WO2016181422A1 - 転写形感光性屈折率調整フィルム、屈折率調整パターンの形成方法及び電子部品 - Google Patents
転写形感光性屈折率調整フィルム、屈折率調整パターンの形成方法及び電子部品 Download PDFInfo
- Publication number
- WO2016181422A1 WO2016181422A1 PCT/JP2015/002379 JP2015002379W WO2016181422A1 WO 2016181422 A1 WO2016181422 A1 WO 2016181422A1 JP 2015002379 W JP2015002379 W JP 2015002379W WO 2016181422 A1 WO2016181422 A1 WO 2016181422A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- refractive index
- resin layer
- compound
- photosensitive resin
- transfer type
- Prior art date
Links
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/10—Removing layers, or parts of layers, mechanically or chemically
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/418—Refractive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
-
- 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
- G06F3/0412—Digitisers structurally integrated in a display
-
- 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
Definitions
- the present invention relates to a transfer type photosensitive refractive index adjusting film, a method for forming a refractive index adjusting pattern, and an electronic component. More specifically, the present invention relates to a transfer type photosensitive refractive index adjusting film capable of easily forming a cured film having both functions of a protective film of a transparent electrode and invisibility of a transparent electrode pattern or improved visibility of a touch screen.
- 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, mobile phones, and electronic dictionaries, and display devices such as OA devices and FA devices.
- These liquid crystal display elements and touch panels are provided with electrodes made of a transparent electrode material.
- ITO Indium-Tin-Oxide
- indium oxide Indium oxide
- tin oxide mainly used because of high visible light transmittance.
- a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure pattern in order to express two-dimensional coordinates by the X axis and the Y axis. Is forming.
- the use of conductive fibers typified by Ag nanowires and carbon nanotubes has been studied as these electrodes, but ITO is still the mainstream.
- the metal wiring is required to transmit a touch position detection signal.
- the metal wiring is generally made of copper.
- the present inventors provide a photosensitive resin layer formed from a specific photosensitive resin composition on a transparent substrate, and the photosensitive resin layer is exposed and developed to be transparent.
- a method for protecting metal wiring on a substrate has been proposed (see, for example, Patent Document 1).
- a plurality of X electrodes made of a transparent electrode material and a plurality of Y electrodes perpendicular to the X electrodes are formed on a base material.
- the color difference increases due to optical reflection between the portion where the transparent electrode pattern is formed and the portion where it is not formed, and the transparent conductive pattern is reflected on the screen when modularized.
- the transparent electrode pattern There is a problem of so-called “bone appearance phenomenon”.
- OCA Optical Clear Adhesive
- Patent Document 1 The method described in Patent Document 1 is effective in protecting the metal wiring, but there is room for improvement in terms of suppressing the bone appearance phenomenon and suppressing the decrease in screen transmittance.
- a low refractive index first curable transparent resin layer and a high refractive index second curable transparent resin layer adjusted to a specific refractive index range.
- the transfer film of Patent Document 2 is not sufficiently transparent, and there is room for further improvement. Further, when a predetermined cured film is formed, developability is not sufficient, and there is room for improvement from the viewpoint of forming a cured film that achieves both suppression of a decrease in screen transmittance and protection of sensor metal wiring. Further, as a specific transfer film configuration, a six-layer film comprising a temporary support / thermoplastic resin layer / intermediate layer / first curable transparent resin layer / second curable transparent resin layer / protective film is disclosed. However, there is room for improvement from the viewpoint of productivity of multilayer films.
- the present invention is capable of easily forming a cured film with sufficient developability, which can suppress the bone-visible phenomenon of the transparent electrode pattern, suppress the decrease in the transmittance of the screen, and protect the sensor metal wiring, and has a highly transparent transfer type photosensitive refraction. It aims at providing a rate adjustment film.
- a transfer-type photosensitive refractive index adjusting film composed of a photosensitive resin layer containing a specific photopolymerization initiator and a high refractive index layer, It is possible to form a thin IM layer (also referred to as an optical adjustment layer or an index matching layer) on the transparent conductive pattern, and to improve the visibility of the touch screen by suppressing the bone-visible phenomenon and reducing the transmittance of the screen.
- the present inventors have found that a cured film that can simultaneously suppress the corrosion of metal wiring can be formed with sufficient developability, and have completed the present invention.
- a transfer type photosensitive refractive index adjusting film comprising a polymerization initiator, wherein the photopolymerization initiator contains an oxime ester compound or a phosphine oxide compound.
- 2. The transfer type photosensitive refractive index adjusting film according to 1, wherein a minimum value of visible light transmittance at a wavelength of 400 to 700 nm of the photosensitive resin layer and the high refractive index layer is 90.00% or more.
- Refractive index adjusting film 7 The transfer type photosensitive refractive index adjusting film according to any one of 1 to 6, wherein the high refractive index layer has a refractive index of 1.50 to 1.90 at a wavelength of 633 nm. 8).
- the binder polymer is (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl 11.
- the transfer type photosensitive refractive index adjusting film according to 9 or 10 which is a binder polymer containing a structural unit derived from at least one compound selected from the group consisting of an ester and 2-ethylhexyl ester of (meth) acrylic acid. 12 12. The transfer type photosensitive refractive index adjusting film according to any one of 1 to 11, wherein the photosensitive resin layer contains a phosphate ester compound. 13 The transfer type photosensitive refractive index adjusting film according to any one of 1 to 12, wherein the total thickness of the photosensitive resin layer and the high refractive index layer is 30 ⁇ m or less. 14.
- a shaped photosensitive refractive index adjusting film can be provided.
- (meth) acrylic acid means acrylic acid or methacrylic acid
- (meth) acrylate means acrylate or a corresponding methacrylate.
- a or B only needs to include one of A and B, or may include both.
- 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.
- the numerical range indicated by 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 sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
- the exemplary materials may be used alone or in combination of two or more unless otherwise specified.
- the transfer type photosensitive refractive index adjusting film of the present invention includes a support film, a photosensitive resin layer provided on the support film, and a high refractive index layer provided on the photosensitive resin layer.
- the photosensitive resin layer includes a photopolymerizable compound and a photopolymerization initiator, and the photopolymerization initiator includes an oxime ester compound or a phosphine oxide compound.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of a transfer type photosensitive refractive index adjusting film of the present invention.
- the transfer type photosensitive refractive index adjusting film 1 shown in FIG. 1 includes a support film 10, a photosensitive resin layer 20 provided on the support film, and a high refractive index layer provided on the photosensitive resin layer. 30.
- the transfer type photosensitive refractive index adjusting film may include a protective film 40 provided on the opposite side of the high refractive index layer 30 to the photosensitive resin layer 20 as shown in FIG.
- the boundary between the high refractive index layer and the photosensitive resin layer is not necessarily clear, and the high refractive index layer may be mixed with the photosensitive resin layer.
- the transfer type photosensitive refractive index adjusting film for example, transparency that satisfies both functions of protecting metal wiring and transparent electrodes on the frame of the touch panel and invisibility of the transparent electrode pattern or improving the visibility of the touch screen.
- High cured film can be formed at a time with sufficient developability.
- FIG. 2 is a schematic cross-sectional view showing an embodiment in which the transfer type photosensitive refractive index adjusting film of the present invention is used for a substrate with a transparent conductive pattern.
- a high refractive index layer 30 is provided on a substrate 50 with a transparent electrode pattern 50a such as ITO so as to cover the pattern 50a, a photosensitive resin layer 20 is provided thereon, and the laminate 100 is formed. It is configured.
- the support film, the photosensitive resin layer, the high refractive index layer, and the protective film will be described.
- a polymer film As the support film 10, a polymer film can be used.
- the polymer film include polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyether sulfone, and cycloolefin polymer. Among these, polyethylene terephthalate or cycloolefin polymer is preferable.
- the thickness of the support film 10 is preferably 5 to 100 ⁇ m from the viewpoint of laminating properties of the photosensitive resin layer and suppressing a reduction in resolution when irradiated with active light through the support film 10. It is more preferably 70 ⁇ m, further preferably 15 to 40 ⁇ m, and particularly preferably 15 to 35 ⁇ m.
- the photosensitive resin layer 20 includes a photopolymerizable compound and a photopolymerization initiator, and the photopolymerization initiator includes an oxime ester compound or a phosphine oxide compound.
- the photopolymerization initiator includes an oxime ester compound or a phosphine oxide compound.
- a cured film having high transparency can be formed with sufficient developability by using an oxime ester compound or a phosphine oxide compound as a photopolymerization initiator.
- the photopolymerizable compound used in the present invention is preferably a compound having an ethylenically unsaturated group.
- the photopolymerizable compound having an ethylenically unsaturated group include a monofunctional vinyl monomer, a bifunctional vinyl monomer, or a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups.
- Examples of the monofunctional vinyl monomer include (meth) acrylic acid, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth ) Acrylic acid 2-ethylhexyl ester and the like.
- bifunctional vinyl monomer examples include polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxypolypropoxy Phenyl) propane, bisphenol A diglycidyl ether di (meth) acrylate, and di (meth) acrylate having a dicyclopentanyl structure or a dicyclopentenyl structure.
- (Meth) acrylate compounds having a skeleton derived from trimethylolpropane, such as trimethylolpropane tri (meth) acrylate; tetramethylolmethanetri (meth) acrylate, tetramethylol, from the viewpoint of corrosion inhibition of metal wiring and transparent electrodes and developability (Meth) acrylate compounds having a skeleton derived from tetramethylolmethane such as methanetetra (meth) acrylate; (meth) acrylates having a skeleton derived from pentaerythritol such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate Compound; (Meth) acrylate compound having a skeleton derived from dipenta
- a (meth) acrylate compound having a skeleton derived from pentaerythritol, a (meth) acrylate compound having a skeleton derived from dipentaerythritol, a (meth) acrylate compound having a skeleton derived from trimethylolpropane, or ditrimethylolpropane It is preferable to include a (meth) acrylate compound having a skeleton derived from, and a (meth) acrylate compound having a skeleton derived from dipentaerythritol, a (meth) acrylate compound having a skeleton derived from trimethylolpropane, or a skeleton derived from ditrimethylolpropane It is more preferable that a (meth) acrylate compound having a skeleton is included, and it is further preferable that a (meth) acrylate compound having a skeleton derived from ditrimethylolpropan
- (meth) acrylate compound having a skeleton derived from will be described by taking a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane as an example.
- (Meth) acrylate having a skeleton derived from ditrimethylolpropane means an esterified product of ditrimethylolpropane and (meth) acrylic acid, and the esterified product includes a compound modified with an alkyleneoxy group.
- the esterified product preferably has a maximum number of 4 ester bonds in one molecule, but a compound having 1 to 3 ester bonds may be mixed.
- the photopolymerizable compound preferably contains a monomer having at least three polymerizable ethylenically unsaturated groups in the molecule.
- the ratio of the monomer having at least three polymerizable ethylenically unsaturated groups in the molecule is from the viewpoint of suppressing photocurability and electrode corrosion.
- the amount of the photopolymerizable compound contained in the photosensitive resin layer is preferably 30 to 100 parts by weight, more preferably 50 to 100 parts by weight, and 75 to 100 parts by weight with respect to 100 parts by weight of the total amount of the photopolymerizable compounds. More preferably.
- the oxime ester compound that is a photopolymerization initiator is preferably a compound represented by the following formula (1), a compound represented by the following formula (2), or a compound represented by the following formula (3). .
- R 11 and R 12 each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group.
- an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group, or a tolyl group is preferable, and an alkyl group having 1 to 4 carbon atoms or a cyclohexane having 4 to 6 carbon atoms is preferable.
- R 13 represents H, OH, COOH, O (CH 2 ) OH, O (CH 2 ) 2 OH, COO (CH 2 ) OH or COO (CH 2 ) 2 OH.
- H, O (CH 2 ) OH, O (CH 2 ) 2 OH, COO (CH 2 ) OH, or COO (CH 2 ) 2 OH are preferred, and H, O (CH 2 ) 2 OH, or COO More preferred is (CH 2 ) 2 OH.
- a plurality of R 14 each independently represents an alkyl group having 1 to 6 carbon atoms, and is preferably a propyl group.
- the plurality of R 14 may be the same or different.
- R 15 represents NO 2 or ArCO (wherein Ar represents a phenyl group or a tolyl group), and Ar is preferably a tolyl group.
- R 16 and R 17 each represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, and is preferably a methyl group, a phenyl group, or a tolyl group.
- R 18 represents an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group.
- R 19 is an organic group having an acetal bond, and is preferably a substituent corresponding to R 19 in a compound represented by the formula (3-1) described later.
- R 20 and R 21 each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, preferably a methyl group, a phenyl group or a tolyl group, and more preferably a methyl group.
- R 22 represents an alkyl group having 1 to 6 carbon atoms.
- n represents an integer of 0 to 4. If R 22 there are a plurality, or different plural R 22 are each identical.
- Examples of the compound represented by the above formula (1) include a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2).
- the compound represented by the following formula (1-1) is available as IRGACURE OXE 01 (manufactured by BASF Japan Ltd., product name).
- Examples of the compound represented by the above formula (2) include a compound represented by the following formula (2-1).
- the compound represented by the following formula (2-1) is available as DFI-091 (product name, manufactured by Daito Chemix Co., Ltd.).
- Examples of the compound represented by the above formula (3) include a compound represented by the following formula (3-1).
- a compound represented by the following formula (3-1) is available as Adekaoptomer N-1919 (manufactured by ADEKA, product name).
- oxime ester compounds are preferably compounds represented by the following formula (4) and compounds represented by the following formula (5).
- phosphine oxide compound As a phosphine oxide compound, the compound represented by following formula (6) and following formula (7) is mentioned, for example. From the viewpoint of fast curability and transparency, a compound represented by the following formula (6) is preferable.
- R 31 , R 32 and R 33 each independently represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a xylyl group or a mesityl group.
- R 34 , R 35 and R 36 each independently represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a xylyl group, a mesityl group or a dimethoxyphenyl group.
- the alkyl group having 1 to 20 carbon atoms may be any of linear, branched and cyclic alkyl groups.
- the alkyl group preferably has 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.
- R 31 , R 32 and R 33 are a phenyl group, a tolyl group, a xylyl group or a mesityl group are preferable.
- R 34 , R 35 and R 36 are a phenyl group, a tolyl group, a xylyl group, a mesityl group or a dimethoxyphenyl group are preferable.
- 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide is preferable 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.
- This compound is commercially available, for example, as LUCIRIN TPO (manufactured by BASF Japan Ltd., product name).
- the photosensitive resin layer may contain a photopolymerization initiator other than the oxime ester compound and the phosphine oxide compound described above.
- photopolymerization initiators other than oxime ester compounds and phosphine oxide compounds include benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone.
- benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzoin, Benzoin compounds such as methylbenzoin and ethylbenzoin; benzyl derivatives such as benzyldimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane; N-phenylglycine, N Phenylglycine derivatives; coumarin compounds; oxazole-based compounds.
- the photosensitive resin layer preferably contains a binder polymer in addition to the above-described photopolymerizable compound and photopolymerization initiator.
- a binder polymer a polymer having a carboxyl group is preferably used from the viewpoint of enabling patterning by alkali development.
- the binder polymer is preferably a copolymer containing structural units derived from (meth) acrylic acid and (meth) acrylic acid alkyl ester.
- the copolymer may contain other monomers that can be copolymerized with the (meth) acrylic acid and the (meth) acrylic acid alkyl ester as constituent units. Specific examples include (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, and styrene.
- Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid-2-ethylhexyl ester, (meth) acrylic And acid hydroxyl ethyl ester.
- (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic particularly from the viewpoint of alkali developability, patterning properties, and transparency with respect to an inorganic alkaline aqueous solution
- a binder polymer comprising a structural unit derived from at least one compound selected from the group consisting of acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester and (meth) acrylic acid 2-ethylhexyl ester preferable.
- the weight average molecular weight of the binder polymer is preferably 10,000 to 200,000, more preferably 15,000 to 150,000, and more preferably 30,000 to 150,000 from the viewpoint of developability. More preferably, it is particularly preferably 30,000 to 100,000, particularly preferably 40,000 to 100,000.
- the weight average molecular weight can be measured by a gel permeation chromatography method with reference to the examples of the present specification.
- the acid value of the binder polymer is preferably 75 mgKOH / g or more from the viewpoint of alkali developability. Further, from the viewpoint of achieving both controllability of the shape of the protective film and rust prevention of the protective film, it is preferably 75 to 200 mgKOH / g, more preferably 75 to 150 mgKOH / g, and 75 to 120 mgKOH. / G is more preferable, and 78 mg to 120 mg KOH / g is particularly preferable.
- an acid value can be measured with reference to the Example of this-application specification.
- the hydroxyl value of the binder polymer is preferably 50 mgKOH / g or less, more preferably 45 mgKOH / g or less, from the viewpoint of further improving the rust prevention property.
- the hydroxyl value can be measured with reference to the examples in the present specification.
- the content of the binder polymer (hereinafter also referred to as component (A)) and the photopolymerizable compound (hereinafter also referred to as component (B)) is the total amount of component (A) and component (B).
- the component (A) is preferably 0 to 85 parts by weight, more preferably 15 to 80 parts by weight, still more preferably 20 to 80 parts by weight, and more preferably 50 to 70 parts by weight with respect to 100 parts by weight. Parts are particularly preferred, and 55 to 65 parts by mass are very particularly preferred.
- the component (A) is 15 parts by mass or more with respect to 100 parts by mass of the total amount of the component (A) and the component (B) in terms of maintaining the pattern formability and the transparency of the protective film. 40 parts by mass or more, more preferably 50 parts by mass or more, and particularly preferably 55 parts by mass or more.
- the content of the photopolymerization initiator (hereinafter also referred to as “component (C)”) is 0.1 mass relative to 100 parts by mass of the total amount of component (A) and component (B) in terms of excellent photosensitivity and resolution. In terms of excellent visible light transmittance, it is preferably 20 parts by mass or less.
- the oxime ester compound is included as a photopolymerization initiator, the content thereof is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). 0.5 to 3.0 parts by mass, more preferably 1.0 to 3.0 parts by mass, and particularly preferably 1.5 to 2.5 parts by mass.
- the content thereof is preferably 3.0 to 15 parts by mass with respect to 100 parts by mass as a total of the components (A) and (B). More preferably, the amount is from 5 to 15 parts by mass, still more preferably from 4.0 to 15 parts by mass, and particularly preferably from 5.0 to 15 parts by mass.
- the photosensitive resin layer includes a triazole compound having a mercapto group, a tetrazole compound having a mercapto group, a thiadiazole compound having a mercapto group, a triazole compound having an amino group, or an amino group from the viewpoint of further improving the rust prevention property of the protective film. It is preferable to further include a tetrazole compound (hereinafter also referred to as component (D)).
- component (D) tetrazole compound
- the triazole compound having a mercapto group include 3-mercapto-triazole (manufactured by Wako Pure Chemical Industries, Ltd., product name “3MT”).
- Examples of the thiadiazole compound having a mercapto group include 2-amino-5-mercapto-1,3,4-thiadiazole (product name “ATT” manufactured by Wako Pure Chemical Industries, Ltd.).
- triazole compound having an amino group examples include benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, etc. , 3-mercaptotriazole, 5-mercaptotriazole, and other triazole compounds containing a mercapto group are substituted with amino groups.
- tetrazole compound having an amino group examples include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-carboxymethyl-5-amino-tetrazole and the like. These tetrazole compounds may be water-soluble salts thereof. Specific examples thereof include alkali metal salts such as sodium, potassium and lithium of 1-methyl-5-amino-tetrazole.
- the content thereof is preferably 0.05 to 5.0 parts by weight, and preferably 0.1 to 2.0 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B) Part by mass is more preferable, 0.2 to 1.0 part by mass is further preferable, and 0.3 to 0.8 part by mass is particularly preferable.
- the photosensitive resin layer preferably contains a phosphate ester compound (hereinafter also referred to as component (E)) from the viewpoint of preventing the occurrence of undeveloped residues, and the phosphate ester compound contains a photopolymerizable unsaturated bond. Is more preferable.
- a phosphate ester compound shall not be included in the photopolymerizable compound of (B) component.
- the phosphoric acid ester compound as the component (E) includes a phosphor series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-, from the viewpoint of achieving both high levels of rust prevention and developability of the protective film to be formed.
- a phosphor series Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-, from the viewpoint of achieving both high levels of rust prevention and developability of the protective film to be formed.
- KAYAMER series PM21, PM-2, etc., manufactured by Nippon Kayaku Co., Ltd., product name
- the content thereof is preferably 0.05 to 5.0 parts by mass, preferably 0.1 to 2.0 parts per 100 parts by mass of the total amount of the components (A) and (B). Mass parts are more preferred, 0.2 to 1.0 parts by mass are more preferred, and 0.2 to 0.6 parts by mass are particularly preferred.
- the high refractive index layer is a layer having a refractive index higher than that of the photosensitive resin layer.
- the refractive index of the photosensitive resin layer with respect to light having a wavelength of 633 nm is usually 1.40 to 1.49.
- the high refractive index layer preferably has a refractive index of 1.50 to 1.90, more preferably 1.53 to 1.85, and more preferably 1.55 to 1.75 in light having a wavelength of 633 nm. More preferably. Since the refractive index at 633 nm of the high refractive index layer is 1.50 to 1.90, the laminate shown in FIG. 2 is used on the transparent electrode pattern 50a such as ITO and the photosensitive resin layer 20.
- the refractive index of various members for example, OCA that bonds a cover glass and a transparent electrode pattern used when modularizing
- a transparent electrode pattern such as ITO
- the refractive index of a transparent electrode such as ITO is preferably 1.80 to 2.10, more preferably 1.85 to 2.05, and even more preferably 1.90 to 2.00.
- the refractive index of a member such as OCA is preferably 1.45 to 1.55, more preferably 1.47 to 1.53, and further preferably 1.48 to 1.51. .
- the film thickness of the high refractive index layer is preferably from 10 to 500 nm, more preferably from 20 to 300 nm, further preferably from 30 to 250 nm, particularly preferably from 40 to 200 nm, and from 45 to A thickness of 150 nm is very preferable.
- the film thickness is 10 to 500 nm, the reflected light intensity of the entire screen can be further reduced.
- the high refractive index layer preferably contains a compound having a triazine ring, a compound having an isocyanuric acid skeleton, a compound having a fluorene skeleton, or a metal oxide (hereinafter also referred to as (F) component).
- a compound having a triazine ring preferably contains a compound having an isocyanuric acid skeleton, a compound having a fluorene skeleton, or a metal oxide (hereinafter also referred to as (F) component).
- the high refractive index layer is preferably a combination of a compound having a triazine ring or a compound having an isocyanuric acid skeleton and a compound having a fluorene skeleton from the viewpoints of refractive index, developability, patternability, and transparency. .
- Ar represents a divalent group containing at least one selected from an aromatic ring (having 6 to 20 carbon atoms) and a heterocyclic ring (having 5 to 20 atoms).
- Each X independently represents NR 1 .
- R 1 is each independently a hydrogen atom, an alkyl group (carbon number is 1 to 20 for example), an alkoxy group (carbon number is 1 to 20), an aryl group (carbon number is 6 to 20) or an aralkyl group (carbon The number indicates, for example, 7 to 20).
- a plurality of X may be the same or different.
- a hyperbranched polymer having a triazine ring is preferable, and is commercially available, for example, as the HYPERTECH series (manufactured by Nissan Chemical Industries, Ltd., product name).
- This hyperbranched polymer is polymerized by, for example, dropping a 2,4,6-trichloro-1,3,5-triazine dimethylacetamide solution into a dimethylacetamide solution of m-phenyldiamine to give 2-aminopropanol Furthermore, it is made to react by dripping and making it precipitate in aqueous ammonia solution.
- the obtained hyperbranched polymer having a triazine ring can be modified with phthalic acid or succinic acid to contain an acid value.
- the “isocyanuric acid skeleton” of the compound having an isocyanuric acid skeleton refers to a group obtained by removing three hydrogen atoms from isocyanuric acid, and examples of the compound having an isocyanuric acid skeleton include compounds represented by the following formula (9). It is done. Specifically, triallyl isocyanurate is preferred.
- each R independently represents a hydrogen atom, a halogen atom, R 2 OH (R 2 is alkylene having 1 to 6 carbon atoms) or an allyl group, preferably an allyl group.
- R 2 OH is preferably a methylol group or a hydroxyethyl group.
- a compound having a 9,9-bis [4-2 (meth) acryloyloxyethoxy) phenyl] fluorene skeleton is preferable.
- the compound may be modified with (poly) oxyethylene or (poly) oxypropylene. These are commercially available, for example, as EA-0200 (product name, manufactured by Osaka Gas Chemical Co., Ltd.). Further, it may be epoxy-modified with epoxy acrylate. These are commercially available, for example, as GA5000 and EG200 (product name, manufactured by Osaka Gas Chemical Co., Ltd.).
- the component (F) contains a metal oxide
- the polymer having a carboxyl group described in the binder polymer of the photosensitive resin layer, or the ethylenically unsaturated group described in the photopolymerizable compound is used. It is preferable to form a high refractive index layer by using a single photopolymerizable compound or a combination thereof.
- the metal oxide examples include zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, silicon oxide, and glass. Among these, zirconium oxide is preferable.
- the metal oxide is preferably in the form of fine particles.
- the metal oxide include nano-use OZ-S30K, OZ-S40K-AC, OZ-S30M (product name, manufactured by Nissan Chemical Industries, Ltd.), NANON5ZR-010, NANONZR-020 (product name, manufactured by Solar Corporation), SZR-K and SZR-M (Sakai Chemical Industry Co., Ltd., product name) are commercially available.
- Zirconium oxide is preferably used in combination with amorphous silica or tin oxide. Thereby, when adjusting the transfer type photosensitive refractive index adjusting film, it becomes possible to further improve the transparency and developability of the high refractive index layer. Furthermore, zirconium oxide is also preferably used in combination with yttrium oxide. Thereby, when adjusting the transfer type photosensitive refractive index adjusting film, it becomes possible to further improve the transparency and refractive index of the high refractive index layer. Note that nanouse OZ-S30K, OZ-S40K-AC, and OZ-S30M are mixed with amorphous silica or tin oxide in addition to zirconium oxide.
- SZR-K and SZR-M are mixed with yttrium oxide.
- Zirconium oxide and tin oxide can be identified by detecting and mapping a zirconium element, an oxygen element, and a tin element using STEM-EDX.
- the content of the component (F) in the high refractive index layer is preferably in the following range in order to adjust the refractive index of light having a wavelength of 633 nm of the high refractive index layer to a range of 1.5 to 1.9.
- a compound having a triazine ring When a compound having a triazine ring is contained, it is preferably contained in an amount of 10 to 100 parts by mass, more preferably 10 to 70 parts by mass, and more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the total amount of component (F). Is more preferable, and 10 to 55 parts by mass is particularly preferable.
- the compound having an isocyanuric acid skeleton is included, it is preferably included in an amount of 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, and more preferably 30 to 70 parts by weight with respect to 100 parts by weight of the total amount of the component (F). More preferably.
- a compound having a fluorene skeleton When a compound having a fluorene skeleton is included, it is preferably included in an amount of 10 to 100 parts by weight, more preferably 20 to 90 parts by weight, and more preferably 30 to 90 parts by weight with respect to 100 parts by weight of the total amount of component (F). Is more preferable, and 40 to 90 parts by mass is particularly preferable.
- the metal oxide when included, it is preferably 10 to 100 parts by mass, more preferably 20 to 93 parts by mass, and further preferably 30 to 90 parts by mass with respect to 100 parts by mass of the total amount of the component (F). preferable.
- the high refractive index layer may contain one or more components among the components (A) to (E) of the photosensitive resin layer as necessary. Further, the high refractive index layer may consist essentially of at least one of the above-described component (F). That is, the high refractive index layer in the present invention may consist essentially of the component (F).
- “substantially” means that 95% by mass or more and 100% by mass or less (preferably 98% by mass or more and 100% by mass or less) of the component constituting the layer is the component (F).
- additives may be added as necessary.
- the additive include organosiloxanes such as octamethylcyclotetrasiloxane, and polymerization inhibitors such as 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol).
- the minimum value of the visible light transmittance at 400 to 700 nm of the laminate of the photosensitive resin layer and the high refractive index layer is preferably 90.00% or more. It is more preferably 90.50% or more, and further preferably 90.70% or more. If the minimum value of transmittance in a general visible light wavelength range of 400 to 700 nm is 90.00% or more, an image in the sensing area can be used to protect the transparent electrode in the sensing area of the touch panel (touch sensor). It can suppress sufficiently that display quality, a hue, and a brightness
- the maximum visible light transmittance is usually 100% or less. The visible light transmittance can be measured with reference to the examples in the present specification.
- the photosensitive resin layer 20 and the high refractive index layer 30 of the transfer type photosensitive refractive index adjusting film are, for example, a coating liquid containing a photosensitive resin composition for forming the photosensitive resin layer and a high component containing the component (F). It can be formed by preparing a coating liquid containing a refractive index composition, applying the coating liquid onto the support film 10 or the protective film 40, drying and bonding them. Further, a coating liquid containing a photosensitive resin composition is applied on the support film 10 and dried, and then a coating liquid containing a high refractive index composition is applied and dried on the photosensitive resin layer 20, and the protective film 40. It can also be formed by pasting.
- the coating solution can be obtained by uniformly dissolving or dispersing the above-described photosensitive resin composition or high refractive index composition in a solvent.
- the solvent used for the coating solution is not particularly limited, and known ones can be used. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, methanol, ethanol, propanol, butanol, methylene glycol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, 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, methylene chloride and the like.
- Application methods include doctor blade coating method, Mayer 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, and die coating method. Etc.
- the drying conditions are not particularly limited, but the drying temperature is preferably 60 to 130 ° C., and the drying time is preferably 0.5 to 30 minutes.
- the total thickness of the photosensitive resin layer and the high refractive index layer is preferably 30 ⁇ m or less, and preferably 20 ⁇ m or less from the viewpoint of improving the followability during lamination. Is more preferably 10 ⁇ m or less. Furthermore, from the viewpoint of suppressing the occurrence of pinholes due to the protrusions of the base material, the thickness is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and further preferably 3 ⁇ m or more. If it is 3 micrometers or more, it will become easy to suppress the influence by the protrusion of a base material as much as possible, and to maintain rust prevention property.
- the viscosity of the photosensitive refractive index adjusting layer is determined from the viewpoint of suppressing the composition from exuding from the end face of the transfer type photosensitive refractive index adjusting film when the transfer type photosensitive refractive index adjusting film is stored in a roll. 15 to 100 mPa ⁇ s at 30 ° C. from the viewpoint of suppressing fragmentation and adhesion to the substrate as a result of the photosensitive refractive index adjustment layer becoming too hard when cutting the photosensitive refractive index adjustment film. It is preferably 20 to 90 mPa ⁇ s, more preferably 25 to 80 mPa ⁇ s.
- Examples of the protective film 40 include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, a laminated film of polyethylene-vinyl acetate copolymer and polyethylene, and the like.
- the thickness of the protective film 40 is preferably 5 to 100 ⁇ m, but is preferably 70 ⁇ m or less, more preferably 60 ⁇ m or less, and even more preferably 50 ⁇ m or less from the viewpoint of storing in a roll. 40 ⁇ m or less is particularly preferable.
- the high refractive index layer 30 is adhered to the surface of the substrate 50 (substrate with a transparent conductive pattern).
- the high refractive index layer and the photosensitive resin layer are laminated (transferred).
- the pressing means include a pressing 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 10 in order to prevent the adhesiveness between the high refractive index layer 30 and the substrate 50 and the constituent components of the photosensitive resin layer and the high refractive index layer from being hard-cured or thermally decomposed. It is preferably set to ⁇ 160 ° C., more preferably 20 to 150 ° C., and further preferably 30 to 150 ° C.
- the pressure during thermocompression bonding is 50 to 1 ⁇ 10 5 N in terms of linear pressure from the viewpoint of suppressing deformation of the base material 50 while ensuring sufficient adhesion between the high refractive index layer 30 and the base material 50.
- / M preferably 2.5 ⁇ 10 2 to 5 ⁇ 10 4 N / m, more preferably 5 ⁇ 10 2 to 4 ⁇ 10 4 N / m.
- the transfer-type photosensitive refractive index adjusting film is thermocompression bonded as described above, pre-heat treatment of the base material before lamination is not necessarily required, but the adhesion between the high refractive index layer 30 and the base material 50 is further improved.
- the substrate 50 may be preheated.
- the treatment temperature at this time is preferably 30 to 150 ° C.
- the substrate examples include substrates such as glass plates, plastic plates, ceramic plates and films used for touch panels (touch sensors).
- an electrode to be a target for forming a cured film is provided on this base material.
- the electrode examples include electrodes such as ITO, Cu, Al, and Mo.
- an insulating layer may be provided on the base material between the base material and the electrode.
- a predetermined portion of the photosensitive refractive index adjusting layer after the transfer is irradiated with actinic rays in a pattern form through a photomask.
- actinic light if the support film 10 on the photosensitive refractive index adjusting layer is transparent, the actinic light can be irradiated as it is, and if it is opaque, the actinic light is irradiated after removal.
- a known active light source can be used as the active light source.
- the irradiation amount of actinic rays is 1 ⁇ 10 2 to 1 ⁇ 10 4 J / m 2 , and heating can be accompanied during irradiation. If the irradiation amount of this actinic ray is 1 ⁇ 10 2 J / m 2 or more, photocuring can sufficiently proceed, and if it is 1 ⁇ 10 4 J / m 2 or less, the photosensitive refractive index is adjusted. There exists a tendency which can suppress that a layer discolors.
- the unexposed portions of the photosensitive resin layer and the high refractive index layer after irradiation with actinic rays are removed with a developer to form a refractive index adjustment pattern that covers part or all of the transparent electrode.
- the image development process is performed.
- the development step can be performed by a known method such as spraying, showering, rocking dipping, brushing, scraping, or the like using a known developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent.
- spray development is preferably performed using an alkaline aqueous solution from the viewpoint of environment and safety.
- the development temperature and time can be adjusted within a conventionally known range.
- the electronic component according to the present embodiment includes a refractive index adjustment pattern formed using a transfer type photosensitive refractive index adjustment film.
- Examples of the electronic component include a touch panel, a liquid crystal display, an organic electroluminescence, a solar cell module, a printed wiring board, and electronic paper.
- FIG. 3 is a schematic top view showing an example of a capacitive touch panel.
- the touch panel shown in FIG. 3 has a touch screen 102 for detecting a touch position coordinate on one side of a transparent base material 101, and is based on a transparent electrode 103 and a transparent electrode 104 for detecting a capacitance change in this region. It is provided on the material 101.
- 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 is provided.
- 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 refractive index adjustment pattern 123 As shown in FIG. 3, by forming the refractive index adjustment pattern 123, the transparent electrode 103, the transparent electrode 104, the lead-out wiring 105, the connection electrode 106, the function of the protective film of the connection terminal 107, and the transparent electrode pattern are formed.
- the refractive index adjustment function of the sensing area is simultaneously performed.
- the weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) and was converted by using a standard polystyrene calibration curve.
- GPC gel permeation chromatography
- Acid value 0.1 ⁇ Vf ⁇ 56.1 / (Wp ⁇ I / 100)
- Vf represents the titration amount (mL) of the KOH aqueous solution
- Wp represents the mass (g) of the measured resin solution
- I represents the proportion (mass%) of the non-volatile content in the measured resin solution.
- hydroxyl value (A ⁇ B) ⁇ f ⁇ 28.05 / sample (g) + acid value
- A represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test
- B represents the amount (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for titration
- f represents a factor.
- binder polymer solution (A2)] (2) shown in Table 1 is 12 parts by weight of methacrylic acid, 38 parts by weight of methyl methacrylate, 30 parts by weight of ethyl acrylate, 20 parts by weight of cyclohexyl methacrylate and 1.1 parts by weight of 2,2′-azobis (isobutyronitrile).
- the binder polymer solution was synthesized in the same manner as (A1) except that the weight average molecular weight was 65,000, the acid value was 78 mgKOH / g, and the hydroxyl value was 2 mgKOH / g (solid content 45% by mass) (A2 )
- binder polymer solution (A3)) (2) shown in Table 1 is 24 parts by weight of methacrylic acid, 44 parts by weight of methyl methacrylate, 15 parts by weight of butyl acrylate, 17 parts by weight of butyl methacrylate and 3 parts by weight of 2,2′-azobis (isobutyronitrile).
- binder polymer solution (A4) (2) shown in Table 1 is 30 parts by weight of methacrylic acid, 22 parts by weight of methyl methacrylate, 10 parts by weight of ethyl acrylate, 8 parts by weight of butyl methacrylate, 30 parts by weight of styrene and 2,2′-azobis (isobutyro (Nitrile)
- a binder polymer solution (solid content) having a weight average molecular weight of 50,000, an acid value of 196 mgKOH / g, and a hydroxyl value of 2 mgKOH / g was synthesized in the same manner as (A1) except that the amount was changed to 1.1 parts by mass. 45% by mass) (A4) was obtained.
- T-1420 (T): Ditrimethylolpropane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., product name)
- FA321M (meth) acrylic compound / bisphenol AEO-modified dimethacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.)
- IRGACURE OXE 01 1,2-octanedione, 1-[(4-phenylthio) phenyl-, 2- (O-benzoyloxime)] (product name, manufactured by BASF Corporation)
- IRGACURE 379 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (product name, manufactured by BASF Japan Ltd.)
- DETX 2,4-diethyl thioxanthone (Nippon Kayaku Co., Ltd., product name)
- TPO 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF Japan Ltd., product name “LUCIRIN TPO”)
- Component PM-21 Phosphate ester containing photopolymerizable unsaturated bond (product name, manufactured by Nippon Kayaku Co., Ltd.)
- Phosmer-M 2- (methacryloyloxy) ethyl phosphate (product name, manufactured by Unichemical Co., Ltd.)
- Component UR658 a polymer having a triazine skeleton (manufactured by Nissan Chemical Industries, Ltd., product name “HYPERTECH series UR658” (trade name)) Triallyl isocyanurate: Tokyo Chemical Industry Co., Ltd.
- OZ-S40K-AC Zirconia dispersion (Nissan Chemical Industry Co., Ltd., product name “Nanouse OZ-S40K-AC”)
- OZ-S30K Zirconia dispersion (manufactured by Nissan Chemical Industries, Ltd., product name “Nanouse OZ-S30K”)
- EA0200 polyoxyethylene-modified 9,9-bis (4-hydroxyphenyl) full orange acrylate (product name, manufactured by Osaka Gas Chemical Co., Ltd.)
- EAF5503 Mixture of polyoxyethylene-modified 9,9-bis (4-hydroxyphenyl) fluorene acrylate / benzyl acrylate / 9,9-bis (4-hydroxyphenyl) fluorene skeleton compound (manufactured by Osaka Gas Chemical Co., Ltd., product name) )
- EA-HC931 polyoxyethylene modified 9,9-bis (4-hydroxyphenyl) full orange acrylate and other mixture (product name, manufactured
- the protective film having the high refractive index layer prepared above and the support film having the photosensitive resin layer prepared above are used for high refraction.
- the transfer type photosensitive refractive index adjusting film was prepared by bonding at 23 ° C. so that the refractive index layer and the photosensitive resin layer were in close contact with each other.
- the refractive index of the single refractive index layer in the form of the transfer type photosensitive refractive index adjusting film is the value of the outermost surface layer on the support film side of the high refractive index layer.
- the photosensitive resin layer is exposed at an exposure amount of 5 ⁇ 10 2 J / m 2 from the upper side of the photosensitive resin layer (i Line (measured value at a wavelength of 365 nm), after irradiating ultraviolet rays, the support film is removed, and further at an exposure amount of 1 ⁇ 10 4 J / m 2 from above the photosensitive resin layer side (measurement at the i-line (wavelength 365 nm)) Value)
- An ultraviolet ray was irradiated to obtain a measurement sample having a cured film of a photosensitive resin layer having a thickness of 8 ⁇ m.
- the obtained hue measurement sample was subjected to a light source setting D65 using a spectrocolorimeter (manufactured by Konica Minolta, product name “CM-5”) so that a light source was present on the photosensitive resin layer side.
- the Y value in the XYZ color system (referred to as reflectance R) was measured using a SCI (including regular reflection light) method with a viewing angle of 2 °, a measurement diameter of 30 mm ⁇ , and normalization was performed using the following formula.
- Reflectivity R normalization actual reflectance value / reflectance actual value of measurement sample (Comparative Example 16) in which only the photosensitive resin layer is laminated ⁇ 100
- the measured values of the transparent conductive film alone are shown in Table 5.
- HLM-3000 type Using a product name “HLM-3000 type”, a roll temperature of 120 ° C., a substrate feed speed of 1 m / min, a pressure of pressure (cylinder pressure) of 4 ⁇ 10 5 Pa (thickness of 1 mm, length 10 cm ⁇ width 10 cm) Since the material was used, the lamination was performed under the condition that the linear pressure at this time was 9.8 ⁇ 10 3 N / m), and the high refractive index layer, the photosensitive resin layer, and the support film were laminated on the sputtered copper. The body was made.
- a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd., product name “EXM1201”) is used for the photosensitive resin layer of the obtained laminate, and the exposure amount is 5 ⁇ 10 2 J from above the photosensitive resin layer side.
- / M 2 (measured value at a wavelength of 365 nm)
- the support film was removed, and the exposure amount was 1 ⁇ 10 4 J / m 2 (measured value at a wavelength of 365 nm) from above the photosensitive resin layer side. It was allowed to stand for 30 minutes in a box dryer (model number “NV50-CA” manufactured by Mitsubishi Electric Corporation) irradiated with ultraviolet rays and heated to 140 ° C. Thereby, a sample for artificial sweat resistance evaluation was obtained.
- the visible light transmittance and haze were measured in the measurement wavelength range of 400 to 700 nm.
- the measured values of the glass substrate alone are shown in Table 5.
- roll temperature is 120 ° C.
- substrate feed speed is 1 m / min
- pressure (cylinder pressure) is 4 ⁇ 10 5 Pa (thickness is 125 ⁇ m) Since a substrate of 10 cm in length and 10 cm in width was used, the linear pressure at this time was laminated under the condition of 9.8 ⁇ 10 3 N / m), and a high refractive index layer, a photosensitive resin layer, and A laminate in which a support film was laminated was produced.
- compositions of the components listed in Tables 2 to 5 are parts by mass. As shown in Tables 2 to 5, in the examples, the reflectance R normalized value was 90% or less, the reflectance was sufficiently reduced, and the resistance to the salt spray test was sufficient. Further, there was no development residue and the developability was sufficient. Furthermore, it was confirmed that the light transmittance of the transferred photosensitive resin layer and high refractive index layer was high. Comparative Example 15 is a result when only the photosensitive resin layer is provided.
- SYMBOLS 1 Transfer type photosensitive refractive index adjustment film, 10 ... Support film, 20 ... Photosensitive resin layer, 30 ... High refractive index layer, 40 ... Protective film, 50 ... Base material with a transparent electrode pattern, 50a ... Transparent electrode pattern, DESCRIPTION OF SYMBOLS 100 ... Laminated body, 101 ... Transparent base material, 102 ... Touch screen, 103 ... Transparent electrode (X position coordinate), 104 ... Transparent electrode (Y position coordinate), 105 ... Lead-out wiring, 106 ... Connection electrode, 107 ... Connection terminal 123: Refractive index adjustment pattern.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Theoretical Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Human Computer Interaction (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Laminated Bodies (AREA)
Abstract
Description
1.支持フィルムと、該支持フィルム上に設けられた感光性樹脂層と、該感光性樹脂層上に設けられた高屈折率層とを備え、前記感光性樹脂層が、光重合性化合物と、光重合開始剤とを含み、前記光重合開始剤がオキシムエステル化合物又はホスフィンオキサイド化合物を含む転写形感光性屈折率調整フィルム。
2.前記感光性樹脂層及び前記高屈折率層の、波長400~700nmにおける可視光透過率の最小値が90.00%以上である1に記載の転写形感光性屈折率調整フィルム。
3.前記高屈折率層がトリアジン環を有する化合物又はイソシアヌル酸を有する化合物を含む1又は2に記載の転写形感光性屈折率調整フィルム。
4.前記高屈折率層がフルオレン骨格を有する化合物を含む1~3のいずれかに記載の転写形感光性屈折率調整フィルム。
5.前記高屈折率層が金属酸化物を含む1~4のいずれかに記載の転写形感光性屈折率調整フィルム。
6.前記金属酸化物が酸化ジルコニウム、酸化チタン、酸化スズ、酸化亜鉛、酸化インジウムスズ、酸化インジウム、酸化アルミウム、酸化ケイ素及び酸化イットリウムからなる群より選択される少なくとも一種である5に記載の転写形感光性屈折率調整フィルム
7.前記高屈折率層の波長633nmにおける屈折率が1.50~1.90である1~6のいずれかに記載の転写形感光性屈折率調整フィルム。
8.前記高屈折率層の膜厚が10~500nmである1~7のいずれかに記載の転写形感光性屈折率調整フィルム。
9.前記感光性樹脂層がバインダーポリマーを含む1~8のいずれかに記載の転写形感光性屈折率調整フィルム。
10.前記バインダーポリマーがカルボキシル基を有する9に記載の転写形感光性屈折率調整フィルム。
11.前記バインダーポリマーが(メタ)アクリル酸、(メタ)アクリル酸グリシジルエステル、(メタ)アクリル酸ベンジルエステル、スチレン、(メタ)アクリル酸メチルエステル、(メタ)アクリル酸エチルエステル、(メタ)アクリル酸ブチルエステル及び(メタ)アクリル酸2-エチルヘキシルエステルからなる群より選択される少なくとも一種の化合物に由来する構造単位を含むバインダーポリマーである9又は10に記載の転写形感光性屈折率調整フィルム。
12.前記感光性樹脂層がリン酸エステル化合物を含む1~11のいずれかに記載の転写形感光性屈折率調整フィルム。
13.前記感光性樹脂層と前記高屈折率層の合計の厚みが30μm以下である1~12のいずれかに記載の転写形感光性屈折率調整フィルム。
14.1~13のいずれかに記載の転写形感光性屈折率調整フィルムを用いて基材上に前記高屈折率層が密着するように前記高屈折率層及び前記感光性樹脂層をラミネートする工程と、前記基材上の前記高屈折率層及び前記感光性樹脂層の所定部分を露光後、前記所定部分以外を除去し、屈折率調整パターンを形成する工程とを備える屈折率調整パターンの形成方法。
15.14に記載の形成方法により得られる屈折率調整パターンを有する電子部品。
なお、本明細書において、「(メタ)アクリル酸」とは、アクリル酸又はメタクリル酸を意味し、「(メタ)アクリレート」とは、アクリレート又はそれに対応するメタクリレートを意味する。「A又はB」とは、AとBのどちらか一方を含んでいればよく、両方とも含んでいてもよい。
本発明の転写形感光性屈折率調整フィルムは、支持フィルムと、該支持フィルム上に設けられた感光性樹脂層と、該感光性樹脂層上に設けられた高屈折率層とを備える。そして、感光性樹脂層が光重合性化合物及び光重合開始剤を含み、該光重合開始剤がオキシムエステル化合物又はホスフィンオキサイド化合物を含むことを特徴とする。
以下、支持フィルム、感光性樹脂層、高屈折率層及び保護フィルムについて説明する。
支持フィルム10としては、重合体フィルムを用いることができる。重合体フィルムとしては、ポリエチレンテレフタレート、ポリカーボネート、ポリエチレン、ポリプロピレン、ポリエーテルサルフォン、シクロオレフィンポリマー等が挙げられる。これらの中でも、ポリエチレンテレフタレート、又はシクロオレフィンポリマーが好ましい。
本発明において感光性樹脂層20は、光重合性化合物と、光重合開始剤とを含み、上記光重合開始剤がオキシムエステル化合物又はホスフィンオキサイド化合物を含む。本発明では、光重合開始剤としてオキシムエステル化合物又はホスフィンオキサイド化合物を使用することにより、透明性の高い硬化膜を充分な現像性で形成することができる。
R13は、H、OH、COOH、O(CH2)OH、O(CH2)2OH、COO(CH2)OH又はCOO(CH2)2OHを示す。H、O(CH2)OH、O(CH2)2OH、COO(CH2)OH、又はCOO(CH2)2OHであることが好ましく、H、O(CH2)2OH、又はCOO(CH2)2OHであることがより好ましい。
R16及びR17は、それぞれ炭素数1~12のアルキル基、フェニル基、又はトリル基を示し、メチル基、フェニル基又はトリル基であることが好ましい。
R19はアセタール結合を有する有機基であり、後述する式(3-1)に示す化合物が有するR19に対応する置換基であることが好ましい。
R20及びR21は、それぞれ炭素数1~12のアルキル基、フェニル基又はトリル基を示し、メチル基、フェニル基又はトリル基であることが好ましく、メチル基であることがより好ましい。
R22は、炭素数1~6のアルキル基を示す。nは0~4の整数を示す。R22が複数存在する場合、複数のR22はそれぞれ同一でも異なっていてもよい。
式(7)中、R34、R35及びR36は各々独立に、炭素数1~20のアルキル基、フェニル基、トリル基、キシリル基、メシチル基、又はジメトキシフェニル基を示す。
式(7)で表わされる化合物のなかでも、R34、R35及びR36がフェニル基、トリル基、キシリル基、メシチル基又はジメトキシフェニル基であるものが好ましい。
バインダーポリマーとしては、アルカリ現像によりパターニングを可能とする観点から、カルボキシル基を有するポリマーを用いることが好ましい。
これらの中でも、特に無機アルカリ水溶液に対するアルカリ現像性、パターニング性、透明性の観点から、(メタ)アクリル酸、(メタ)アクリル酸グリシジルエステル、(メタ)アクリル酸ベンジルエステル、スチレン、(メタ)アクリル酸メチルエステル、(メタ)アクリル酸エチルエステル、(メタ)アクリル酸ブチルエステル及び(メタ)アクリル酸2-エチルヘキシルエステルからなる群より選択される少なくとも一種の化合物に由来する構造単位を含むバインダーポリマーが好ましい。
光重合開始剤として、オキシムエステル化合物を含む場合、その含有量は、(A)成分及び(B)成分の合計量100質量部に対し、0.1~5.0質量部であることが好ましく、0.5~3.0質量部であることがより好ましく、1.0~3.0質量部であることがさらに好ましく、1.5~2.5質量部であることが特に好ましい。
光重合開始剤として、ホスフィンオキサイド化合物を含む場合、その含有量は、(A)成分及び(B)成分の合計量100質量部に対し、3.0~15質量部であることが好ましく、3.5~15質量部であることがより好ましく、4.0~15質量部であることがさらに好ましく、5.0~15質量部であることが特に好ましい。
高屈折率層は、上記の感光性樹脂層よりも屈折率が高い層である。なお、感光性樹脂層の波長633nmの光における屈折率は、通常、1.40~1.49である。
高屈折率層は、波長633nmの光における屈折率が1.50~1.90であることが好ましく、1.53~1.85であることがより好ましく、1.55~1.75であることがさらに好ましい。高屈折率層の633nmにおける屈折率が1.50~1.90であることにより、図2に示す積層体とした場合、ITO等の透明電極パターン50aと、感光性樹脂層20の上に使用される各種部材(例えば、モジュール化する際に使用するカバーガラスと透明電極パターンとを接着するOCA)との屈折率の中間値となりやすく、ITO等の透明電極パターンが形成されている部分と形成されていない部分での光学的な反射による色差を小さくすることが可能となり、骨見え現象を抑制できる。また、画面全体の反射光強度を低減することが可能となり、画面上の透過率低下を抑制することが可能となる。なお、屈折率は、本願明細書の実施例を参考に測定することができる。
得られたトリアジン環を有するハイパーブランチポリマーを、フタル酸やコハク酸等で変性することにより酸価を含有させることも可能である。
具体的には、イソシアヌル酸トリアリルが好ましい。
ハロゲン原子としては、塩素原子が好ましい。
R2OHとしては、メチロール基、ヒドロキシエチル基が好ましい。
(F)成分が金属酸化物を含む場合、現像性を向上する観点から、感光性樹脂層のバインダーポリマーで説明したカルボキシル基を有するポリマー、又は光重合性化合物に記載のエチレン性不飽和基を有する光重合性化合物を、単独又は複数組み合わせて高屈折率層を形成することが好ましい。
また、金属酸化物は微粒子状であることが好ましい。
金属酸化物は、例えば、ナノユースOZ―S30K、OZ-S40K-AC、OZ-S30M(日産化学工業株式会社製、製品名)、NANON5ZR-010、NANONZR-020(株式会社ソーラー製、製品名)、SZR-K、SZR-M(堺化学工業株式会社、製品名)が商業的に入手可能である。
さらに、酸化ジルコニウムは、酸化イットリウムと併用して用いることも好ましい。これにより転写形感光性屈折率調整フィルムを調整した際、高屈折率層の透明性及び屈折率をより向上させることが可能となる。
なお、ナノユースOZ―S30K、OZ-S40K-AC、及びOZ-S30Mは酸化ジルコニウムの他にアモルファスシリカ又は酸化スズを混合させている。SZR-K、及びSZR-Mは、酸化イットリウムを混合させている。
なお、酸化ジルコニウムや酸化スズは、STEM-EDXを用いて、ジルコニウム元素、酸素元素、スズ元素を検出してマッピングすることで特定できる。
また、高屈折率層は、実質的に上述した(F)成分の少なくとも1つのみからなってもよい。即ち、本発明における高屈折率層は、実質的に(F)成分のみからなっていてもよい。
ここで「実質的」とは、層を構成する成分の95質量%以上100質量%以下(好ましくは98質量%以上100質量%以下)が(F)成分であることを意味する。
保護フィルム40としては、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリカーボネート、ポリエチレン-酢酸ビニル共重合体、ポリエチレン-酢酸ビニル共重合体とポリエチレンの積層フィルム等が挙げられる。
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65,000、酸価が78mgKOH/g、水酸基価が2mgKOH/gのバインダーポリマーの溶液(固形分45質量%)(A1)を得た。
ポンプ:L-6000(株式会社日立製作所製、製品名)
カラム:Gelpack GL-R420、Gelpack GL-R430、Gelpack GL-R440(以上、日立化成株式会社製、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:L-3300(RI検出器、株式会社日立製作所製、製品名)
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、上記固形分のポリマー1gを精秤した後、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/100)
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質量(g)を示し、Iは測定した樹脂溶液中の不揮発分の割合(質量%)を示す。
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、上記固形分のポリマー1gを精秤した後、ポリマーを三角フラスコに入れ、10質量%の無水酢酸ピリジン溶液を10mL加えてこれを均一に溶解し、100℃で1時間加熱した。加熱後、水10mLとピリジン10mLを加えて100℃で10分間加熱後、自動滴定機(平沼産業株式会社製、製品名「COM-1700」)を用いて、0.5mol/Lの水酸化カリウムのエタノール溶液により中和滴定を行った。そして、次式により水酸基価を算出した。
水酸基価=(A-B)×f×28.05/試料(g)+酸価
式中、Aは空試験に用いた0.5mol/L水酸化カリウムエタノール溶液の量(mL)を示し、Bは滴定に用いた0.5mol/L水酸化カリウムエタノール溶液の量(mL)を示し、fはファクターを示す。
表1に示す(2)をメタクリル酸12質量部、メタクリル酸メチル38質量部、アクリル酸エチル30質量部、シクロヘキシルメタクリレート20質量部及び2,2’-アゾビス(イソブチロニトリル)1.1質量部に変更した他は(A1)と同様に合成し、重量平均分子量が65,000、酸価が78mgKOH/g、水酸基価が2mgKOH/gのバインダーポリマーの溶液(固形分45質量%)(A2)を得た。
表1に示す(2)をメタクリル酸24質量部、メタクリル酸メチル44質量部、アクリル酸ブチル15質量部、メタクリル酸ブチル17質量部及び2,2’-アゾビス(イソブチロニトリル)3質量部に変更した他は(A1)と同様に合成し、重量平均分子量が25,000、酸価が157mgKOH/g、水酸基価が2mgKOH/gのバインダーポリマーの溶液(固形分45質量%)(A3)を得た。
表1に示す(2)をメタクリル酸30質量部、メタクリル酸メチル22質量部、アクリル酸エチル10質量部、メタクリル酸ブチル8質量部、スチレン30質量部及び2,2’-アゾビス(イソブチロニトリル)1.1質量部に変更した他は(A1)と同様に合成し、重量平均分子量が50,000、酸価が196mgKOH/g、水酸基価が2mgKOH/gのバインダーポリマーの溶液(固形分45質量%)(A4)を得た。
[感光性樹脂層を形成する塗布液の作製]
表2~5の「感光性樹脂層」に示す成分を、撹拌器を用いて15分間混合し、感光性樹脂層を形成するための塗布液を作製した。
表2~5の「高屈折率層」に示す成分を、撹拌機を用いて15分間混合し高屈折率層を形成するための塗布液を作製した。
(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、水酸基価2mgKOH/g、Tg60℃
(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/シクロヘキシルメタクリレート=12/38/30/20(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、水酸基価2mgKOH/g、Tg54℃
(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=24/44/15/17(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25,000、酸価157mgKOH/g、水酸基価2mgKOH/g、Tg65℃
(A4):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/メタクリル酸ブチル/スチレン=30/22/10/8/30(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50,000、酸価196mgKOH/g、水酸基価2mgKOH/g、Tg96℃
T-1420(T):ジトリメチロールプロパンテトラアクリレート(日本化薬株式会社製、製品名)
FA321M:(メタ)アクリル系化合物・ビスフェノールAEO変性ジメタクリレート(日立化成株式会社製、製品名)
IRGACURE OXE 01:1,2-オクタンジオン,1-[(4-フェニルチオ)フェニル-,2-(O-ベンゾイルオキシム)](BASF株式会社製、製品名)
IRGACURE 379:2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン(BASFジャパン株式会社製、製品名)
DETX:2,4-ジエチル チオキサントン(日本化薬株式会社製、製品名)
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ジャパン株式会社製、製品名「LUCIRIN TPO」)
HAT:5-アミノ-1H-テトラゾール(東洋紡績株式会社製、製品名)
3MT:3-メルカプト-トリアゾール(和光純薬株式会社製、製品名)
PM-21:光重合性不飽和結合を含むリン酸エステル(日本化薬株式会社製、製品名)
Phosmer-M:りん酸2-(メタクリロイルオキシ)エチル(ユニケミカル株式会社製、製品名)
(F)成分
UR658:トリアジン骨格を有するポリマー(日産化学工業株式会社製、製品名「HYPERTECHシリーズ UR658」(商標名))
イソシアヌル酸トリアリル:東京化成工業株式会社製
OZ-S40K-AC:ジルコニア分散液(日産化学工業株式会社製、製品名「ナノユースOZ-S40K-AC」)
OZ-S30K:ジルコニア分散液(日産化学工業株式会社製、製品名「ナノユースOZ-S30K」)
EA0200:ポリオキシエチレン変性9,9-ビス(4-ヒドロキシフェニル)フルオレンジアクリレート(大阪ガスケミカル株式会社製、製品名)
EAF5503:ポリオキシエチレン変性9,9-ビス(4-ヒドロキシフェニル)フルオレンジアクリレート/ベンジルアクリレート/9,9-ビス(4-ヒドロキシフェニル)フルオレン骨格化合物の混合物(大阪ガスケミカル株式会社製、製品名)
EA-HC931:ポリオキシエチレン変性9,9-ビス(4-ヒドロキシフェニル)フルオレンジアクリレート他混合物(大阪ガスケミカル株式会社製、製品名)
・その他の成分
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)(川口化学株式会社製、製品名)
SH-30:オクタメチルシクロテトラシロキサン(東レ・ダウコーニング株式会社製、製品名)
メチルエチルケトン(東燃化学株式会社製)
L-7001:オクタメチルシクロテトラシロキサン(東レ・ダウコーニング株式会社製、製品名)
保護フィルムとして厚さ30μmのポリプロピレンフィルム(王子エフテックス株式会社製、製品名「E-201F」)を使用し、上記で作製した高屈折率層を形成するための塗布液を保護フィルム上にダイコーターを用いて均一に塗布し、100℃の熱風滞留式乾燥機で3分間乾燥して溶剤を除去し、高屈折率層を形成した。
[高屈折率層の屈折率の測定]
高屈折率層を形成するための塗布液を厚さ0.7mmのガラス基材上にスピンコーターで均一に塗布し、100℃の熱風滞留式乾燥機で3分間乾燥して溶剤を除去し、高屈折率層を形成した。
なお、転写形感光性屈折率調整フィルムの形態における屈折率層単層の屈折率は、高屈折率層の支持フィルム側の最表面層の値とする。
高屈折率層を有する保護フィルムと、感光性樹脂層を有する支持フィルムを貼り合わせる前の試料で測定した。上記で作製した高屈折率層を有する保護フィルムの高屈折率層をF20(FILMETRICS株式会社製、製品名)で測定することにより高屈折率層の膜厚を測定した。また、上記で作製した感光性樹脂層を有する支持フィルムを、デジタルシックネスゲージ(ニコン株式会社製、製品名「DIGIMICROSTAND MS-5C」)で測定することにより感光性樹脂層の膜厚を測定した。
得られた転写形感光性屈折率調整フィルムの保護フィルムをはがしながら、厚さ0.7mmのガラス基材上に、高屈折率層が接するようにラミネータ(日立化成株式会社製、製品名「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、ガラス基材上に、高屈折率層、感光性樹脂層及び支持フィルムが積層された基板を作製した。
なお、参考としてガラス基材単体の測定値を表5に示す。
得られた転写形感光性屈折率調整フィルムの保護フィルムをはがしながら、透明導電性フィルム(東洋紡株式会社製、製品名「300R」)上に、高屈折率層が接するようにラミネータ(日立化成株式会社製、製品名「HLM-3000型」)を用いて、ロール温度120℃、基材送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基材を用いたため、このときの線圧は9.8×103N/m)の条件でラミネートして、透明導電性フィルム上に、高屈折率層、感光性樹脂層及び支持フィルムが積層された積層体を作製した。
反射率R規格化=反射率実測値/感光性樹脂層のみ積層した測定試料(比較例16)の反射率実測値×100
なお、参考として透明導電性フィルム単体の測定値を表5に示す。
得られた転写形感光性屈折率調整フィルムの保護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式会社製)上に、高屈折率層が接するようにラミネータ(日立化成株式会社製、製品名「HLM-3000型」)を用いて、ロール温度120℃、基材送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基材を用いたため、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、高屈折率層、感光性樹脂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。
なお、参考としてスパッタ銅付きポリイミドフィルム単体の測定値を表5に示す。
上記で作製した転写形感光性屈折率調整フィルムの保護フィルムをはがしながら、厚さ0.7mmのガラス基材上に、高屈折率層が接するようにラミネータ(日立化成株式会社製、製品名「HLM-3000型」)を用いて、ロール温度120℃、基材送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが1mm、縦10cm×横10cmの基材を用いたため、このときの線圧は9.8×103N/m)の条件でラミネートして、ガラス基材上に、高屈折率層、感光性樹脂層及び支持フィルムが積層された積層体を作製した。
なお、参考としてガラス基材単体の測定値を表5に示す。
得られた転写形感光性屈折率調整フィルムの保護フィルムをはがしながら、易接着層付PETフィルム(東洋紡株式会社製、製品名「A4300」、125μm厚)上に、高屈折率層が接するようにラミネータ(日立化成株式会社製、製品名「HLM-3000型」)を用いて、ロール温度120℃、基材送り速度1m/分、圧着圧力(シリンダ圧力)4×105Pa(厚さが125μm、縦10cm×横10cmの基材を用いたため、この時の線圧は9.8×103N/m)の条件でラミネートして、A4300上に、高屈折率層、感光性樹脂層及び支持フィルムが積層された積層体を作製した。
A : 現像残渣が発生しない。
B : 現像残渣がわずかに発生するが、その後の工程への影響はない。
C : 現像残渣が発生する。
D : 現像残渣が多く発生する。
表2~5に示すように、実施例では反射率R規格化の値が90%以下となり、反射率を充分に低減しているとともに、塩水噴霧試験に対する耐性も充分であった。また、現像残渣がなく現像性が充分であった。さらに、転写された感光性樹脂層及び高屈折率層の光線透過率が高いことも確認できた。なお、比較例15は感光性樹脂層のみを設けた場合の結果である。
この明細書に記載の文献の内容を全てここに援用する。
Claims (15)
- 支持フィルムと、該支持フィルム上に設けられた感光性樹脂層と、該感光性樹脂層上に設けられた高屈折率層とを備え、
前記感光性樹脂層が、光重合性化合物と、光重合開始剤とを含み、
前記光重合開始剤がオキシムエステル化合物又はホスフィンオキサイド化合物を含む転写形感光性屈折率調整フィルム。 - 前記感光性樹脂層及び前記高屈折率層の、波長400~700nmにおける可視光透過率の最小値が90.00%以上である請求項1に記載の転写形感光性屈折率調整フィルム。
- 前記高屈折率層がトリアジン環を有する化合物又はイソシアヌル酸を有する化合物を含む請求項1又は2に記載の転写形感光性屈折率調整フィルム。
- 前記高屈折率層がフルオレン骨格を有する化合物を含む請求項1~3のいずれか一項に記載の転写形感光性屈折率調整フィルム。
- 前記高屈折率層が金属酸化物を含む請求項1~4のいずれか一項に記載の転写形感光性屈折率調整フィルム。
- 前記金属酸化物が酸化ジルコニウム、酸化チタン、酸化スズ、酸化亜鉛、酸化インジウムスズ、酸化インジウム、酸化アルミウム、酸化ケイ素及び酸化イットリウムからなる群より選択される少なくとも一種である請求項5に記載の転写形感光性屈折率調整フィルム
- 前記高屈折率層の波長633nmにおける屈折率が1.50~1.90である請求項1~6のいずれか一項に記載の転写形感光性屈折率調整フィルム。
- 前記高屈折率層の膜厚が10~500nmである請求項1~7のいずれか一項に記載の転写形感光性屈折率調整フィルム。
- 前記感光性樹脂層がバインダーポリマーを含む請求項1~8のいずれか一項に記載の転写形感光性屈折率調整フィルム。
- 前記バインダーポリマーがカルボキシル基を有する請求項9に記載の転写形感光性屈折率調整フィルム。
- 前記バインダーポリマーが(メタ)アクリル酸、(メタ)アクリル酸グリシジルエステル、(メタ)アクリル酸ベンジルエステル、スチレン、(メタ)アクリル酸メチルエステル、(メタ)アクリル酸エチルエステル、(メタ)アクリル酸ブチルエステル及び(メタ)アクリル酸2-エチルヘキシルエステルからなる群より選択される少なくとも一種の化合物に由来する構造単位を含むバインダーポリマーである請求項9又は10に記載の転写形感光性屈折率調整フィルム。
- 前記感光性樹脂層がリン酸エステル化合物を含む請求項8~11のいずれか一項に記載の転写形感光性屈折率調整フィルム。
- 前記感光性樹脂層と前記高屈折率層の合計の厚みが30μm以下である請求項1~12のいずれか一項に記載の転写形感光性屈折率調整フィルム。
- 請求項1~13のいずれか一項に記載の転写形感光性屈折率調整フィルムを用いて基材上に前記高屈折率層が密着するように前記高屈折率層及び前記感光性樹脂層をラミネートする工程と、
前記基材上の前記高屈折率層及び前記感光性樹脂層の所定部分を露光後、前記所定部分以外を除去し、屈折率調整パターンを形成する工程と、を備える屈折率調整パターンの形成方法。 - 請求項14に記載の形成方法により得られる屈折率調整パターンを有する電子部品。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017517451A JPWO2016181422A1 (ja) | 2015-05-11 | 2015-05-11 | 転写形感光性屈折率調整フィルム、屈折率調整パターンの形成方法及び電子部品 |
KR1020177031128A KR20180004717A (ko) | 2015-05-11 | 2015-05-11 | 전사형 감광성 굴절률 조정 필름, 굴절률 조정 패턴의 형성 방법 및 전자 부품 |
CN201580079850.8A CN107531031A (zh) | 2015-05-11 | 2015-05-11 | 转印型感光性折射率调整膜、折射率调整图案的形成方法及电子部件 |
US15/573,150 US20180107112A1 (en) | 2015-05-11 | 2015-05-11 | Transfer-type photosensitive refractive index adjustment film, method for forming refractive index adjustment pattern, and electronic component |
PCT/JP2015/002379 WO2016181422A1 (ja) | 2015-05-11 | 2015-05-11 | 転写形感光性屈折率調整フィルム、屈折率調整パターンの形成方法及び電子部品 |
TW105112575A TW201706134A (zh) | 2015-05-11 | 2016-04-22 | 轉印型感光性折射率調整膜、折射率調整圖案的形成方法及電子零件 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2015/002379 WO2016181422A1 (ja) | 2015-05-11 | 2015-05-11 | 転写形感光性屈折率調整フィルム、屈折率調整パターンの形成方法及び電子部品 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016181422A1 true WO2016181422A1 (ja) | 2016-11-17 |
Family
ID=57247931
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/002379 WO2016181422A1 (ja) | 2015-05-11 | 2015-05-11 | 転写形感光性屈折率調整フィルム、屈折率調整パターンの形成方法及び電子部品 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20180107112A1 (ja) |
JP (1) | JPWO2016181422A1 (ja) |
KR (1) | KR20180004717A (ja) |
CN (1) | CN107531031A (ja) |
TW (1) | TW201706134A (ja) |
WO (1) | WO2016181422A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110462560A (zh) * | 2017-03-28 | 2019-11-15 | 日立化成株式会社 | 转印型感光性膜、固化膜图案的形成方法、固化膜及触摸面板 |
WO2020079992A1 (ja) * | 2018-10-18 | 2020-04-23 | 富士フイルム株式会社 | 転写フィルム、硬化膜の製造方法、積層体の製造方法、及び、タッチパネルの製造方法 |
WO2023148123A1 (en) | 2022-02-01 | 2023-08-10 | Merck Patent Gmbh | Composition, cured film, device including the same, and manufacturing method for the cured film |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104699309B (zh) * | 2015-03-31 | 2017-06-13 | 合肥京东方光电科技有限公司 | 一种触摸屏、其制作方法及显示装置 |
CN111279804B (zh) * | 2017-12-20 | 2023-10-24 | 住友电气工业株式会社 | 制造印刷电路板和层压结构的方法 |
KR102614299B1 (ko) * | 2019-11-18 | 2023-12-19 | 도레이 카부시키가이샤 | 감광성 수지 조성물, 감광성 수지 시트, 중공 구조체, 경화물, 중공 구조체의 제조 방법, 전자 부품 및 탄성파 필터 |
CN113655907A (zh) * | 2021-08-18 | 2021-11-16 | 业成科技(成都)有限公司 | 触控面板、其制备方法及电子装置 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
JP2013200891A (ja) * | 2011-12-05 | 2013-10-03 | Hitachi Chemical Co Ltd | タッチパネル用電極の保護膜及びタッチパネル |
JP2014108541A (ja) * | 2012-11-30 | 2014-06-12 | Fujifilm Corp | 転写フィルムおよび透明積層体、それらの製造方法、静電容量型入力装置ならびに画像表示装置 |
JP2014126570A (ja) * | 2012-12-25 | 2014-07-07 | Toray Advanced Film Co Ltd | 反射防止フィルム |
WO2014208745A1 (ja) * | 2013-06-28 | 2014-12-31 | 住友理工株式会社 | 光透過性積層体 |
WO2015029996A1 (ja) * | 2013-08-30 | 2015-03-05 | 電気化学工業株式会社 | 被覆材用樹脂組成物 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013084883A1 (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、並びに、タッチパネルの製造方法 |
-
2015
- 2015-05-11 US US15/573,150 patent/US20180107112A1/en not_active Abandoned
- 2015-05-11 KR KR1020177031128A patent/KR20180004717A/ko unknown
- 2015-05-11 CN CN201580079850.8A patent/CN107531031A/zh active Pending
- 2015-05-11 WO PCT/JP2015/002379 patent/WO2016181422A1/ja active Application Filing
- 2015-05-11 JP JP2017517451A patent/JPWO2016181422A1/ja not_active Withdrawn
-
2016
- 2016-04-22 TW TW105112575A patent/TW201706134A/zh unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
JP2013200891A (ja) * | 2011-12-05 | 2013-10-03 | Hitachi Chemical Co Ltd | タッチパネル用電極の保護膜及びタッチパネル |
JP2014108541A (ja) * | 2012-11-30 | 2014-06-12 | Fujifilm Corp | 転写フィルムおよび透明積層体、それらの製造方法、静電容量型入力装置ならびに画像表示装置 |
JP2014126570A (ja) * | 2012-12-25 | 2014-07-07 | Toray Advanced Film Co Ltd | 反射防止フィルム |
WO2014208745A1 (ja) * | 2013-06-28 | 2014-12-31 | 住友理工株式会社 | 光透過性積層体 |
WO2015029996A1 (ja) * | 2013-08-30 | 2015-03-05 | 電気化学工業株式会社 | 被覆材用樹脂組成物 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110462560A (zh) * | 2017-03-28 | 2019-11-15 | 日立化成株式会社 | 转印型感光性膜、固化膜图案的形成方法、固化膜及触摸面板 |
WO2020079992A1 (ja) * | 2018-10-18 | 2020-04-23 | 富士フイルム株式会社 | 転写フィルム、硬化膜の製造方法、積層体の製造方法、及び、タッチパネルの製造方法 |
JPWO2020079992A1 (ja) * | 2018-10-18 | 2021-09-16 | 富士フイルム株式会社 | 転写フィルム、硬化膜の製造方法、積層体の製造方法、及び、タッチパネルの製造方法 |
WO2023148123A1 (en) | 2022-02-01 | 2023-08-10 | Merck Patent Gmbh | Composition, cured film, device including the same, and manufacturing method for the cured film |
Also Published As
Publication number | Publication date |
---|---|
JPWO2016181422A1 (ja) | 2018-03-01 |
US20180107112A1 (en) | 2018-04-19 |
TW201706134A (zh) | 2017-02-16 |
CN107531031A (zh) | 2018-01-02 |
KR20180004717A (ko) | 2018-01-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2016181422A1 (ja) | 転写形感光性屈折率調整フィルム、屈折率調整パターンの形成方法及び電子部品 | |
JP2017223994A (ja) | 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 | |
WO2016001955A1 (ja) | 転写形感光性屈折率調整フィルム | |
JP6551277B2 (ja) | 硬化膜付きタッチパネル用基材の製造方法、それに用いる感光性樹脂組成物、感光性エレメント及びタッチパネル | |
JP2017116774A (ja) | 転写形感光性屈折率調整フィルム | |
JP2019175226A (ja) | タッチセンサの保護膜形成用感光性フィルム、タッチセンサの保護膜形成用感光性屈折率調整フィルム、タッチセンサの保護膜の形成方法及びタッチパネル | |
WO2016132401A1 (ja) | 転写形感光性屈折率調整フィルム、屈折率調整パターンの形成方法及び電子部品 | |
JP2017201352A (ja) | 転写形感光性屈折率調整フィルム、屈折率調整パターンの形成方法及び電子部品 | |
WO2017175642A1 (ja) | 感光性屈折率調整フィルム、硬化膜パターンの形成方法、硬化膜及び電子部品 | |
WO2017056131A1 (ja) | 転写形感光性屈折率調整フィルム | |
JP2017181541A (ja) | 感光性フィルム、感光性屈折率調整フィルム、屈折率調整パターンの形成方法、硬化膜及び電子部品 | |
WO2018179096A1 (ja) | 転写型感光性フィルム、硬化膜パターンの形成方法及びタッチパネル | |
JP2019219631A (ja) | 転写フィルム、硬化膜及びその形成方法、並びに、電子部品 | |
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 | |
JP2019035801A (ja) | 転写型感光性フィルム、硬化膜パターンの形成方法、硬化膜及び電子部品 | |
JP2019215395A (ja) | 転写型感光性フィルム、硬化膜パターンの形成方法、積層体及びタッチパネル | |
JP2017009854A (ja) | 転写形感光性屈折率調整フィルムとその製造方法、及びそれを用いた屈折率調整パターンの形成方法、電子部品 | |
WO2019224887A1 (ja) | 転写型感光性フィルム、樹脂硬化膜付き電極基板及びタッチパネル | |
JP2018045126A (ja) | 真空ラミネート用感光性フィルム、転写型感光性屈折率調整フィルム、及び硬化樹脂パターンの形成方法 | |
JP7210091B2 (ja) | 転写型感光性フィルム、硬化膜パターンの形成方法、硬化膜及びタッチパネル | |
JP2019148614A (ja) | 感光性樹脂組成物、感光性エレメント及びタッチパネル用電極の保護膜の製造方法 | |
WO2018179102A1 (ja) | 転写型感光性屈折率調整フィルム、屈折率調整パターンの形成方法、硬化膜及びタッチパネル | |
WO2018134883A1 (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及びタッチパネル | |
WO2019186781A1 (ja) | 転写フィルム、硬化膜及びその形成方法、並びに、電子部品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15891750 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017517451 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20177031128 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15573150 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15891750 Country of ref document: EP Kind code of ref document: A1 |