was obtained. Obtained.
- binder polymer solution (A2) Preparation of binder polymer solution (A2)
- a binder polymer solution (solid content 45% by mass) (A2) having a weight average molecular weight of about 80,000 and an acid value of 115 mgKOH / g was obtained.
- binder polymer solution (A3) Preparation of binder polymer solution (A3)
- a binder polymer solution (solid content 45% by mass) (A3) having a weight average molecular weight of about 35,000 and an acid value of 156 mgKOH / g was obtained.
- binder polymer solution (A4) In the same manner as in the above (A1), a binder polymer solution (solid content 45% by mass) (A4) having a weight average molecular weight of about 45,000 and an acid value of 195 mgKOH / g was obtained.
- binder polymer solution (A5) In the same manner as in the above (A1), a binder polymer solution (solid content 45% by mass) (A5) having a weight average molecular weight of about 45,000 and an acid value of 155 mgKOH / g was obtained.
- the weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve.
- GPC condition Pump Hitachi L-6000 type (product name, manufactured by Hitachi, Ltd.) Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., product name) Eluent: Tetrahydrofuran Measurement temperature: 40 ° C Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)
- the acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components to obtain a solid content. Then, after precisely weighing 1 g of the polymer whose acid value is to be measured, the precisely weighed polymer was put into an Erlenmeyer flask, 30 g of acetone was added to this polymer, and this was uniformly dissolved. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula.
- Acid value 0.1 ⁇ Vf ⁇ 56.1 / (Wp ⁇ I)
- Vf represents the titration amount (mL) of the KOH aqueous solution
- Wp represents the weight (g) of the measured resin solution
- I represents the ratio (mass%) of the non-volatile content in the measured resin solution.
- Example 1 [Preparation of Coating Solution (V-1) Containing Photosensitive Resin Composition]
- the materials shown in Table 2 were mixed for 15 minutes using a stirrer to prepare a coating solution (V-1) containing a photosensitive resin composition for forming a protective film.
- a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) is used for the photosensitive layer of the obtained laminate, and the exposure amount is 5 ⁇ 10 2 J / m 2 from the upper side of the photosensitive layer (i line).
- the support film was removed to obtain a transmittance measurement sample having a protective film made of a cured film of a photosensitive layer having a thickness of 5.0 ⁇ m.
- the visible light transmittance of the obtained sample was measured in a measurement wavelength range of 400 to 700 nm using an ultraviolet-visible spectrophotometer (U-3310) manufactured by Hitachi.
- the transmittance of the obtained protective film at a wavelength of 400 nm is 97% at a wavelength of 700 nm, 96% at a wavelength of 550 nm, and 94% at a wavelength of 400 nm, and the minimum value of the transmittance at 400 to 700 nm is 94%.
- the transmittance was secured.
- the obtained photosensitive layer was subjected to an exposure amount of 5 ⁇ 10 2 J / m 2 (i-line (wavelength 365 nm) from the upper side of the photosensitive layer side using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.). )), After irradiating with ultraviolet rays, the support film is removed and further irradiated with ultraviolet rays (measured value at i-line (wavelength 365 nm)) with an exposure amount of 1 ⁇ 10 4 J / m 2 from above the photosensitive layer side.
- a b * measurement sample having a protective film made of a cured film of a photosensitive layer having a thickness of 5.0 ⁇ m was obtained.
- CM-5 spectrocolorimeter
- the b * of the protective film was 0.44, and it was confirmed that the protective film had a good b * .
- a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) was used for the photosensitive layer of the obtained laminate, and the exposure amount was 5 ⁇ 10 2 J / m 2 (i-line ( Measured value at a wavelength of 365 nm), after irradiating with ultraviolet rays, the support film is removed, and further the ultraviolet ray is irradiated at an exposure amount of 1 ⁇ 10 4 J / m 2 from above the photosensitive layer side (measured value at i-line (wavelength 365 nm)). Irradiated to obtain an artificial sweat resistance evaluation sample having a protective film made of a cured film of a photosensitive layer having a thickness of 5.0 ⁇ m.
- C Traces are visible on the surface of the protective film, but copper is unchanged.
- D There is a trace on the surface of the protective film, and copper is discolored. When the surface state of the sample for evaluation was observed, a very slight trace was seen on the surface of the protective film, but copper was unchanged and the evaluation was B.
- the laminate obtained above was prepared, it was stored for 24 hours at 23 ° C. and 60%, and then the actinic ray transmitting portion and the actinic ray shielding portion were alternately patterned, and a photo with a line / space of 300 ⁇ m / 300 ⁇ m.
- a photomask is placed on a support film, and using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.), the exposure amount is 5 ⁇ 10 2 J / m 2 from above the photomask surface. (Measured value at i-line (wavelength 365 nm)), ultraviolet rays were imagewise irradiated.
- the support film laminated on the photosensitive layer is removed, and spray development is performed at 30 ° C. for 40 seconds using a 1.0% by mass aqueous sodium carbonate solution to selectively remove the photosensitive layer, and a protective film pattern Formed.
- the substrate surface state of the portion of the obtained substrate with the protective film pattern where the photosensitive layer was selectively removed was observed with a microscope, and the development residue was evaluated according to the following ratings.
- B Copper on the substrate surface is slightly discolored, but there is no development residue.
- C Copper on the surface of the substrate is slightly discolored, and a development residue is slightly generated.
- D Development residue is generated. When the surface state of the sample for evaluation was observed, the copper on the surface of the base material was slightly discolored, a slight amount of development residue was generated, and the evaluation was C.
- a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) is used for the photosensitive layer of the obtained laminate, and the exposure amount is 5 ⁇ 10 2 J / m 2 from the upper side of the photosensitive layer (i line).
- the support film is removed, and further at an exposure amount of 1 ⁇ 10 4 J / m 2 from above the photosensitive layer side (measured value at i-line (wavelength 365 nm))
- a cross-cut adhesion test sample having a protective film made of a cured film of a photosensitive layer having a thickness of 5.0 ⁇ m was obtained.
- C 65% or more and less than 85% of the total area remains adhered.
- C to D 35% or more and less than 65% of the total area remains adhered.
- D 0% or more and less than 35% of the total area remains adhered.
- Examples 2 to 12 A photosensitive element was prepared in the same manner as in Example 1 except that the photosensitive resin composition shown in Tables 3 and 4 (the unit of numerical values in the table is part by mass) and a solution containing a solvent were used. Measurement, salt spray test, development residue test, and cross-cut adhesion test were performed. As shown in Table 5, in Examples 1 to 12, all the measurements of transmittance, salt spray resistance evaluation, and cross-cut adhesion were good results.
- a photosensitive element was prepared in the same manner as in Example 1 except that the photosensitive resin composition shown in Tables 6 and 7 (the unit of numerical values in the table is part by mass) and a solution containing a solvent were used. Measurement, b * measurement, salt spray test, development residue test, and cross-cut adhesion test were performed.
- IRGACURE OXE 01 1,2-octanedione, 1-[(4-phenylthio)-, 2- (O-benzoyloxime)] (manufactured by BASF Corporation)
- IRGACURE 369 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by BASF Corp.)
- Lucirin TPO 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF Corporation)
- Antage W-500 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd.) Methyl ethyl ketone: manufactured by Tonen Chemical Co., Ltd.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Human Computer Interaction (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
すなわち、まず、酸価の測定対象であるバインダーポリマー1gを精秤する。上記精秤したバインダーポリマーにアセトンを30g添加し、これを均一に溶解する。次いで、指示薬であるフェノールフタレインをその溶液に適量添加して、0.1NのKOH水溶液を用いて滴定を行う。そして、次式により酸価を算出する。
酸価=0.1×Vf×56.1/(Wp×I)
式中、VfはKOH水溶液の滴定量(mL)を示し、Wpは測定したバインダーポリマーを含有する溶液の重量(g)を示し、Iは測定したバインダーポリマーを含有する溶液中の不揮発分の割合(質量%)を示す。
なお、バインダーポリマーを合成溶媒や希釈溶媒などの揮発分と混合した状態で配合する場合は、精秤前に予め、揮発分の沸点よりも10℃以上高い温度で1~4時間加熱し、揮発分を除去してから酸価を測定する。
まず、支持フィルム上に感光性樹脂組成物を含有する塗布液を乾燥後の厚みが10μm以下となるように塗布し、これを乾燥することにより、感光性樹脂組成物層を形成する。次に、ガラス基板上に、感光性樹脂組成物層が接するようにラミネータを用いてラミネートする。こうして、ガラス基板上に、感光性樹脂組成物層及び支持フィルムが積層された測定用試料を得る。次に、得られた測定用試料に紫外線を照射して感光性樹脂組成物層を光硬化した後、紫外可視分光光度計を用いて、測定波長域400~700nmにおける透過率を測定する。
撹拌機、還流冷却機、不活性ガス導入口及び温度計を備えたフラスコに、表1に示す(1)を仕込み、窒素ガス雰囲気下で80℃に昇温し、反応温度を80℃±2℃に保ちながら、表1に示す(2)を4時間かけて均一に滴下した。(2)の滴下後、80℃±2℃で6時間撹拌を続け、重量平均分子量が約65,000、酸価が78mgKOH/gのバインダーポリマーの溶液(固形分45質量%)(A1)を得た。
上記(A1)と同様にし、重量平均分子量が約80,000、酸価が115mgKOH/gのバインダーポリマーの溶液(固形分45質量%)(A2)を得た。
上記(A1)と同様にし、重量平均分子量が約35,000、酸価が156mgKOH/gのバインダーポリマーの溶液(固形分45質量%)(A3)を得た。
上記(A1)と同様にし、重量平均分子量が約45,000、酸価が195mgKOH/gのバインダーポリマーの溶液(固形分45質量%)(A4)を得た。
上記(A1)と同様にし、重量平均分子量が約45,000、酸価が155mgKOH/gのバインダーポリマーの溶液(固形分45質量%)(A5)を得た。
GPC条件
ポンプ:日立 L-6000型((株)日立製作所製、製品名)
カラム:Gelpack GL-R420、Gelpack GL-R430、Gelpack GL-R440(以上、日立化成工業(株)製、製品名)
溶離液:テトラヒドロフラン
測定温度:40℃
流量:2.05mL/分
検出器:日立 L-3300型RI((株)日立製作所製、製品名)
酸価は、次のようにして測定した。まず、バインダーポリマーの溶液を、130℃で1時間加熱し、揮発分を除去して、固形分を得た。そして、酸価を測定すべきポリマー1gを精秤した後、精秤したポリマーを三角フラスコに入れ、このポリマーにアセトンを30g添加し、これを均一に溶解した。次いで、指示薬であるフェノールフタレインをその溶液に適量添加して、0.1NのKOH水溶液を用いて滴定を行った。そして、次式により酸価を算出した。
酸価=0.1×Vf×56.1/(Wp×I)
式中、VfはKOH水溶液の滴定量(mL)を示し、Wpは測定した樹脂溶液の重量(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。
[感光性樹脂組成物を含有する塗布液(V-1)の作製]
表2に示す材料を、攪拌機を用いて15分間混合し、保護膜を形成するための感光性樹脂組成物を含有する塗布液(V-1)を作製した。
支持フィルムとして厚さ50μmのポリエチレンテレフタレートフィルムを使用し、上記で作製した感光性樹脂組成物及び溶媒を含有する塗布液(V-1)を支持フィルム上にコンマコーターを用いて均一に塗布し、100℃の熱風対流式乾燥機で3分間乾燥して溶媒を除去し、感光性樹脂組成物からなる感光層(感光性樹脂組成物層)を形成した。得られた感光層の厚さは5μmであった。
得られた感光性エレメント(E-1)のカバーフィルムであるポリエチレンフィルムをはがしながら、厚さ1mmのガラス基板上に、感光層が接するようにラミネータ(日立化成工業(株)製、商品名HLM-3000型)を用いて、ロール温度120℃、基板送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基板を用いたため、このときの線圧は9.8×103N/m)の条件でラミネートして、ガラス基板上に、感光層及び支持フィルムが積層された積層体を作製した。
得られた感光性エレメント(E-1)のポリエチレンフィルムをはがしながら、厚さ0.7mmのガラス基板上に、感光層が接するようにラミネータ(日立化成工業(株)製、商品名HLM-3000型)を用いて、ロール温度120℃、基板送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基板を用いたため、この時の線圧は9.8×103N/m)の条件でラミネートして、ガラス基板上に、感光層及び支持体フィルムが積層された基板を作製した。
得られた感光性エレメント(E-1)のカバーフィルムであるポリエチレンフィルムをはがしながら、スパッタ銅付きポリイミドフィルム(東レフィルム加工(株)製)上に、感光層が接するようにラミネータ(日立化成工業(株)製、商品名HLM-3000型)を用いて、ロール温度120℃、基板送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基板を用いたため、この時の線圧は9.8×103N/m)の条件でラミネートして、スパッタ銅上に、感光層及び支持フィルムが積層された積層体を作製した。
A : 保護膜表面に全く変化なし。
B : 保護膜表面にごくわずかな痕跡が見えるが、銅は変化なし。
C : 保護膜表面に痕跡が見えるが、銅は変化なし。
D : 保護膜表面に痕跡があり、かつ銅が変色する。
評価用試料の表面状態を観察したところ、保護膜表面にごくわずかな痕跡が見えるが、銅は変化なく評価はBであった。
得られた感光性エレメントのカバーフィルムであるポリエチレンフィルムをはがしながら、スパッタ銅付きポリイミドフィルム(東レフィルム加工(株)製)上に、感光層が接するようにラミネータ(日立化成工業(株)製、商品名HLM-3000型)を用いて、ロール温度120℃、基板送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基板を用いたため、この時の線圧は9.8×103N/m)の条件でラミネートして、スパッタ銅上に、感光層及び支持フィルムが積層された積層体を作製した。
A : 基材表面に全く変化なし。
B : 基材表面の銅がわずかに変色するが、現像残渣はない。
C : 基材表面の銅がわずかに変色し、現像残渣がわずかに発生する。
D : 現像残渣が発生する。
評価用試料の表面状態を観察したところ、基材表面の銅がわずかに変色し、現像残渣がわずかに発生し、評価はCであった。
得られた感光性エレメントのカバーフィルムであるポリエチレンフィルムをはがしながら、スパッタ銅付きポリイミドフィルム(東レフィルム加工(株)製)上に、感光層が接するようにラミネータ(日立化成工業(株)製、商品名HLM-3000型)を用いて、ロール温度120℃、基板送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基板を用いたため、この時の線圧は9.8×103N/m)の条件でラミネートして、スパッタ銅上に、感光層及び支持フィルムが積層された積層体を作製した。
A : 全面積のほぼ100%が密着している。
B : 全面積のうち95%以上100%未満が密着し残っている。
B~C: 全面積のうち85%以上95%未満が密着し残っている。
C : 全面積のうち65%以上85%未満が密着し残っている。
C~D: 全面積のうち35%以上65%未満が密着し残っている。
D : 全面積のうち0%以上35%未満が密着し残っている。
評価用試料の碁盤目の状態を観察したところ、スパッタ銅上に全面積のうち95%以上が密着し残っている状態で、評価はBであった。
表3、4(表中の数値の単位は質量部)に示す感光性樹脂組成物及び溶媒を含有する溶液を用いた以外は、実施例1と同様に感光性エレメントを作製し、透過率の測定、塩水噴霧試験、現像残渣試験、クロスカット密着性試験を行った。表5に示すように、実施例1~12においては、透過率の測定、塩水噴霧耐性評価、クロスカット密着性のいずれも良好な結果であった。
表6、7(表中の数値の単位は質量部)に示す感光性樹脂組成物及び溶媒を含有する溶液を用いた以外は、実施例1と同様に感光性エレメントを作製し、透過率の測定、b*の測定、塩水噴霧試験、現像残渣試験、クロスカット密着性試験を行った。
(A)成分
(A1):モノマー配合比(メタクリル酸/メタクリル酸メチル/アクリル酸エチル=12/58/30(質量比))である共重合体のプロピレングリコールモノメチルエーテル/トルエン溶液、重量平均分子量65,000、酸価78mgKOH/g
(A2):モノマー配合比(メタクリル酸/メタクリル酸メチル/アクリル酸エチル=17.5/52.5/30(質量比))である共重合体のプロピレングリコールモノメチルエーテル/トルエン溶液、重量平均分子量80,000、酸価115mgKOH/g
他のバインダーポリマー
(A3):モノマー配合比(メタクリル酸/メタクリル酸メチル/アクリル酸ブチル/メタクリル酸ブチル=24/43.5/15/17.5(質量比))である共重合体のプロピレングリコールモノメチルエーテル/トルエン溶液、重量平均分子量35,000、酸価156mgKOH/g
(A4):モノマー配合比(メタクリル酸/メタクリル酸メチル/メタクリル酸ブチル=30/35/35(質量比))である共重合体のプロピレングリコールモノメチルエーテル/トルエン溶液、重量平均分子量45,000、酸価195mgKOH/g
(A5):モノマー配合比(メタクリル酸/メタクリル酸メチル/アクリル酸エチル=24/46/30(質量比))である共重合体のプロピレングリコールモノメチルエーテル/トルエン溶液、重量平均分子量45,000、酸価155mgKOH/g
A-TMMT:ペンタエリスリトールテトラアクリレート(新中村化学工業(株)製)
TMPTA:トリメチロールプロパントリアクリレート(日本化薬(株)製)
RP-1040:EO変性ペンタエリスリトールテトラアクリレート(日本化薬(株)製)
DPHA:ジペンタエリスリトールヘキサアクリレート(日本化薬(株)製)
他の光重合性化合物
BPE-500:エトキシ化ビスフェノールAジメタクリレート(新中村化学工業(株)製)
9G:ポリエチレングリコール#400ジメタクリレート(新中村化学工業(株)製)
UA-11:ウレタンジアクリレート(新中村化学工業(株)製)
IRGACURE OXE 01:1,2-オクタンジオン,1-[(4-フェニルチオ)-,2-(O-ベンゾイルオキシム)](BASF(株)製)
IRGACURE 369:2-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(BASF(株)製)
Lucirin TPO:2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド(BASF(株)製)
1HT:1H-テトラゾール(東洋紡績(株)製)
MMT:1-メチル-5-メルカプト-1H-テトラゾール(東洋紡績(株)製)
HAT:5-アミノ-1H-テトラゾール(東洋紡績(株)製)
3MT:3-メルカプト-トリアゾール(和光純薬(株)製)
ATT:2-アミノ-5-メルカプト-1,3,4-チアジアゾール(和光純薬(株)製)
AMT:3-アミノ-5-メルカプトトリアゾール(和光純薬(株)製)
Antage W-500:2,2’-メチレン-ビス(4-エチル-6-tert-ブチルフェノール)(川口化学(株)製)
メチルエチルケトン:東燃化学(株)製
Claims (16)
- タッチパネル用電極を有する基材上に、カルボキシル基を有し、酸価が30~120mgKOH/gであるバインダーポリマーと、少なくとも3つのエチレン性不飽和基を有する光重合性化合物と、光重合開始剤と、を含有する感光性樹脂組成物からなる感光層を設け、当該感光層の所定部分を活性光線の照射により硬化させた後に前記所定部分以外を除去し、前記電極の一部又は全部を被覆する前記感光層の前記所定部分の硬化物からなる保護膜を形成する、タッチパネル用電極の保護膜の形成方法。
- 前記光重合性化合物が、ペンタエリスリトール由来の骨格を有する(メタ)アクリレート化合物、ジペンタエリスリトール由来の骨格を有する(メタ)アクリレート化合物、トリメチロールプロパン由来の骨格を有する(メタ)アクリレート化合物、及びグリセリン由来の骨格を有する(メタ)アクリレート化合物からなる群より選択される少なくとも1種の化合物を含む、請求項1に記載のタッチパネル用電極の保護膜の形成方法。
- 前記感光層は、400~700nmにおける可視光透過率の最小値が90%以上である、請求項1又は2に記載のタッチパネル用電極の保護膜の形成方法。
- 前記感光層は、CIELAB表色系でのb*が-0.2~1.0である、請求項1~3のいずれか一項に記載のタッチパネル用電極の保護膜の形成方法。
- 前記感光性樹脂組成物が、トリアゾール化合物、チアジアゾール化合物、及びテトラゾール化合物からなる群より選択される少なくとも1種の化合物を更に含有する、請求項1~4のいずれか一項に記載のタッチパネル用電極の保護膜の形成方法。
- 前記光重合開始剤が、オキシムエステル化合物及び/又はホスフィンオキサイド化合物を含有する、請求項1~5のいずれか一項に記載のタッチパネル用電極の保護膜の形成方法。
- 支持フィルムと、該支持フィルム上に設けられた前記感光性樹脂組成物からなる感光層と、を備える感光性エレメントを用意し、当該感光性エレメントの感光層を前記基材上に転写して前記感光層を設ける、請求項1~6のいずれか一項に記載のタッチパネル用電極の保護膜の形成方法。
- カルボキシル基を有し、酸価が30~120mgKOH/gであるバインダーポリマーと、少なくとも3つのエチレン性不飽和基を有する光重合性化合物と、光重合開始剤と、を含有し、タッチパネル用電極の保護膜形成に用いられる、感光性樹脂組成物。
- 前記光重合性化合物が、ペンタエリスリトール由来の骨格を有する(メタ)アクリレート化合物、ジペンタエリスリトール由来の骨格を有する(メタ)アクリレート化合物、トリメチロールプロパン由来の骨格を有する(メタ)アクリレート化合物、及びグリセリン由来の骨格を有する(メタ)アクリレート化合物からなる群より選択される少なくとも1種の化合物を含む、請求項8に記載の感光性樹脂組成物。
- 保護膜を形成したときの可視光線透過率の最小値が90%以上である、請求項8又は9に記載の感光性樹脂組成物。
- 保護膜を形成したときのCIELAB表色系でのb*が-0.2~1.0である、請求項8~10のいずれか一項に記載の感光性樹脂組成物。
- トリアゾール化合物、チアジアゾール化合物、及びテトラゾール化合物からなる群より選択される少なくとも1種の化合物を更に含有する、請求項8~11のいずれか一項に記載の感光性樹脂組成物。
- 前記光重合開始剤が、オキシムエステル化合物及び/又はホスフィンオキサイド化合物を含有する、請求項8~12のいずれか一項に記載の感光性樹脂組成物。
- 支持フィルムと、該支持フィルム上に設けられた請求項8~13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層と、を備える、感光性エレメント。
- 前記感光層の厚みが10μm以下である、請求項14に記載の感光性エレメント。
- タッチパネル用電極を有する基材上に、請求項1~7のいずれか一項に記載の方法により前記電極の一部又は全部を被覆する保護膜を形成する工程、を備える、タッチパネルの製造方法。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013516864A JP5304973B1 (ja) | 2011-12-05 | 2012-12-04 | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント、並びに、タッチパネルの製造方法 |
US14/362,743 US9488912B2 (en) | 2011-12-05 | 2012-12-04 | Method of forming protective film for touch panel electrode, photosensitive resin composition and photosensitive element, and method of manufacturing touch panel |
KR1020187015625A KR20180063374A (ko) | 2011-12-05 | 2012-12-04 | 터치패널용 전극의 보호막의 형성 방법, 감광성 수지 조성물 및 감광성 엘리먼트, 및, 터치패널의 제조 방법 |
KR1020147016025A KR20140097353A (ko) | 2011-12-05 | 2012-12-04 | 터치패널용 전극의 보호막의 형성 방법, 감광성 수지 조성물 및 감광성 엘리먼트, 및, 터치패널의 제조 방법 |
KR1020177004626A KR20170021909A (ko) | 2011-12-05 | 2012-12-04 | 터치패널용 전극의 보호막의 형성 방법, 감광성 수지 조성물 및 감광성 엘리먼트, 및, 터치패널의 제조 방법 |
CN201280059909.3A CN103975296A (zh) | 2011-12-05 | 2012-12-04 | 触摸面板用电极的保护膜的形成方法、感光性树脂组合物及感光性元件、以及触摸面板的制造方法 |
US15/239,855 US10042254B2 (en) | 2011-12-05 | 2016-08-18 | Method of forming protective film for touch panel electrode photosensitive resin composition and photosensitive element, and method of manufacturing touch panel |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2011/078107 WO2013084283A1 (ja) | 2011-12-05 | 2011-12-05 | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント |
JPPCT/JP2011/078107 | 2011-12-05 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/362,743 A-371-Of-International US9488912B2 (en) | 2011-12-05 | 2012-12-04 | Method of forming protective film for touch panel electrode, photosensitive resin composition and photosensitive element, and method of manufacturing touch panel |
US15/239,855 Division US10042254B2 (en) | 2011-12-05 | 2016-08-18 | Method of forming protective film for touch panel electrode photosensitive resin composition and photosensitive element, and method of manufacturing touch panel |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013084873A1 true WO2013084873A1 (ja) | 2013-06-13 |
Family
ID=48573691
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/078107 WO2013084283A1 (ja) | 2011-12-05 | 2011-12-05 | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント |
PCT/JP2012/081380 WO2013084884A1 (ja) | 2011-12-05 | 2012-12-04 | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及びタッチパネル用電極の保護膜 |
PCT/JP2012/081362 WO2013084873A1 (ja) | 2011-12-05 | 2012-12-04 | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント、並びに、タッチパネルの製造方法 |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/078107 WO2013084283A1 (ja) | 2011-12-05 | 2011-12-05 | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント |
PCT/JP2012/081380 WO2013084884A1 (ja) | 2011-12-05 | 2012-12-04 | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及びタッチパネル用電極の保護膜 |
Country Status (5)
Country | Link |
---|---|
US (2) | US9488912B2 (ja) |
KR (6) | KR20140097354A (ja) |
CN (3) | CN110554813A (ja) |
TW (6) | TWI689850B (ja) |
WO (3) | WO2013084283A1 (ja) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015108881A (ja) * | 2013-12-03 | 2015-06-11 | 日立化成株式会社 | 硬化膜付きタッチパネル用基材の製造方法、感光性樹脂組成物、感光性エレメント及びタッチパネル |
JP2016040123A (ja) * | 2014-08-12 | 2016-03-24 | 富士フイルム株式会社 | 転写フィルム、転写フィルムの製造方法、積層体、積層体の製造方法、静電容量型入力装置、及び、画像表示装置 |
WO2016047691A1 (ja) * | 2014-09-24 | 2016-03-31 | 旭化成イーマテリアルズ株式会社 | 感光性樹脂組成物、感光性樹脂積層体、樹脂パターンの製造方法、硬化膜及び表示装置 |
US20160122562A1 (en) * | 2014-10-29 | 2016-05-05 | C3Nano Inc. | Stable transparent conductive elements based on sparse metal conductive layers |
JP2017009702A (ja) * | 2015-06-18 | 2017-01-12 | 日立化成株式会社 | 感光性樹脂組成物及び感光性エレメント |
JP2017044965A (ja) * | 2015-08-28 | 2017-03-02 | 富士フイルム株式会社 | 転写フィルム、静電容量型入力装置の電極保護膜、積層体、積層体の製造方法および静電容量型入力装置 |
WO2018042833A1 (ja) * | 2016-08-30 | 2018-03-08 | 富士フイルム株式会社 | 感光性樹脂組成物、転写フィルム、タッチパネル用保護膜、タッチパネル及びその製造方法、並びに画像表示装置 |
WO2018096616A1 (ja) * | 2016-11-24 | 2018-05-31 | 日立化成株式会社 | 感光性樹脂組成物、感光性エレメント、保護膜及びタッチパネル |
US10040967B2 (en) | 2015-11-06 | 2018-08-07 | Hitachi Chemical Company, Ltd. | Photosensitive film, photosensitive element, cured product and touch panel |
JP2020027220A (ja) * | 2018-08-16 | 2020-02-20 | 旭化成株式会社 | 感光性樹脂積層体、感光性樹脂積層体を用いたパターン製造方法及び装置 |
KR20230019036A (ko) | 2021-07-30 | 2023-02-07 | 후지필름 가부시키가이샤 | 조성물, 건조물, 경화물, 전사 필름, 전사 필름의 제조 방법 및 패턴 형성 방법 |
US11773275B2 (en) | 2016-10-14 | 2023-10-03 | C3 Nano, Inc. | Stabilized sparse metal conductive films and solutions for delivery of stabilizing compounds |
US11842828B2 (en) | 2019-11-18 | 2023-12-12 | C3 Nano, Inc. | Coatings and processing of transparent conductive films for stabilization of sparse metal conductive layers |
US11999157B2 (en) | 2021-06-24 | 2024-06-04 | Fujifilm Corporation | Transfer film, laminate, acoustic speaker, and method for producing laminate |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013084282A1 (ja) | 2011-12-05 | 2013-06-13 | 日立化成株式会社 | 樹脂硬化膜パターンの形成方法、感光性樹脂組成物及び感光性エレメント |
WO2013084283A1 (ja) | 2011-12-05 | 2013-06-13 | 日立化成株式会社 | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント |
TW201510798A (zh) * | 2013-09-13 | 2015-03-16 | Hon Hai Prec Ind Co Ltd | 單片式玻璃觸控屏及其製造方法 |
JP6643802B2 (ja) * | 2014-05-09 | 2020-02-12 | キヤノン株式会社 | 硬化性組成物、その硬化物、硬化物の製造方法、光学部品の製造方法、回路基板の製造方法、および電子部品の製造方法 |
TWI564762B (zh) | 2015-04-22 | 2017-01-01 | 恆顥科技股份有限公司 | 觸控薄膜疊層卷的製作方法與所製得之觸控薄膜疊層片 |
CN108027675B (zh) | 2015-09-30 | 2021-10-08 | 富士胶片株式会社 | 静电电容型输入装置及其电极保护膜及其膜用组合物、转印薄膜、层叠体、图像显示装置 |
CN112860086A (zh) | 2015-12-07 | 2021-05-28 | 大日本印刷株式会社 | 触控面板笔用书写片、触控面板、显示装置和触控面板笔用书写片的筛选方法 |
JP6919255B2 (ja) * | 2017-03-22 | 2021-08-18 | 東洋インキScホールディングス株式会社 | 活性エネルギー線硬化型組成物 |
JP6915333B2 (ja) * | 2017-03-22 | 2021-08-04 | 東洋インキScホールディングス株式会社 | 活性エネルギー線硬化型組成物 |
CN110462560B (zh) * | 2017-03-28 | 2023-07-28 | 株式会社力森诺科 | 转印型感光性膜 |
KR102401215B1 (ko) * | 2017-03-28 | 2022-05-24 | 쇼와덴코머티리얼즈가부시끼가이샤 | 전사형 감광성 필름, 경화막 패턴의 형성 방법 및 터치 패널 |
CN109961692A (zh) * | 2017-12-26 | 2019-07-02 | 昆山维信诺科技有限公司 | 柔性显示器件及其制备方法 |
CN110221731B (zh) * | 2018-03-02 | 2023-03-28 | 宸鸿光电科技股份有限公司 | 触控面板的直接图案化方法及其触控面板 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011001961A1 (ja) * | 2009-06-30 | 2011-01-06 | Dic株式会社 | 透明導電層パターンの形成方法 |
Family Cites Families (116)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63113585A (ja) | 1986-10-06 | 1988-05-18 | アンダス・コーポレイション | 透明電極ならびにその製法および用途 |
JPH01253666A (ja) | 1988-04-02 | 1989-10-09 | Hitachi Electron Eng Co Ltd | 演算回路内蔵lsi用テスタ |
JPH03281622A (ja) | 1990-03-30 | 1991-12-12 | Hitachi Ltd | 光硬化性ジアリルフタレート樹脂組成物及びそれを用いたプリント回路板 |
JPH06306145A (ja) | 1993-04-23 | 1994-11-01 | Nippon Kayaku Co Ltd | エポキシ樹脂組成物及びその硬化物 |
JPH07159998A (ja) * | 1993-12-06 | 1995-06-23 | Japan Synthetic Rubber Co Ltd | レジスト組成物 |
JP3363232B2 (ja) * | 1993-12-29 | 2003-01-08 | 東京応化工業株式会社 | 耐熱性感光性樹脂組成物およびこれを用いた感光性ドライフィルム |
JP3380616B2 (ja) | 1994-03-16 | 2003-02-24 | 日立化成工業株式会社 | カバーレイ形成用感光性樹脂組成物、感光性フィルム、カバーレイの製造方法及びカバーレイ |
JP3882232B2 (ja) | 1996-09-27 | 2007-02-14 | 三菱化学株式会社 | 透明タッチパネル |
JPH11133617A (ja) | 1997-10-28 | 1999-05-21 | Hitachi Chem Co Ltd | ケミカルミーリング用感光性樹脂組成物及びこれを用いた感光性フィルム |
JP2001162757A (ja) | 1999-12-10 | 2001-06-19 | Hitachi Chem Co Ltd | ラミネート方法 |
KR100761184B1 (ko) | 2000-04-20 | 2007-10-04 | 디에스엠 아이피 어셋츠 비.브이. | 경화성 수지 조성물, 경화 필름 및 복합 제품 |
TWI296738B (ja) * | 2001-03-29 | 2008-05-11 | Hitachi Chemical Co Ltd | |
KR100905478B1 (ko) | 2001-10-05 | 2009-07-02 | 가부시키가이샤 브리지스톤 | 투명 전도성 필름 및 터치패널 |
JP3901543B2 (ja) | 2002-02-26 | 2007-04-04 | 株式会社カネカ | 感光性樹脂組成物及び感光性カバーレイフィルム |
JP3855998B2 (ja) | 2002-02-28 | 2006-12-13 | 日立化成工業株式会社 | 感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法 |
JP2003345015A (ja) | 2002-05-29 | 2003-12-03 | Sumitomo Chem Co Ltd | 感光性樹脂組成物 |
JP2005039097A (ja) | 2003-07-16 | 2005-02-10 | Matsushita Electric Ind Co Ltd | 銅箔の配線形成方法と配線転写基材及び配線基板 |
CN1580953A (zh) * | 2003-08-15 | 2005-02-16 | 富士胶片株式会社 | 感光性转印片、感光性层合体、图像花样的形成方法以及布线花样的形成方法 |
JP4449402B2 (ja) | 2003-08-25 | 2010-04-14 | 日立化成工業株式会社 | 永久レジスト用感光性樹脂組成物、永久レジスト用感光性フィルム、レジストパターンの形成方法及びプリント配線板 |
JP4555938B2 (ja) | 2003-09-24 | 2010-10-06 | 日立化成工業株式会社 | 液晶表示装置用スペーサー及びこれの製造方法、並びにこれを製造するための感光性エレメント |
JP4539165B2 (ja) | 2004-05-12 | 2010-09-08 | Jsr株式会社 | 感放射線性樹脂組成物、スペーサー、およびその形成方法、並びに液晶表示素子 |
TW200613903A (en) | 2004-05-26 | 2006-05-01 | Showa Denko Kk | Photosensitive resin composition, and cured product and use thereof |
JP2006023716A (ja) | 2004-06-08 | 2006-01-26 | Sumitomo Chemical Co Ltd | 感光性樹脂組成物 |
TW200540565A (en) | 2004-06-08 | 2005-12-16 | Sumitomo Chemical Co | Photosensitive resin composition |
CN1707385A (zh) * | 2004-06-11 | 2005-12-14 | 瀚群科技股份有限公司 | 具生物辨识功能的计算机无线周边装置 |
US20080268374A1 (en) | 2004-07-14 | 2008-10-30 | Fujifilm Corporation | Photosensitive Composition, Pattern Forming Material, Photosensitive Laminate, Pattern Forming Apparatus, and Pattern Forming Process |
JP2006065073A (ja) | 2004-08-27 | 2006-03-09 | Fuji Photo Film Co Ltd | 感光性平版印刷版 |
JP2006085053A (ja) | 2004-09-17 | 2006-03-30 | Fuji Photo Film Co Ltd | ネガ型画像形成材料 |
KR101225525B1 (ko) | 2004-10-26 | 2013-01-23 | 쇼와 덴코 가부시키가이샤 | 티올 화합물 및 이를 사용한 감광성 조성물 |
JP2006221099A (ja) * | 2005-02-14 | 2006-08-24 | Hitachi Chem Co Ltd | 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法。 |
JP2006243464A (ja) | 2005-03-04 | 2006-09-14 | Konica Minolta Medical & Graphic Inc | 平版印刷版材料及び画像形成方法 |
JP2006350297A (ja) | 2005-05-19 | 2006-12-28 | Hitachi Chem Co Ltd | 液晶スペーサー及びその製造方法、液晶スペーサー用感光性樹脂組成物並びに感光性エレメント |
CN104133343B (zh) | 2005-05-23 | 2016-11-16 | 日立化成株式会社 | 感光性树脂组合物,感光性元件,光致抗蚀图形的形成方法及印刷电路板的制造方法 |
US20100129752A1 (en) | 2005-05-30 | 2010-05-27 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element employing the same, method of forming resist pattern, and process for producing printed wiring board |
KR100787341B1 (ko) | 2005-09-06 | 2007-12-18 | 다이요 잉키 세이조 가부시키가이샤 | 수지 조성물 및 그의 경화물 및 그것을 이용하여 얻어지는인쇄 배선판 |
JP5384785B2 (ja) | 2005-09-06 | 2014-01-08 | 太陽ホールディングス株式会社 | 樹脂組成物及びその硬化物並びにそれを用いて得られるプリント配線板 |
JP4678271B2 (ja) | 2005-09-26 | 2011-04-27 | Jsr株式会社 | 感光性樹脂組成物、液晶表示パネル用保護膜およびスペーサー、それらを具備してなる液晶表示パネル |
CN100568097C (zh) * | 2005-10-05 | 2009-12-09 | 旭化成电子材料株式会社 | 感光性树脂组合物及层压体 |
US7700264B2 (en) | 2005-10-31 | 2010-04-20 | Nippon Paint Co., Ltd. | Photosensitive resin composition, image forming material and image forming method using thereof |
CN101384961A (zh) * | 2006-02-21 | 2009-03-11 | 日立化成工业株式会社 | 感光性树脂组合物、抗蚀图案的形成方法、印刷电路板的制造方法以及等离子显示屏用基板的制造方法 |
JP4711862B2 (ja) * | 2006-03-08 | 2011-06-29 | 富士フイルム株式会社 | 感光性組成物、感光性フィルム、永久パターン形成方法、及びプリント基板 |
JP4635925B2 (ja) | 2006-03-22 | 2011-02-23 | Tdk株式会社 | 転写用導電性フィルム及びそれを用いた透明導電層が付与された物体 |
JP5188391B2 (ja) * | 2006-05-09 | 2013-04-24 | 旭化成イーマテリアルズ株式会社 | 感光性樹脂組成物 |
JP4733184B2 (ja) | 2006-06-12 | 2011-07-27 | シャープ株式会社 | タッチパネル、表示装置及びタッチパネルの製造方法 |
JP4994136B2 (ja) * | 2006-07-26 | 2012-08-08 | 富士フイルム株式会社 | 感光性組成物、感光性樹脂転写フイルム及びフォトスペーサーの製造方法並びに液晶表示装置用基板、及び液晶表示装置 |
JP5051365B2 (ja) | 2006-08-24 | 2012-10-17 | Jsr株式会社 | 感光性樹脂組成物、表示パネル用スペーサーおよび表示パネル |
JP2008127545A (ja) | 2006-11-24 | 2008-06-05 | Emulsion Technology Co Ltd | 粘着性樹脂組成物、粘着テープ及び電子部品の加工方法 |
KR20080053199A (ko) | 2006-12-08 | 2008-06-12 | 미쓰비시 가가꾸 가부시키가이샤 | 보호막용 열경화성 조성물, 경화물, tft 액티브매트릭스 기판, 및 액정 표시 장치 |
EP1958994B1 (en) | 2007-01-31 | 2010-12-08 | FUJIFILM Corporation | Ink set for inkjet recording and inkjet recording method |
JP5013913B2 (ja) | 2007-03-23 | 2012-08-29 | 富士フイルム株式会社 | 離画壁用感光性樹脂膜の形成方法、感光性転写材料、離画壁付基板、カラーフィルタ及びその製造方法、並びに表示装置 |
JP2009048170A (ja) | 2007-07-24 | 2009-03-05 | Kaneka Corp | 感光性ドライフィルムレジスト、これを用いたプリント配線板、及び、プリント配線板の製造方法 |
TW200910005A (en) | 2007-07-26 | 2009-03-01 | Fujifilm Corp | Photosensitive composition, photosensitive resin transfer film, and method for producing a photospacer, and substrate for a liquid crystal display device and liquid crystal display device |
JP2009073022A (ja) | 2007-09-20 | 2009-04-09 | Fujifilm Corp | 転写用積層材料及び画像形成方法 |
JP2009122224A (ja) | 2007-11-13 | 2009-06-04 | Tokyo Ohka Kogyo Co Ltd | 着色感光性樹脂組成物 |
JP5257648B2 (ja) | 2007-11-27 | 2013-08-07 | 日立化成株式会社 | 感光性エレメント及びその製造方法 |
KR101418735B1 (ko) | 2007-12-25 | 2014-07-11 | 가부시키가이샤 아데카 | 옥심에스테르 화합물 및 상기 화합물을 함유하는 광중합 개시제 |
JP2009186838A (ja) | 2008-02-07 | 2009-08-20 | Fujifilm Corp | 感光性樹脂組成物、フォトスペーサー及びその形成方法、保護膜、着色パターン、表示装置用基板、並びに表示装置 |
KR20090101848A (ko) | 2008-03-24 | 2009-09-29 | 제이에스알 가부시끼가이샤 | 감방사선성 수지 조성물, 스페이서 및 그의 제조 방법 및 액정 표시 소자 |
JP5516844B2 (ja) | 2008-03-24 | 2014-06-11 | Jsr株式会社 | 感放射線性樹脂組成物、スペーサーおよびその製造方法ならびに液晶表示素子 |
WO2009125940A2 (ko) * | 2008-04-10 | 2009-10-15 | 주식회사 엘지화학 | 광활성 화합물 및 이를 포함하는 감광성 수지 조성물 |
JP2010000434A (ja) | 2008-06-19 | 2010-01-07 | Jsr Corp | タッチパネルの製造方法 |
JP5201066B2 (ja) | 2008-06-19 | 2013-06-05 | Jsr株式会社 | タッチパネルの保護膜形成用感放射線性樹脂組成物とその形成方法 |
KR20090132499A (ko) | 2008-06-19 | 2009-12-30 | 제이에스알 가부시끼가이샤 | 감방사선성 수지 조성물과 그로부터 형성된 터치 패널용 보호막 및 그 형성 방법 |
JP5179988B2 (ja) | 2008-07-29 | 2013-04-10 | 富士フイルム株式会社 | 感光性組成物、並びに感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板 |
JP5274151B2 (ja) | 2008-08-21 | 2013-08-28 | 富士フイルム株式会社 | 感光性樹脂組成物、カラーフィルタ及びその製造方法、並びに、固体撮像素子 |
KR101316977B1 (ko) * | 2008-08-22 | 2013-10-11 | 히타치가세이가부시끼가이샤 | 감광성 도전 필름, 도전막의 형성 방법, 도전 패턴의 형성 방법 및 도전막 기판 |
JP2010085929A (ja) | 2008-10-02 | 2010-04-15 | Jsr Corp | 感放射線性樹脂組成物および液晶表示素子用スペーサーとその製造法 |
US8486591B2 (en) | 2008-10-24 | 2013-07-16 | Cheil Industries Inc. | Photosensitive resin composition for color filter and color filter prepared using the same |
TWI521300B (zh) | 2008-11-18 | 2016-02-11 | Sumitomo Chemical Co | Photosensitive resin composition and display device |
JP5396833B2 (ja) | 2008-11-28 | 2014-01-22 | Jsr株式会社 | 感放射線性樹脂組成物、液晶表示素子のスペーサーおよび保護膜ならびにそれらの形成方法 |
JP5504689B2 (ja) | 2008-11-28 | 2014-05-28 | 東レ株式会社 | ネガ型感光性樹脂組成物およびそれを用いたタッチパネル用材料 |
JP5607346B2 (ja) | 2009-01-06 | 2014-10-15 | 住友化学株式会社 | 感光性樹脂組成物、塗膜、パターン及び表示装置 |
JP2010160670A (ja) | 2009-01-08 | 2010-07-22 | Seiko Epson Corp | タッチパネルの製造方法、タッチパネル、表示装置、及び電子機器 |
JP5435596B2 (ja) | 2009-02-13 | 2014-03-05 | エルジー ケム. エルティーディ. | 光活性化合物及びそれを含む感光性樹脂組成物 |
JP4344400B1 (ja) * | 2009-02-16 | 2009-10-14 | 株式会社日本化学工業所 | オキシムエステル化合物及びこれらを用いた感光性樹脂組成物 |
JP2010204532A (ja) | 2009-03-05 | 2010-09-16 | Dnp Fine Chemicals Co Ltd | 保護膜用熱硬化性樹脂組成物およびカラーフィルタ |
CN102378940A (zh) | 2009-03-30 | 2012-03-14 | 旭化成电子材料株式会社 | 感光性树脂组合物及其层压体 |
JP5383288B2 (ja) | 2009-03-31 | 2014-01-08 | 富士フイルム株式会社 | 感光性組成物、感光性樹脂転写フイルム、樹脂パターン及び樹脂パターンの製造方法、並びに液晶表示装置用基板及び液晶表示装置 |
JP2010237449A (ja) | 2009-03-31 | 2010-10-21 | Hitachi Chem Co Ltd | 感光性樹脂組成物、カラーフィルタの製造方法及びカラー表示装置 |
JP2010254966A (ja) | 2009-03-31 | 2010-11-11 | Jsr Corp | 電線被覆用放射線硬化性樹脂組成物 |
JP5593790B2 (ja) | 2009-04-27 | 2014-09-24 | Jsr株式会社 | 感放射線性樹脂組成物、硬化膜及びその形成方法 |
KR20110002609A (ko) | 2009-07-02 | 2011-01-10 | 동우 화인켐 주식회사 | 착색 감광성 수지 조성물, 이를 이용한 컬러 필터 및 이를 포함하는 표시 장치 |
JP2011028594A (ja) | 2009-07-28 | 2011-02-10 | Toshiba Mobile Display Co Ltd | タッチパネル |
JP2011039165A (ja) | 2009-08-07 | 2011-02-24 | Hitachi Chem Co Ltd | アルカリ可溶性光硬化型組成物、該組成物を使用した硬化塗膜及び透明部材 |
KR101144152B1 (ko) | 2009-11-17 | 2012-05-09 | (주)삼원에스티 | 터치패널센서 |
JP5259539B2 (ja) | 2009-09-16 | 2013-08-07 | 日本写真印刷株式会社 | 保護フィルム付き狭額縁タッチ入力シート、保護フィルム付き積層狭額縁タッチ入力シート及びこれらの製造方法 |
JP4601710B1 (ja) | 2009-09-11 | 2010-12-22 | 日本写真印刷株式会社 | 狭額縁タッチ入力シートとその製造方法 |
JP5435556B2 (ja) | 2009-09-16 | 2014-03-05 | 日本写真印刷株式会社 | 導電性シート、積層導電性シート及び導電性パターンシート、並びに積層導電性シートの製造方法、透明アンテナ又は透明ディスプレイ又はタッチ入力シートの製造方法 |
CN102576581B (zh) | 2009-10-15 | 2015-07-22 | 东洋纺织株式会社 | 导电性膏、导电性膜、触摸面板以及导电性薄膜的制造方法 |
CN102597042A (zh) | 2009-10-29 | 2012-07-18 | 日本化药株式会社 | 光半导体密封用可固化树脂组合物及其固化物 |
JP2011128674A (ja) | 2009-12-15 | 2011-06-30 | Sony Corp | 静電容量型入力装置およびその製造方法 |
JP5413228B2 (ja) | 2010-02-09 | 2014-02-12 | 大日本印刷株式会社 | タッチパネルセンサ製造方法およびタッチパネルセンサ |
JP2011186208A (ja) | 2010-03-09 | 2011-09-22 | Asahi Kasei E-Materials Corp | 感光性樹脂組成物 |
TWI477904B (zh) | 2010-03-26 | 2015-03-21 | Sumitomo Chemical Co | Photosensitive resin composition |
JP2011227467A (ja) | 2010-03-31 | 2011-11-10 | Toray Ind Inc | 感光性黒色樹脂組成物、樹脂ブラックマトリクス基板 |
CN102214024B (zh) | 2010-04-08 | 2013-06-26 | 新应材股份有限公司 | 触控板与其制造方法以及具有该触控板的触控显示面板 |
WO2011129210A1 (ja) | 2010-04-14 | 2011-10-20 | 東レ株式会社 | ネガ型感光性樹脂組成物、それを用いた保護膜およびタッチパネル部材 |
JP5627273B2 (ja) | 2010-04-15 | 2014-11-19 | 東洋インキScホールディングス株式会社 | 感光性着色組成物およびカラーフィルタ |
WO2011129312A1 (ja) * | 2010-04-16 | 2011-10-20 | 東レ株式会社 | ネガ型感光性樹脂組成物、硬化膜、およびタッチパネル用部材 |
JP5617329B2 (ja) | 2010-04-28 | 2014-11-05 | 東洋インキScホールディングス株式会社 | 感光性樹脂組成物およびタッチパネル用絶縁膜 |
JP2011237736A (ja) | 2010-05-13 | 2011-11-24 | Hitachi Chem Co Ltd | 感光性樹脂組成物、感光性フィルム及び永久レジスト |
TW201214033A (en) | 2010-06-17 | 2012-04-01 | Sumitomo Chemical Co | Photosensitive resin composition |
TWI417657B (zh) | 2010-09-01 | 2013-12-01 | Daxin Materials Corp | 感光性樹脂組成物 |
US9051397B2 (en) | 2010-10-05 | 2015-06-09 | Basf Se | Oxime ester |
JP5150842B2 (ja) | 2011-02-25 | 2013-02-27 | 綜研化学株式会社 | タッチパネル用部材およびタッチパネル |
JP5729329B2 (ja) | 2011-03-31 | 2015-06-03 | Jsr株式会社 | 感放射線性組成物、並びに硬化膜及びその形成方法 |
EP2692525B1 (en) * | 2011-03-28 | 2015-10-28 | Toray Industries, Inc. | Conductive laminated body and touch panel |
US9164642B2 (en) | 2011-08-02 | 2015-10-20 | Panasonic Intellectual Property Management Co., Ltd. | Touch panel |
WO2013018978A1 (ko) | 2011-08-04 | 2013-02-07 | 주식회사 엘지화학 | 광활성 화합물 및 이를 포함하는 감광성 수지 조성물 |
JP5257558B1 (ja) | 2011-10-03 | 2013-08-07 | 日立化成株式会社 | 導電パターンの形成方法、導電パターン基板及びタッチパネルセンサ |
JP2013238837A (ja) | 2011-11-21 | 2013-11-28 | Toyo Ink Sc Holdings Co Ltd | 感光性ドライフィルム、ならびにそれを用いた保護膜およびタッチパネル用絶縁膜 |
WO2013084282A1 (ja) | 2011-12-05 | 2013-06-13 | 日立化成株式会社 | 樹脂硬化膜パターンの形成方法、感光性樹脂組成物及び感光性エレメント |
JP2013200577A (ja) | 2011-12-05 | 2013-10-03 | Hitachi Chemical Co Ltd | 樹脂硬化膜パターンの形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及び樹脂硬化膜 |
JP5304971B1 (ja) | 2011-12-05 | 2013-10-02 | 日立化成株式会社 | タッチパネル用電極の保護膜及びタッチパネル |
WO2013084284A1 (ja) | 2011-12-05 | 2013-06-13 | 日立化成株式会社 | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント |
WO2013084283A1 (ja) | 2011-12-05 | 2013-06-13 | 日立化成株式会社 | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント |
-
2011
- 2011-12-05 WO PCT/JP2011/078107 patent/WO2013084283A1/ja active Application Filing
-
2012
- 2012-12-04 KR KR1020147016027A patent/KR20140097354A/ko active Application Filing
- 2012-12-04 WO PCT/JP2012/081380 patent/WO2013084884A1/ja active Application Filing
- 2012-12-04 CN CN201910778499.1A patent/CN110554813A/zh active Pending
- 2012-12-04 KR KR1020177026227A patent/KR20170109683A/ko not_active Application Discontinuation
- 2012-12-04 KR KR1020147016025A patent/KR20140097353A/ko active Application Filing
- 2012-12-04 KR KR1020187015625A patent/KR20180063374A/ko not_active Application Discontinuation
- 2012-12-04 KR KR1020177004626A patent/KR20170021909A/ko active Search and Examination
- 2012-12-04 WO PCT/JP2012/081362 patent/WO2013084873A1/ja active Application Filing
- 2012-12-04 US US14/362,743 patent/US9488912B2/en active Active
- 2012-12-04 CN CN201280059909.3A patent/CN103975296A/zh active Pending
- 2012-12-04 CN CN201280059838.7A patent/CN103975295A/zh active Pending
- 2012-12-04 KR KR1020167013378A patent/KR20160065980A/ko active IP Right Grant
- 2012-12-05 TW TW104138855A patent/TWI689850B/zh active
- 2012-12-05 TW TW104125481A patent/TW201543159A/zh unknown
- 2012-12-05 TW TW101145683A patent/TWI510858B/zh not_active IP Right Cessation
- 2012-12-05 TW TW101145693A patent/TWI685776B/zh active
- 2012-12-05 TW TW106134615A patent/TWI689852B/zh active
- 2012-12-05 TW TW105132461A patent/TW201706713A/zh unknown
-
2016
- 2016-08-18 US US15/239,855 patent/US10042254B2/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011001961A1 (ja) * | 2009-06-30 | 2011-01-06 | Dic株式会社 | 透明導電層パターンの形成方法 |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015108881A (ja) * | 2013-12-03 | 2015-06-11 | 日立化成株式会社 | 硬化膜付きタッチパネル用基材の製造方法、感光性樹脂組成物、感光性エレメント及びタッチパネル |
JP2016040123A (ja) * | 2014-08-12 | 2016-03-24 | 富士フイルム株式会社 | 転写フィルム、転写フィルムの製造方法、積層体、積層体の製造方法、静電容量型入力装置、及び、画像表示装置 |
US10059087B2 (en) | 2014-08-12 | 2018-08-28 | Fujifilm Corporation | Transfer film, method for manufacturing transfer film, laminate, method for manufacturing laminate, capacitive input device, and image display device |
WO2016047691A1 (ja) * | 2014-09-24 | 2016-03-31 | 旭化成イーマテリアルズ株式会社 | 感光性樹脂組成物、感光性樹脂積層体、樹脂パターンの製造方法、硬化膜及び表示装置 |
JPWO2016047691A1 (ja) * | 2014-09-24 | 2017-05-25 | 旭化成株式会社 | 感光性樹脂組成物、感光性樹脂積層体、樹脂パターンの製造方法、硬化膜及び表示装置 |
US20160122562A1 (en) * | 2014-10-29 | 2016-05-05 | C3Nano Inc. | Stable transparent conductive elements based on sparse metal conductive layers |
JP2017009702A (ja) * | 2015-06-18 | 2017-01-12 | 日立化成株式会社 | 感光性樹脂組成物及び感光性エレメント |
JP2017044965A (ja) * | 2015-08-28 | 2017-03-02 | 富士フイルム株式会社 | 転写フィルム、静電容量型入力装置の電極保護膜、積層体、積層体の製造方法および静電容量型入力装置 |
WO2017038278A1 (ja) * | 2015-08-28 | 2017-03-09 | 富士フイルム株式会社 | 転写フィルム、静電容量型入力装置の電極保護膜、積層体、積層体の製造方法および静電容量型入力装置 |
US10040967B2 (en) | 2015-11-06 | 2018-08-07 | Hitachi Chemical Company, Ltd. | Photosensitive film, photosensitive element, cured product and touch panel |
US10717893B2 (en) | 2015-11-06 | 2020-07-21 | Hitachi Chemical Company, Ltd. | Photosensitive film, photosensitive element, cured product and touch panel |
WO2018042833A1 (ja) * | 2016-08-30 | 2018-03-08 | 富士フイルム株式会社 | 感光性樹脂組成物、転写フィルム、タッチパネル用保護膜、タッチパネル及びその製造方法、並びに画像表示装置 |
JPWO2018042833A1 (ja) * | 2016-08-30 | 2019-03-07 | 富士フイルム株式会社 | 感光性樹脂組成物、転写フィルム、タッチパネル用保護膜、タッチパネル及びその製造方法、並びに画像表示装置 |
US11773275B2 (en) | 2016-10-14 | 2023-10-03 | C3 Nano, Inc. | Stabilized sparse metal conductive films and solutions for delivery of stabilizing compounds |
WO2018096616A1 (ja) * | 2016-11-24 | 2018-05-31 | 日立化成株式会社 | 感光性樹脂組成物、感光性エレメント、保護膜及びタッチパネル |
JP2020027220A (ja) * | 2018-08-16 | 2020-02-20 | 旭化成株式会社 | 感光性樹脂積層体、感光性樹脂積層体を用いたパターン製造方法及び装置 |
JP7260264B2 (ja) | 2018-08-16 | 2023-04-18 | 旭化成株式会社 | 感光性樹脂積層体、感光性樹脂積層体を用いたパターン製造方法及び装置 |
US11842828B2 (en) | 2019-11-18 | 2023-12-12 | C3 Nano, Inc. | Coatings and processing of transparent conductive films for stabilization of sparse metal conductive layers |
US11999157B2 (en) | 2021-06-24 | 2024-06-04 | Fujifilm Corporation | Transfer film, laminate, acoustic speaker, and method for producing laminate |
KR20230019036A (ko) | 2021-07-30 | 2023-02-07 | 후지필름 가부시키가이샤 | 조성물, 건조물, 경화물, 전사 필름, 전사 필름의 제조 방법 및 패턴 형성 방법 |
Also Published As
Publication number | Publication date |
---|---|
KR20170109683A (ko) | 2017-09-29 |
TWI689852B (zh) | 2020-04-01 |
TW201337677A (zh) | 2013-09-16 |
KR20160065980A (ko) | 2016-06-09 |
TW201706713A (zh) | 2017-02-16 |
US20160357102A1 (en) | 2016-12-08 |
TW201608439A (zh) | 2016-03-01 |
CN110554813A (zh) | 2019-12-10 |
TWI689850B (zh) | 2020-04-01 |
KR20140097354A (ko) | 2014-08-06 |
TW201802654A (zh) | 2018-01-16 |
KR20170021909A (ko) | 2017-02-28 |
TW201543159A (zh) | 2015-11-16 |
TWI510858B (zh) | 2015-12-01 |
US10042254B2 (en) | 2018-08-07 |
KR20140097353A (ko) | 2014-08-06 |
CN103975296A (zh) | 2014-08-06 |
CN103975295A (zh) | 2014-08-06 |
US20140377704A1 (en) | 2014-12-25 |
KR20180063374A (ko) | 2018-06-11 |
US9488912B2 (en) | 2016-11-08 |
WO2013084283A1 (ja) | 2013-06-13 |
WO2013084884A1 (ja) | 2013-06-13 |
TWI685776B (zh) | 2020-02-21 |
TW201331708A (zh) | 2013-08-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2013084873A1 (ja) | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント、並びに、タッチパネルの製造方法 | |
JP6589953B2 (ja) | 感光性エレメント | |
TWI625655B (zh) | 觸控式面板用電極的保護膜的形成方法、感光性樹脂組成物與感光性元件、以及觸控式面板的製造方法 | |
JP6645185B2 (ja) | 硬化膜付き透明基材の製造方法 | |
JP6212970B2 (ja) | タッチパネル用電極の保護膜及びタッチパネル | |
WO2013084284A1 (ja) | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント | |
JP2013200577A (ja) | 樹脂硬化膜パターンの形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及び樹脂硬化膜 | |
JP5304973B1 (ja) | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント、並びに、タッチパネルの製造方法 | |
JP5304971B1 (ja) | タッチパネル用電極の保護膜及びタッチパネル | |
JP2015146038A (ja) | 樹脂硬化膜パターンの形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及び樹脂硬化膜 | |
WO2018008697A1 (ja) | 感光性樹脂組成物、感光性エレメント、タッチパネル電極の保護膜、タッチパネル、及びタッチパネル電極の保護膜の製造方法 | |
JP5304970B1 (ja) | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物、感光性エレメント、タッチパネルの製造方法及びタッチパネル用電極の保護膜 | |
JP6236885B2 (ja) | 保護膜付きタッチパネル用基材の製造方法、感光性樹脂組成物、感光性エレメント、及び、タッチパネル | |
JP5304969B1 (ja) | タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント、並びに、タッチパネルの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013516864 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12855791 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14362743 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20147016025 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12855791 Country of ref document: EP Kind code of ref document: A1 |