WO2013141286A1 - Composition de résine photosensible, procédé de fabrication d'un substrat de verre traité l'utilisant, et écran tactile et son procédé de fabrication - Google Patents

Composition de résine photosensible, procédé de fabrication d'un substrat de verre traité l'utilisant, et écran tactile et son procédé de fabrication Download PDF

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Publication number
WO2013141286A1
WO2013141286A1 PCT/JP2013/058027 JP2013058027W WO2013141286A1 WO 2013141286 A1 WO2013141286 A1 WO 2013141286A1 JP 2013058027 W JP2013058027 W JP 2013058027W WO 2013141286 A1 WO2013141286 A1 WO 2013141286A1
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WIPO (PCT)
Prior art keywords
photosensitive resin
touch panel
glass substrate
resist
resin composition
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PCT/JP2013/058027
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English (en)
Japanese (ja)
Inventor
山口　正利
俊彦 高崎
杉本　靖
健男 富山
貴子 江尻
山本　和徳
川口　卓
泰洋 瀬里
真弓 佐藤
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日立化成株式会社
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Priority to KR1020147025839A priority Critical patent/KR20140148379A/ko
Priority to CN201380015589.6A priority patent/CN104204948A/zh
Publication of WO2013141286A1 publication Critical patent/WO2013141286A1/fr

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    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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 photosensitive resin composition and a method for producing a processed glass substrate using the same.
  • the present invention also relates to a touch panel and a manufacturing method thereof.
  • the touch panel according to the present invention can be used in a liquid crystal display, an organic EL display and the like.
  • Photofabrication is the application of a photosensitive resin composition to the surface of a workpiece, patterning the coating film of the photosensitive resin composition by photolithography technology to form a resist, and using this as a mask to chemically etch the surface of the workpiece. It is a general term for technologies for manufacturing various precision parts singly or in combination with electroforming technology mainly composed of electrolytic etching or electroplating. Photofabrication has become the mainstream of current precision micromachining technology.
  • the back cap of an organic electroluminescence display in order to reduce the thickness of the panel, it has been studied to use glass as the back cap.
  • This glass back cap is manufactured by processing a glass substrate by etching.
  • a resist photoresist film
  • a photosensitive resin composition that covers a part of the surface of the glass substrate is formed, and only a desired region is etched with an etchant containing hydrofluoric acid as a component.
  • the tempered glass used for the cover glass of the touch panel of a smart phone and mobile PC is processed using methods, such as a router, before and after a tempering process.
  • Patent Document 1 a photocurable resist resin composition comprising an acrylic resin having an ethylenically unsaturated double bond in a side chain, polysilane, and a photosensitizer has been proposed (Patent Document 1). reference).
  • Patent Document 2 a radiation-sensitive resin composition containing (A) an unsaturated group-containing alkali-soluble resin, (B) a compound having an ethylenically unsaturated double bond, and (C) a radiation radical polymerization initiator,
  • A an unsaturated group-containing alkali-soluble resin
  • B a compound having an ethylenically unsaturated double bond
  • C a radiation radical polymerization initiator
  • a transparent cover base material such as a glass substrate is provided to protect a liquid crystal panel or the like.
  • a decoration part may be provided on the back side (surface opposite to the input surface) of such a transparent cover substrate for the purpose of decoration.
  • the touch panel sensor is usually disposed further back than the decoration portion as viewed from the input surface.
  • the decoration portion is formed using, for example, an ink mainly composed of a polymer. Therefore, in general, an overcoat layer that covers the decorative portion is provided for the purpose of preventing discharge of low molecular gas due to decomposition of the residual organic solvent or the resin binder.
  • the touch panel sensor is disposed on the overcoat layer.
  • Patent Document 5 a concave portion having the same shape and the same size as the decorative portion is formed on the transparent cover base material before the decorative portion is formed, and the decorative portion is formed at the position. It has been proposed (Patent Document 5).
  • the present invention when used to form a resist as a mask when etching a glass substrate with hydrofluoric acid, while maintaining close contact with the glass substrate during etching with hydrofluoric acid,
  • the main object is to provide a photosensitive resin composition capable of forming a resist that can be easily peeled off from a glass substrate after etching.
  • the touch panel manufacturing method of Patent Document 5 it has been clarified that the touch panel sensor tends to be disconnected, and a practically sufficient yield may not be obtained. This is thought to be due to the fact that it is difficult to dig deep into the glass substrate by etching because a liquid resist is used.
  • Another object of the present invention is to suppress the occurrence of disconnection of the touch panel sensor in the method for manufacturing a touch panel having a decorative portion.
  • the present invention relates to a photosensitive resin composition used for forming a resist as a mask when a glass substrate is etched with hydrofluoric acid.
  • the present invention relates to application of a composition as a photosensitive resin composition used for forming a resist as a mask when a glass substrate is etched with hydrofluoric acid, or production of the photosensitive resin composition.
  • the photosensitive resin composition according to the present invention contains (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a silane compound, and (B)
  • the photopolymerizable compound includes (B1) a compound having an unsaturated group and an isocyanuric ring.
  • the photosensitive resin composition according to the present invention contains (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, and (B) the photopolymerizable compound is (B1).
  • Including a compound having an unsaturated group and an isocyanuric ring, and (B1) the content of the compound having an unsaturated group and an isocyanuric ring is 100 parts by mass of the total amount of the component (A), the component (B) and the component (C). On the other hand, it may be 25 to 40 parts by mass.
  • the photosensitive resin composition of the present invention can form a resist that can be easily peeled off from a glass substrate after etching while maintaining close contact with the glass substrate during etching with hydrofluoric acid by having the above-described configuration. Is possible.
  • the content of (D) the silane compound is (A) component, (B)
  • the total amount of the component and the component (C) may be 0.5 to 12 parts by mass with respect to 100 parts by mass.
  • a part or all of the compound having an unsaturated group and an isocyanuric ring may further have a hydroxyl group.
  • the photosensitive resin composition according to the present invention may be in the form of a film. That is, this invention can provide the photosensitive resin film which consists of the said photosensitive resin composition.
  • the present invention also includes a step of forming a resist covering a part of the surface of the glass substrate using the photosensitive resin composition, and a step of etching the surface of the glass substrate with hydrofluoric acid using the resist as a mask.
  • a process for producing a processed glass substrate is provided.
  • the manufacturing method may further include a step of removing the resist by heating after the step of etching the surface of the glass substrate with hydrofluoric acid.
  • the touch panel manufacturing method of the present invention relates to a touch panel manufacturing method including a touch panel sensor and a transparent cover base material facing the touch panel sensor, and having an input surface on the transparent cover base material side.
  • the method for manufacturing a touch panel according to the present invention includes a step of forming a resist that covers a part of the back surface of the transparent cover substrate, which is the surface on the touch panel sensor side of the touch panel, using a photosensitive resin film.
  • etching the back surface to form a recess having a depth of 40 ⁇ m or more etching the back surface to form a recess having a depth of 40 ⁇ m or more, removing the resist, forming a decorative portion filled in a part or all of the recess, And a step of forming an overcoat layer extending from the transparent cover base material to the decorative portion on the back surface side, and a step of arranging a touch panel sensor on the overcoat layer.
  • the manufacturing method it is possible to manufacture a touch panel having a decorative portion while sufficiently suppressing occurrence of disconnection of the touch panel sensor. Even when it is intended to form a decorative part of the same type and the same size as the concave part when forming the decorative part filling the concave part, it is actually a minute at the boundary between the decorative part and the transparent cover substrate.
  • a step may be formed. Reflecting this step, a step can be formed on the surface of the overcoat layer. If the step on the surface of the overcoat layer is larger than expected, it is considered that the disconnection of the touch panel sensor formed there is likely to occur.
  • the depth of the recess formed by etching is generally about 20 ⁇ m or less, but by forming a recess with a depth of 40 ⁇ m or more on the surface of the transparent cover substrate, the boundary between the decorative portion and the transparent cover substrate is formed.
  • the decorative portion can be easily formed without excessively increasing the step.
  • the depth of the concave portion is less than 40 ⁇ m, for example, when the ink used for forming the decorative portion has a high viscosity, it is difficult to reduce the step to a range where there is no problem in design.
  • the thickness of the photosensitive resin film may be 10 to 200 ⁇ m.
  • the transparent cover substrate may be a glass substrate.
  • the photosensitive resin film contains, for example, (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a silane compound.
  • the photopolymerizable compound may contain a compound having an unsaturated group and an isocyanuric ring.
  • the decoration unit may be provided so as to overlap with the peripheral edge of the input surface when viewed from a direction perpendicular to the input surface.
  • the present invention also provides a touch panel that can be obtained by the above manufacturing method.
  • the resist and the glass substrate are kept in close contact during etching with hydrofluoric acid, and the resist is removed after etching. It can be easily peeled from the glass substrate.
  • the processed glass substrate which has a smooth process surface and is excellent in intensity
  • the present invention it is possible to suppress the occurrence of disconnection of the touch panel sensor in the method for manufacturing a touch panel having a decorative portion. As a result, the touch panel can be stably manufactured with high quality.
  • FIG. 2 is a sectional view taken along line II-II in FIG. It is sectional drawing which shows one Embodiment of the manufacturing method of a process glass substrate. It is sectional drawing which shows one Embodiment of a touch panel. It is sectional drawing which shows one Embodiment of the manufacturing method of a touchscreen. It is sectional drawing which shows one Embodiment of the manufacturing method of a touchscreen. It is sectional drawing which shows one Embodiment of the manufacturing method of a touchscreen.
  • the photosensitive resin composition according to the present embodiment is used for forming a resist as a mask when a glass substrate is etched with hydrofluoric acid. Details of the application will be described later.
  • the photosensitive resin composition contains (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a silane compound.
  • the photopolymerizable compound may include (B1) a compound having an unsaturated group and an isocyanuric ring.
  • the photosensitive resin composition according to another embodiment contains (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator.
  • the photopolymerizable compound includes (B1) a compound having an unsaturated group and an isocyanuric ring, and the content of the component (B1) is the total amount of the component (A), the component (B), and the component (C) 100. It may be 25 to 40 parts by mass with respect to parts by mass.
  • the binder polymer is, for example, an acrylic resin (homopolymer or copolymer containing (meth) acrylic acid ester as a monomer unit), a styrene resin (homopolymer or copolymer containing styrene as a monomer unit), It is selected from epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. An acrylic resin is preferable from the viewpoint of alkali developability. These polymers can be used alone or in combination of two or more as a binder polymer.
  • Examples of the combination of two or more types of polymers include two or more types of binder polymers composed of different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion. .
  • a polymer having a multimode molecular weight distribution described in JP-A-11-327137 can also be used. If necessary, the binder polymer may have a photosensitive group.
  • the acrylic resin and the styrene resin can be produced, for example, by radical polymerization of a polymerizable monomer.
  • Polymerizable monomers include, for example, styrene; polymerizable styrene derivatives such as vinyl toluene, ⁇ -methyl styrene, p-methyl styrene, and p-ethyl styrene; acrylamide; acrylonitrile; vinyl alcohol such as vinyl-n-butyl ether.
  • (Meth) acrylic acid in this specification means acrylic acid and methacrylic acid corresponding to it. The same applies to other similar expressions such as (meth) acrylic acid esters.
  • a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms can be selected from the viewpoints of film formability and adhesiveness.
  • Examples of the (meth) acrylic acid alkyl ester having 1 to 10 carbon atoms in the alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate.
  • the binder polymer may have a carboxyl group from the viewpoint of alkali developability.
  • the binder polymer having a carboxyl group can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer.
  • As the polymerizable monomer having a carboxyl group (meth) acrylic acid can be selected from the viewpoint of stability.
  • the acid value of the binder polymer may be 30 mgKOH / g or more, or 45 mgKOH / g or more from the viewpoint of development time.
  • the acid value of the binder polymer may be 250 mgKOH / g or less, or 200 mgKOH / g or less, from the viewpoint of resist resistance of the developing solution.
  • the weight average molecular weight of the binder polymer (measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene) is 20000 or more, 25000 or more, or 30000 or more from the viewpoint of developer resistance. It may be. From the viewpoint of shortening the development time, the weight average molecular weight of the binder polymer may be 300,000 or less, 150,000 or less, or 100,000 or less.
  • the (B) component photopolymerizable compound may contain a compound having an unsaturated group and an isocyanuric ring. According to a resist formed using a photosensitive resin composition containing a compound having an unsaturated group and an isocyanuric ring, a recess having a depth of 40 ⁇ m or more can be easily formed because peeling with an etchant is difficult to occur. it can.
  • the compound having an unsaturated group and an isocyanuric ring may further have a hydroxyl group.
  • the photopolymerizable compound of the component (B) can include both a compound having an unsaturated group and an isocyanuric ring and not having a hydroxyl group, and a compound having a hydroxyl group, an unsaturated group and an isocyanuric ring.
  • Examples of the compound having an unsaturated group and an isocyanuric ring include compounds represented by the general formula (I) from the viewpoint of adhesion.
  • R 1 represents a group represented by the following Formula (II), (III), or (IV), and at least one of R 1 is represented by Formula (II) or Formula (IV). And a plurality of R 1 in the same molecule may be the same or different.
  • R 2 represents a hydrogen atom or a methyl group, and m is an integer of 1 to 14.
  • m is an integer of 1 to 14.
  • R 2 represents a hydrogen atom or a methyl group
  • n is an integer of 1 to 9
  • m is an integer of 1 to 14.
  • R 1 when at least one of R 1 is a group represented by formula (III) and at least one of R 1 is a group represented by formula (II) or formula (IV),
  • the compound has a hydroxyl group, an unsaturated group, and an isocyanuric ring.
  • n in formula (IV) When m in formula (II) or formula (III) exceeds 14, chemical resistance may be deteriorated. From the same viewpoint, m in formula (II) or formula (III) may be 1-6. When m in the formula (IV) is 14 or less, chemical resistance tends to be further improved. From the same viewpoint, m in formula (IV) may also be 1-6. There exists a tendency for the mechanical strength of a resist to improve that n in Formula (IV) is 9 or less. From the same viewpoint, n in the formula (IV) may be 3 to 6.
  • the compound having an unsaturated group and an isocyanuric ring may be a compound represented by the following formula (V).
  • the compound having a hydroxyl group, an unsaturated group and an isocyanuric ring structure may be a compound represented by the following formula (VI).
  • Examples of commercially available compounds represented by the above formula (I) include, for example, NK oligo UA-21 (trade name of Shin-Nakamura Chemical Co., Ltd., general formula (I), wherein R 1 is all represented by the general formula (III).
  • M-315 (trade name of Toa Gosei Co., Ltd., R 1 in the general formula (I) represents a group represented by the general formula (II)
  • M-215 (Toa Gosei Co., Ltd. trade name, in general formula (I), two R 1 s represent groups represented by general formula (II), and one R 1 represents a group represented by general formula (III) .).
  • Examples of photopolymerizable compounds having an ethylenically unsaturated group other than compounds having an unsaturated group and an isocyanuric ring include bisphenol A-based (meth) acrylate compounds.
  • the bisphenol A (meth) acrylate compound is not particularly limited, and examples thereof include a compound represented by the following formula (VII).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • X and Y each independently represent an alkylene group having 2 to 6 carbon atoms. Examples of the alkylene group having 2 to 6 carbon atoms include ethylene group, propylene group, isopropylene group, butylene group, pentylene group and hexylene group. X and Y may be an ethylene group or a propylene group, or may be an ethylene group.
  • the aromatic ring (benzene ring) in formula (VII) may have a substituent.
  • substituents include a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, and an alkyl group having 1 to 10 carbon atoms.
  • a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in an alkyl group, an acyl group having 1 to 10 carbon atoms in an alkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms Includes an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, and a heterocyclic ring , And an aryl group substituted by these substituents.
  • the above substituents may form a condensed ring together with the aromatic ring.
  • the hydrogen atom of the formed condensed ring may be substituted with the above substituent.
  • the number of substituents is 2 or more, the two or more substituents may be the same as or different from each other.
  • Examples of the compound represented by the formula (VII) include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypoly). Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc.
  • Bisphenol A-based (meth) acrylate compounds are examples of the compound represented by the formula (VII) propane, etc.
  • 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane examples include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonato) C) phenyl) propane, 2,2-bis (4-((meth) acryloxydeca
  • 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).
  • 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). These may be used alone or in combination of two or more.
  • 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane examples include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) actyl) Roxinonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phen
  • Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, Examples include 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane, and the like. These may be used alone or in combination of two or more.
  • photopolymerizable compounds include, for example, tricyclodecane dimethanol, neopentyl glycol-modified trimethylolpropane diacrylate, compounds obtained by reacting polyhydric alcohols with ⁇ , ⁇ -unsaturated carboxylic acids, and glycidyl groups A compound obtained by reacting an ⁇ , ⁇ -unsaturated carboxylic acid with a compound to be reacted, (meth) acrylate having urethane bond, nonylphenyldioxylene (meth) acrylate, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ ′-( (Meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ ′-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxypropyl- ⁇ ′-(meth) acryloyloxyethyl-o-phthalate, (meth ) Acrylic acid alky
  • Examples of the compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, and 2 to 14 propylene groups.
  • Examples of the compound obtained by reacting a compound containing a glycidyl group with an ⁇ , ⁇ -unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4- (meth)).
  • An epoxy acrylate compound obtained by reacting an epoxy resin such as (acryloxy-2-hydroxy-propyloxy) phenyl, a novolac type epoxy resin, a bisphenol type epoxy resin, a salicylaldehyde type epoxy resin with an ⁇ , ⁇ -unsaturated carboxylic acid Can be mentioned.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid include (meth) acrylic acid.
  • An epoxy resin can be used individually by 1 type or in combination of 2 or more types.
  • a compound obtained by adding acrylic acid to diglycidyl ether of bisphenol A, which is a kind of bisphenol type epoxy resin, can be used as the photopolymerizable compound.
  • This compound is commercially available, for example, as Biscote # 540 (product name, manufactured by Osaka Organic Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more.
  • urethane (meth) acrylate examples include, for example, a (meth) acrylic monomer having an OH group at the ⁇ -position, isophorone diisocyanate, and 2,6-toluene.
  • urethane (meth) acrylate is composed of an ethylenically unsaturated group, a polycarbonate skeleton, a polyether skeleton, a polyester skeleton, a polycaprolactone diol skeleton, and a silicone skeleton. And at least one selected skeleton.
  • a compound can be obtained, for example, by an addition reaction of a (meth) acrylic monomer having an OH group at the ⁇ -position, a diisocyanate compound, polycarbonate diol, polyether diol, polyester diol, polycaprolactone diol, and silicone diol. it can. These can be used individually by 1 type or in combination of 2 or more types.
  • EO means “ethylene oxide” and “PO” means “propylene oxide”.
  • EO modified means that a block structure of ethylene oxide unit (—CH 2 CH 2 O—) is included, and “PO modified” means propylene oxide unit (—CH 2 CH (CH 3 ) O—. ) Block structure is included.
  • urethane (meth) acrylate a compound having a polycarbonate skeleton can be used from the viewpoint of improving adhesiveness and improving chemical resistance and water resistance.
  • a compound having a polycarbonate skeleton has high crystallinity at room temperature, but its crystallinity collapses and becomes amorphous at high temperatures. Therefore, when it is pressure-bonded at high temperature (thermocompression bonding), it has high adhesion to the adherend. It is thought that it shows.
  • Examples of the urethane (meth) acrylate having a polycarbonate skeleton include compounds represented by the following general formula (VIII).
  • R represents an alkylene group having 1 to 18 carbon atoms
  • R 2 represents a hydrogen atom or a methyl group
  • X represents a divalent organic group
  • Z represents a divalent to hexavalent organic group.
  • M and n each independently represents an integer of 1 to 30, and p and q each independently represents an integer of 1 to 5.
  • a plurality of R, R 2 , X and Y in the same molecule may be the same or different. When n is 2 or more, the plurality of m may be the same or different.
  • X is selected from, for example, arylene diisocyanate (2,6-toluene diisocyanate, 2,4-toluene diisocyanate, etc.), polymethylene diisocyanate (1,6-hexamethylene diisocyanate, etc.), and cycloalkylene diisocyanate (isophorone diisocyanate, etc.). It may be a residue of a diisocyanate compound (a portion excluding an isocyanate group).
  • the compound represented by the formula (VIII) includes a diisocyanate compound represented by the following formula (IX), 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. It can obtain by making it react with the compound which has an ethylenically unsaturated group and a hydroxyl group.
  • R represents an alkylene group having 1 to 18 carbon atoms
  • X represents a divalent organic group
  • m and n each independently represents an integer of 1 to 30.
  • a plurality of R and X in the same molecule may be the same or different.
  • n is 2 or more, the plurality of m may be the same or different.
  • the number average molecular weight of urethane (meth) acrylate is 500 to 6000, 1000 to 5000, or 1500 to 5000. Also good.
  • the component may contain the compound which has 3 or more ethylenically unsaturated groups from a viewpoint which can improve peelability more. From the viewpoint of storage stability, the number of ethylenically unsaturated groups may be 20 or less. These can be used individually by 1 type or in combination of 2 or more types.
  • the compound having three or more ethylenically unsaturated groups for example, an addition reaction product of a polyfunctional (meth) acrylate compound having a hydroxyl group and a diisocyanate compound, an epoxy resin and (meth) acrylic acid are reacted.
  • the epoxy acrylate compound obtained is mentioned.
  • Polyfunctional (meth) acrylate compounds having a hydroxyl group include, for example, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO or PO-modified tri Methylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) Selected from acrylate and dipentaerythritol pentaacrylate.
  • the diisocyanate compound is selected from, for example, polymethylene diisocyanate such as hexamethylene diisocyanate, arylene diisocyanate such as tolylene diisocyanate, and cycloalkylene diisocyanate such as isophorone diisocyanate.
  • the epoxy resin is selected from, for example, a novolac type epoxy resin, a bisphenol type epoxy resin, and a salicylaldehyde type epoxy resin.
  • the photopolymerization initiator of component (C) is a hexaarylbiimidazole that may have a substituent (hereinafter sometimes simply referred to as hexaarylbiimidazole) or a substituent from the viewpoint of adhesion and sensitivity.
  • 2,4,5-triarylimidazole dimer (hereinafter sometimes simply referred to as 2,4,5-triarylimidazole dimer) may be included.
  • 2,4,5-triarylimidazole dimers include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxy).
  • Phenyl) imidazole dimer 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- Methoxyphenyl) -4,5-diphenylimidazole dimer.
  • the substituents of the aryl groups of the two 2,4,5-triarylimidazoles constituting the dimer may be the same or different.
  • photopolymerization initiator examples include benzophenone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N, N ′, N′-tetraethyl-4 , 4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- ( Aromatic ketones such as methylthio) phenyl] -2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone , 2-phenylanthraquinone
  • a combination of a thioxanthone compound and a tertiary amine compound, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid, may be used. These are used alone or in combination of two or more.
  • the (D) component silane compound is a compound containing one or more silicon atoms, and often has an alkoxysilyl group.
  • the silane compound it is possible to improve adhesion particularly when a glass substrate is used as the transparent cover substrate.
  • a silane compound having an alkoxysilyl group and a reactive substituent can be used.
  • the reactive substituent can be selected from, for example, a carboxyl group, an amino group, an isocyanate group, a methacryloyl group, and an epoxy group.
  • Examples of the silane compound having a carboxyl group include trimethoxysilylbenzoic acid.
  • silane compound having an amino group examples include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
  • examples of the silane compound having an isocyanate group include ⁇ -isocyanatopropyltriethoxysilane.
  • silane compound having a methacryloyl group examples include 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, and 3-methacryloyloxypropyltriethoxysilane.
  • silane compound having an epoxy group examples include 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • a silane compound having a methacryloyl group can be used in consideration of compatibility with the component (A), the component (B), and the component (C) and the adhesion to the glass substrate.
  • 3-Methacryloyloxypropyltriethoxysilane is particularly excellent in terms of handling. These silane compounds can be used alone or in combination of two or more.
  • the content of the component (A) may be 40 to 80 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B).
  • the content of the component (A) is 40 parts by mass or more, it can be prevented that the resist becomes brittle or the coating property is deteriorated.
  • the content of the component (A) is 80 parts by mass or less, higher sensitivity tends to be obtained. From the same viewpoint, the content of the component (A) may be 45 to 70 parts by mass.
  • the content of the component (B) may be 20 to 60 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B).
  • the content of the component (B) is 20 parts by mass or more, particularly excellent resolution can be obtained.
  • the content of the component (B) is 60 parts by mass or less, the occurrence of edge fusion can be effectively suppressed.
  • the content of the component (B) may be 30 to 55 parts by mass.
  • the content of the component (B) may be 10 to 200 parts by mass with respect to 100 parts by mass of the component (A). When the content of the component (B) is 10 parts by mass or more, excellent peelability due to sufficient photocuring tends to be obtained more easily. When the content of the component (B) is 200 parts by mass or less, more excellent characteristics tend to be obtained in terms of adhesiveness and film formability before actinic ray irradiation. From the same viewpoint, the content of the component (B) may be 20 to 150 parts by mass, or 40 to 120 parts by mass.
  • the content of the compound having (B1) an unsaturated group and an isocyanuric ring as the component (B) may be 1 to 40 parts by mass with respect to 100 parts by mass as the total of the components (A) and (B). Good.
  • the content of the component (B1) is 1 part by mass or more, better adhesion with the glass substrate can be obtained.
  • the content of the component (B1) is 40 parts by mass or less, the fluidity of the composition does not become too high, and the component oozes out from the edge of the wound-up photosensitive resin film (edge fusion). Can be suppressed.
  • the content of the component (B1) may be 3 to 30 parts by mass, or 6 to 25 parts by mass.
  • the content of the component (B1) may be 5 to 40 parts by mass or 7 to 35 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B) and (C).
  • the content of the component (B1) is within these numerical ranges, effects relating to adhesion, peelability, and the like can be obtained more remarkably.
  • the content is the total amount of the component (A) and the component (B).
  • the amount may be 1 to 50 parts by mass with respect to 100 parts by mass.
  • the content of the photopolymerizable compound other than the component (B1) may be 10 to 45 parts by mass, or 15 to 43 parts by mass.
  • the content of the component (C) may be 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B).
  • the content of the component (C) is 0.1 parts by mass or more, higher photosensitivity tends to be obtained.
  • the content of the component (C) is 20 parts by mass or less, absorption in the vicinity of the surface of the photosensitive resin film is suppressed at the time of exposure, and there is a tendency that it can be easily photocured to the inside more easily.
  • the content of the component (C) may be 0.2 to 10 parts by mass.
  • component (C) contains hexaarylbiimidazole
  • the content of hexaarylbiimidazole in component (C) may be 10 to 99% by mass based on the total amount of component (C). If this content is 10% by mass or more, the adhesion tends to be further improved, and if it is 99% by mass or less, development sludge during development processing tends to be suppressed. From the same viewpoint, the content of hexaarylbiimidazole may be 20 to 98% by mass.
  • the content of the component (D) may be 0.5 to 12 parts by mass with respect to 100 parts by mass as a total of the components (A), (B) and (C). There exists a tendency for the adhesive force with a board
  • the photosensitive resin composition or the photosensitive resin film formed therefrom may contain a compound having a thiol group as the component (E).
  • the compound having a thiol group functions effectively as a hydrogen donor, and can improve photosensitivity or more adhesion with a transparent cover substrate.
  • the compound having a thiol group examples include mercaptobenzoxazole (MBO), mercaptobenzothiazole (MBT), mercaptobenzimidazole (MBI), ethanethiol, benzenethiol, mercaptophenol, mercaptotoluene, 2-mercaptoethylamine, mercapto Ethyl alcohol, mercaptoxylene, thioxylenol, 2-mercaptoquinoline, mercaptoacetic acid, ⁇ -mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thiosalicylic acid, mercaptocyclohexane, ⁇ -mercaptodiphenylmethane, C-mercaptotetrazole, mercapto Naphthalene, mercaptonaphthol, 4-mercaptobiphenyl, mercaptohypoxanthine, mercaptopyridine
  • the compound having a thiol may contain mercaptobenzoxazole (MBO), mercaptobenzothiazole (MBT), mercaptobenzimidazole (MBI), or a combination thereof.
  • the content of the compound having a thiol group is 0.01 to 2 parts by mass, 0.05 to 1 part by mass, or 100 parts by mass of the total amount of the components (A), (B) and (C), or It may be 0.1 to 0.5 parts by mass.
  • the photosensitive resin composition or photosensitive resin film may be a dye such as malachite green, a photochromic agent such as tribromophenylsulfone or leucocrystal violet, a thermochromic inhibitor, or a plastic such as p-toluenesulfonamide.
  • a dye such as malachite green
  • a photochromic agent such as tribromophenylsulfone or leucocrystal violet
  • a thermochromic inhibitor such as p-toluenesulfonamide
  • Contains other components such as additives, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. May be. These may be used alone or in combination of two or more.
  • the content of each of the other components is, for example, about 0.01 to 20 parts by mass with respect to 100 parts by
  • the photosensitive resin film can be obtained, for example, by molding a photosensitive resin composition obtained by mixing the component (A), the component (B), the component (C), and other appropriately used components into a film shape. it can.
  • the photosensitive resin composition can be obtained, for example, by uniformly kneading and mixing each component with a roll mill, a bead mill or the like. If necessary, each component of the photosensitive resin composition is added to a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. By dissolving, a solution having a solid content of about 30 to 60% by mass can be prepared, and a photosensitive resin film can be formed using this solution.
  • the method for molding the photosensitive resin composition into a film is not particularly limited.
  • a protective film polymer films, such as polyethylene and a polypropylene, are mentioned, for example.
  • coating of a solution can be performed by methods, such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater, for example.
  • the coating film can be dried by heating at 70 to 150 ° C. for about 5 to 30 minutes.
  • the photosensitive sheet comprised from a support body, the photosensitive resin film, and a protective film is obtained.
  • the thickness of the photosensitive resin film after drying varies depending on the application, but may be, for example, 10 to 200 ⁇ m, 20 to 180 ⁇ m, 30 to 160 ⁇ m, or 50 to 160 ⁇ m.
  • the photosensitive resin film having such a thickness deep concave portions or high convex portions can be particularly easily formed on the transparent cover substrate.
  • the photosensitive sheet is usually stored in a state of being wound around a cylindrical core. At this time, it is preferable that the photosensitive sheet is wound in a roll shape so that the protective film is on the outside.
  • An end face separator can be installed on the end face of the roll-shaped photosensitive sheet from the viewpoint of end face protection.
  • a moisture-proof end face separator can be installed from the standpoint of edge fusion resistance.
  • the photosensitive sheet can be wrapped and packaged in a black sheet with low moisture permeability.
  • the winding core include a plastic core such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer).
  • the method for producing a processed glass substrate according to the present invention includes a step of forming a resist covering a part of the surface of the glass substrate using the photosensitive resin composition or the photosensitive resin film, and using the resist as a mask, the glass substrate. Etching the surface of the substrate with hydrofluoric acid.
  • FIG. 1 is a plan view showing an embodiment of a processed glass substrate.
  • 2 is a cross-sectional view taken along line II-II in FIG.
  • a through hole 2 that penetrates the glass substrate is formed.
  • FIG. 3 is a cross-sectional view showing an embodiment of a method for producing a processed glass substrate.
  • a glass substrate 20 is first prepared as shown in FIG.
  • a resist 4 covering a part of the surface of the glass substrate 20 is formed.
  • the resist 4 is formed using a photosensitive resin composition or a photosensitive resin film.
  • the film thickness of the resist 4 is, for example, about 30 to 80 ⁇ m.
  • the photosensitive resin film is laminated on the glass substrate 20, and the laminated photosensitive resin film is exposed through a photomask in which portions other than the region where the through holes 2 are formed are transparent. Then, the resist 4 can be formed by development.
  • the photosensitive resin film can be attached to a glass substrate by hot roll lamination, a vacuum press method, or the like.
  • the photosensitive resin composition the resist 4 is formed by forming a photosensitive resin composition on a glass substrate by a method such as coating, and exposing and developing the formed photosensitive resin composition layer.
  • the photomask may be a negative type or a positive type, and commonly used ones can be used.
  • a known light source such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet light, visible light, or the like is used.
  • Laser direct drawing exposure can also be performed without using a photomask.
  • development is performed by removing unexposed portions by wet development, dry development, or the like using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent.
  • a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent.
  • an alkaline aqueous solution can be selected.
  • the alkaline aqueous solution include a dilute solution of 0.1 to 5% by mass sodium carbonate, a dilute solution of 0.1 to 5% by mass potassium carbonate, and a dilute solution of 0.1 to 5% by mass sodium hydroxide.
  • the pH of the alkaline aqueous solution may be 9-11.
  • the temperature of the alkaline aqueous solution is adjusted according to the developability of the photosensitive resin composition.
  • the alkaline aqueous solution may contain a surface active agent, an antifoaming agent, an organic solvent, and the like.
  • the development method include a dip method, a spray
  • the formed resist 4 may be further cured by heat treatment at about 60 to 250 ° C. as necessary.
  • Mylar tape 6 for protecting from hydrofluoric acid is attached to the back surface (surface opposite to the resist 4) of the glass substrate.
  • an organic material such as a polyester tape or a metal film such as Cr / Au can be applied.
  • Etching methods include, for example, a dipping method in which the substrate is immersed in an etching solution and swinging, a bubble method in which nitrogen gas or air bubbles are traced on the substrate surface to promote liquid convection on the substrate surface, a spray is sprayed, and the substrate is sprayed. Spray methods that promote surface liquid convection can be applied. Instead of forming the through hole, a groove-like recess can be formed.
  • the concentration of hydrofluoric acid may be 0.5 to 20% by mass or 8 to 18% by mass. When the concentration of hydrofluoric acid is within these numerical ranges, a reasonably high etching rate can be obtained, and the etching depth tends to be easily adjusted while maintaining high productivity.
  • the hydrofluoric acid may contain acids such as sulfuric acid, nitric acid and hydrochloric acid, and organic compounds such as surfactants.
  • the resist 4 and the Mylar tape 6 are removed, and a processed glass substrate 10 provided with the through holes 2 can be obtained (FIG. 3D).
  • the resist 4 can be removed by, for example, immersing in an alkaline aqueous solution such as an aqueous sodium hydroxide solution, but from the viewpoint of productivity, the resist 4 may be removed by heating.
  • the resist on the glass substrate after etching can be removed by heating, for example, at 30 to 70 ° C. for 10 to 50 minutes. Since the resist formed from the photosensitive resin composition according to the present embodiment has excellent peelability, it can be easily removed by heating.
  • FIG. 4 is a cross-sectional view showing an embodiment of the touch panel.
  • the touch panel 100 includes a touch panel sensor 40, a transparent cover base material 11 that faces the touch panel sensor 40, and a decoration unit 50 and an overcoat layer 30 that are provided therebetween.
  • the surface of the transparent cover base 11 opposite to the touch panel sensor 40 is the input surface 12 of the touch panel 100.
  • the decoration unit 50 is provided on the back surface 14 of the transparent cover substrate 11 on the touch panel sensor 40 side.
  • the back surface 14 forms a recess at the peripheral edge thereof, and the decorative portion 50 fills the recess of the back surface 14 and forms a substantially flat surface together with the back surface 14.
  • the decorating unit 50 is provided so as to overlap the peripheral edge of the input surface.
  • the overall shape of the decorative portion 50 is a frame shape or a frame shape.
  • the width of the decorative portion 50 may be about 1 to 20 mm.
  • the thickness of the decorating part 50 may be about 5 to 300 ⁇ m.
  • the decoration unit 50 is provided, for example, in order to prevent the input / output wiring provided in the peripheral portion of the information input device and the image display unit from being visually recognized from the input surface 12 side.
  • the decoration part 50 can also be provided for a decoration.
  • the decoration part 50 does not necessarily need to be provided over the whole peripheral part of the transparent cover base material 11.
  • FIG. the decorating unit 50 can be provided along at least one of the four sides of the rectangular input surface.
  • the overcoat layer 30 extends from the transparent cover base material 11 to the decoration portion 50.
  • the thickness of the overcoat layer 30 may be about 1 to 20 ⁇ m.
  • a plurality of touch panel sensors 40 are provided on the surface of the overcoat layer 30 opposite to the transparent cover substrate 11.
  • FIG. 5 is a cross-sectional view showing an embodiment of a touch panel manufacturing method.
  • the sheet-like transparent cover base material 11 which has the input surface 12 of a touchscreen and the back surface 14 of the back side is prepared (FIG.5 (a)).
  • the transparent cover substrate 11 only needs to have transparency, heat resistance, and mechanical strength that do not hinder the manufacturing process.
  • the transparent cover base material 11 for example, a glass substrate, a thermoplastic resin film, or an organic-inorganic composite material substrate is used.
  • the thickness of the transparent cover substrate 11 may be about 30 to 2000 ⁇ m.
  • a resist 4a covering a part of the back surface 14 of the transparent cover substrate 11 is formed.
  • the resist 4a is formed by, for example, a method of exposing and developing a portion other than a region where a later-described concave portion is formed in the photosensitive resin film laminated on the transparent cover substrate 11 using a photomask. be able to.
  • the photosensitive resin film can be laminated by hot roll lamination, a vacuum pressure press method, or the like. After pasting, it can form by exposing and developing the photosensitive resin film mentioned later. The exposure and development can be performed in a state where the mylar tape 6 is attached to the input surface 12 of the transparent cover substrate 11.
  • the back surface 14 of the transparent cover substrate 11 is etched using the resist 4a as a mask to form a recess 22.
  • the depth (maximum depth) d of the recess 22 may be 40 ⁇ m or more.
  • the depth d may be 40 ⁇ m or more in the entire bottom surface, or the depth d may be 40 ⁇ m or more in a part of the bottom surface.
  • the transparent cover substrate can be etched using, for example, an etchant selected from fluoride salts, sulfates, hydrofluoric acid, sulfuric acid, and the like. As will be described later, a concave portion having a depth of 40 ⁇ m or more can be easily formed by appropriately selecting a photosensitive resin film.
  • the resist 16 and the mylar tape 18 are removed as shown in FIG.
  • the resist 16 may be removed by immersing in an alkaline aqueous solution such as an aqueous sodium hydroxide solution. It is also possible to improve productivity by removing the resist 16 by heating.
  • a decorative portion 50 is formed that fills part or all of the recess 22 formed by etching.
  • the decorative portion 50 is made of a light shielding material.
  • This light-shielding material can be, for example, either a resin composition (for example, an acrylic resin composition) containing a pigment (for example, a black pigment) or a low-melting glass containing a metal oxide.
  • the decoration part 50 may be formed using a transparent material.
  • the decorating part 50 can be formed by, for example, filling the recess 22 with ink for forming a decorating part by printing such as screen printing, and drying or curing the filled ink as necessary.
  • the decorative portion 50 is formed such that a step is not substantially formed at the boundary between the decorative portion 50 and the back surface 14 of the transparent cover base material 11. In other words, a flat surface is formed from the transparent cover base material 11 to the decorative portion 50. Since the depth d of the concave portion 22 is large, the decorative portion 50 can be easily formed such that no step is formed or a step having a design-friendly range as described later is formed.
  • an overcoat layer 30 extending from the transparent cover base material 11 to the decorative portion 50 is formed on the back surface 14 side of the transparent cover base material 11.
  • the material of the overcoat layer 30 is selected from those having desired characteristics such as transparency, heat resistance, and mechanical strength in addition to the adhesiveness between the transparent cover substrate 11 and the decorative portion 50.
  • the overcoat layer 30 can be formed using, for example, a photocurable resin such as an acrylic photocurable resin.
  • the touch panel sensor 40 is disposed on the overcoat layer 30.
  • the touch panel sensor 40 includes, for example, a transparent electrode that functions as a touch sensor and a lead wiring.
  • the transparent electrode can be formed by appropriately selecting a thin film forming method such as a vacuum deposition method or a sputtering method.
  • a thin film forming method such as a vacuum deposition method or a sputtering method.
  • a MAM Molybdenum-Aluminum-Molybdenum
  • the transparent cover substrate 11 is cut along with the decorative portion 50 and the overcoat layer 30 along the predetermined cut surface 15, thereby cutting out the touch panel 100 of FIG. 4. It is. Cutting can be performed using a grinder or the like.
  • the cut surface 15 is not necessarily required to include the decorative portion 50 and the overcoat layer 30.
  • FIG. 6 is also a cross-sectional view showing an embodiment of a touch panel manufacturing method.
  • this manufacturing method is characterized in that a recess 23 for cutting located on the back side of the recess 22 is formed on the input surface 12 side of the transparent cover base material 11. Different from method 5.
  • the recess 23 for cutting can be formed by etching using the resist 4b as a mask.
  • the photosensitive resin film used for forming the resist 4b may be the same as or different from the photosensitive resin film used for forming the resist 4a.
  • FIG. 7 is also a cross-sectional view showing an embodiment of a touch panel manufacturing method.
  • a step having a height d2 is formed at the boundary between the decorative portion 50 and the transparent cover substrate 11. Due to this step, a step can also be formed on the surface of the overcoat layer (FIG. 7F).
  • the touch panel sensor 40 is designed on the premise of a step, the occurrence of disconnection can be sufficiently effectively suppressed if the height d2 is controlled to be within a range that does not cause a problem in design.
  • the thickness of the decorative portion 50 is the sum of the depth d of the recess 22 and the height d2.
  • d2 may be 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, or 20 ⁇ m or less.
  • d2 may be substantially zero.
  • the photosensitive resin film used to form the resist 4a is formed, for example, from the above-described photosensitive resin composition.
  • the photosensitive resin film comprises a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a silane compound. There may be.
  • the photosensitive resin film may be provided on the support.
  • Photosensitive resin composition Each component was mixed and stirred with the compounding ratio shown in Table 1, and the solution of the photosensitive resin composition was obtained.
  • the binder polymer (I) as component (A) in Table 1 was synthesized according to the following synthesis example. In Table 1, each numerical value represents a part by mass.
  • methacrylic acid as a polymerizable monomer
  • 110 g of methacrylic acid methyl ester 110 g of methacrylic acid methyl ester, 65 g of acrylic acid ethyl ester, 50 g of butyl methacrylate, 125 g of styrene, and 2.5 g of azobisisobutyronitrile are mixed together.
  • a mass solution was prepared. This polymer solution was added dropwise over 4 hours to the mixture in the flask heated to 85 ° C. Thereafter, the solution in the flask was kept at 85 ° C. for 2 hours with stirring.
  • a solution obtained by dissolving 0.5 g of azobisisobutyronitrile in 150 g of a mixture of methyl cellosolve and toluene having a mass ratio of 3: 2 was dropped into the flask over 10 minutes.
  • the solution after the dropping was stirred and kept at 85 ° C. for 5 hours to produce an acrylic resin as the binder polymer (I).
  • the solution was diluted with a mixed solvent of acetone and propylene glycol monomethyl ether having a mass ratio of 3: 2 to obtain a binder polymer (I) solution having a nonvolatile content (solid content) concentration of 43 mass%.
  • the obtained binder polymer (I) had a weight average molecular weight of 50,000, a dispersity of 2.0, and an acid value of 195 mgKOH / g.
  • the weight average molecular weight of the binder polymer (I) was measured by a gel permeation chromatography method and was derived by conversion using a standard polystyrene calibration curve.
  • the measurement conditions of gel permeation chromatography (GPC) are shown below.
  • Photopolymerizable compound M-215 bis (acryloxyethyl) hydroxyethyl isocyanurate (trade name, manufactured by Toagosei Co., Ltd.)
  • HT-9082-95 Compound obtained by reacting a hydroxyl group-terminated polycarbonate compound, organic isocyanate and 2-hydroxyethyl acrylate (weight average molecular weight 4000, trade name, manufactured by Hitachi Chemical Co., Ltd.)
  • FA-MECH ⁇ -chloro-2-hydroxypropyl- ⁇ '-methacryloyloxyethyl-o-phthalate (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
  • FA-314A Nonylphenyl EO-modified monoacrylate (4 mol of ethylene oxide (EO) group added in one molecule, product name, manufactured by Hitachi Chemical Co., Ltd.)
  • FA-321M EO-modified bisphenol A dimethacrylate (10 mol of
  • the obtained photosensitive resin composition solution is uniformly coated on a 16 ⁇ m thick polyethylene terephthalate film and dried for 10 minutes in a 100 ° C. hot air convection dryer to form a 140 ⁇ m thick photosensitive resin film.
  • a polyethylene film tensile strength in the film longitudinal direction: 16 MPa, tensile strength in the film width direction: 12 MPa, trade name: NF-15, manufactured by Tamapoly Co., Ltd.
  • a photosensitive sheet composed of a polyethylene terephthalate film, a photosensitive resin film and a polyethylene film was obtained.
  • a glass substrate (Corning Gorilla-IOX glass (registered trademark), outer dimensions 100 mm ⁇ 100 mm, thickness 0.55 mm) was washed with isopropyl alcohol and air-dried.
  • the photosensitive sheet was laminated on the surface of the glass substrate heated to 80 ° C. while peeling the polyethylene film. Lamination was performed using a laminate roll heated to 110 ° C. Thereby, the laminated body which has the structure laminated
  • the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 120 seconds to remove an unexposed portion of the photosensitive resin film, thereby forming a resist.
  • the glass substrate was put together with the resist in a box-type dryer heated to 200 ° C., and heat treatment was performed for 1 hour.
  • a polyester tape was applied as a protective film on the back surface of the heated glass substrate, and immersed in hydrofluoric acid (concentration 10%, 25 ° C.) for 4 hours 30 minutes, and the glass substrate surface was etched to form a recess.
  • the glass substrate was washed with water, water was blown off by air blow, and the glass substrate was dried by heating at 80 ° C. for 10 minutes.
  • the state of the resist at this time was observed, and peelability was evaluated according to the following criteria.
  • C The resist was completely peeled when the washed water was blown away. Or the whole resist was closely_contact
  • a resist was formed in the same procedure as the evaluation of peelability. The formed resist was observed with a microscope having a magnification of 50 times, and developability was evaluated according to the following criteria.
  • B Resist having a width of 5 mm remained, and no resist residue was observed in a space of 1 to 4 mm out of a space of 1 to 5 mm.
  • C Resist having a width of 5 mm remained, and a resist residue was observed in all the spaces of 1 to 5 mm. Alternatively, the 5 mm wide resist was lost.
  • the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 120 seconds to remove the unexposed portion of the photosensitive resin film, thereby obtaining a photocured material pattern as a resist.
  • the glass substrate was put together with the resist in a box-type dryer heated to 200 ° C., and heat treatment was performed for 1 hour.
  • a polyester tape was applied as a protective film on the back surface of the heated glass substrate, immersed in hydrofluoric acid (concentration 10%, 25 ° C.) for 30 minutes, and the glass substrate surface was etched to form a recess.
  • the resist was immersed in a 5% aqueous sodium hydroxide solution at 50 ° C. for 1 hour and peeled off.
  • the etching step depth of the concave portion
  • the etching step was measured with a stylus type step gauge DekTak3ST (ULVAC), and the deep digging property was evaluated according to the following criteria.
  • B The etching step was 30 ⁇ m or more and less than 40 ⁇ m.
  • C The etching step was less than 30 ⁇ m.
  • the content of the compound not containing a silane compound and having an unsaturated group and an isocyanuric ring is 100 parts by mass of the total amount of the component (A), the component (B) and the component (C).
  • the photosensitive resin composition of Comparative Example 1 that is not in the range of 25 to 40 parts by mass is inferior in peelability, hydrogen fluoride acid resistance, and deep digging property.
  • the content of the compound containing a silane compound or having an unsaturated group and an isocyanuric ring is 25 to 40 masses per 100 mass parts of the total amount of the component (A), the component (B) and the component (C). It was confirmed that the photosensitive resin composition of the example which is a part has good peelability, acid resistance to hydrogen fluoride, developability and deep digging property.
  • Example 9 A glass substrate (Gorilla-IOX glass (registered trademark) manufactured by Corning, length 100 mm ⁇ width 100 mm ⁇ thickness 0.55 mm) as a transparent cover base was washed with isopropyl alcohol and air-dried. A photosensitive sheet prepared from the solution of the photosensitive resin composition of Example 1 was laminated on the surface of a glass substrate heated to 80 ° C. while peeling the polyethylene film. Lamination was performed using a laminate roll heated to 110 ° C. Thereby, the laminated body which has the structure laminated
  • Gorilla-IOX glass (registered trademark) manufactured by Corning, length 100 mm ⁇ width 100 mm ⁇ thickness 0.55 mm was washed with isopropyl alcohol and air-dried.
  • a photosensitive sheet prepared from the solution of the photosensitive resin composition of Example 1 was laminated on the surface of a glass substrate heated to 80 ° C
  • a photomask was adhered to the polyethylene terephthalate film of the obtained laminate, and 365 nm from the polyethylene terephthalate film side using a parallel light exposure machine (MAP1200, Dainippon Screen Printing Co., Ltd., trade name) having an ultrahigh pressure mercury lamp.
  • the exposure was performed with an energy amount of 400 mJ / cm 2 at a wavelength of.
  • the polyethylene terephthalate film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 120 seconds to remove the unexposed portion of the photosensitive resin film.
  • the heat processing for 1 hour was performed with the box-type dryer heated at 200 degreeC, and the resist which has the pattern which covers a part of glass substrate surface was formed.
  • a chemical etching solution containing 10% hydrofluoric acid as a main component (trade name: hydrogen fluoride, manufactured by Kanto Chemical Co., Inc.) By immersing in acid for 40 minutes, the glass substrate surface (the portion of the back surface not covered with the resist) was etched using the resist as a mask to form a recess having a depth of 70 ⁇ m. Subsequently, the glass substrate was washed with water, and water was blown off by air blow or the like. Thereafter, the resist was removed.
  • thermosetting ink (acrylic thermosetting resin composition containing black pigment, Teikoku Mfg. Co., Ltd., trade name: GLS912) by screen printing (mesh # 250 screen plate) and decorated Part was formed.
  • the thickness of the decoration part was 80 micrometers, and the level
  • an acrylic resin-based photo-curing type negative overcoat agent (manufactured by JSR Corporation, trade name: NN901) was applied on the transparent cover substrate and the decorative portion by a spin coating method.
  • the coated overcoat agent was irradiated with ultraviolet rays and baked in an oven to form an overcoat layer having a thickness of 10 ⁇ m.
  • the level difference formed on the surface of the overcoat layer due to the level difference between the decorative portion and the transparent cover substrate was 5 ⁇ m.
  • An ITO (Indium-Tin-Oxide) film having a thickness of 0.2 ⁇ m was formed on the overcoat layer by a sputtering method, and the ITO film was patterned by photolithography.
  • a MAM (Molybdenum-Aluminum-Molybdenum) electrode having a film thickness of 0.2 ⁇ m was formed by a sputtering method and patterned by photolithography so as to have a predetermined pattern. In this way, a touch panel sensor having an ITO film and a MAM electrode was disposed on the overcoat layer.
  • the glass substrate was cut along a predetermined cut surface using a grinder together with the decorative portion and the overcoat layer to obtain a touch panel.
  • the obtained touch panel had a small step between the decorative portion and the transparent cover base material, no disconnection of the electrode of the touch panel sensor occurred. Moreover, since the formed decoration part was large, it had high optical density.
  • Example 10 At the position on the back side of the concave portion for forming the decorative portion, a concave portion for cutting was formed on the surface on the input surface side of the glass substrate by etching using a resist as a mask. A touch panel was obtained in the same manner as in Example 9 except for this. The width of the recess for cutting was larger than the diameter of the grinder drill.
  • the glass substrate was etched by immersion in a chemical etching solution containing 10% hydrofluoric acid as a main component (manufactured by Kanto Chemical Co., Inc., trade name: hydrofluoric acid).
  • the PMMA resist started to peel off 20 minutes after the immersion, and after 21 minutes, the PMMA resist was completely detached from the glass substrate. It was 20 micrometers when the depth of the recessed part formed by the etching was measured after water washing.
  • thermosetting ink product name: GLS912, manufactured by Teikoku Ink Manufacturing Co., Ltd.
  • the thickness of the decoration part was 80 micrometers
  • step difference of a decoration part and a transparent cover base material was 60 micrometers.
  • an acrylic resin photo-curing type negative overcoat agent (manufactured by JSR Corporation, trade name: NN901) was applied on the transparent cover substrate and the decorative portion by a spin coating method.
  • the coated overcoat agent was irradiated with ultraviolet rays and baked in an oven to form an overcoat layer having a thickness of 10 ⁇ m.
  • the step formed on the surface of the overcoat layer due to the step between the decorative portion and the transparent cover base was 40 ⁇ m.
  • an ITO (Indium-Tin-Oxide) film was formed with a thickness of 0.2 ⁇ m by sputtering, and the ITO film was patterned by photolithography.
  • a MAM (Molybdenum-Aluminum-Molybdenum) electrode was formed with a thickness of 0.2 ⁇ m by a sputtering method, and patterned by photolithography so as to form a predetermined pattern. Since a disconnection due to a step occurred in the vicinity of the boundary between the decorative portion and the transparent cover base material, the yield was about 40%.
  • Example 9 In the touch panels of Example 9 and Example 10, the level difference between the decorative portion and the transparent cover substrate is extremely reduced as compared with the touch panel of Comparative Example 3, and the overcoat layer formed thereon has a flat surface. Had.
  • Example 9 In the resistance value measurement evaluation and operation check of the touch panel sensor arranged on the overcoat layer, in Example 9 and Example 10, a good resistance value was obtained and the operation check was also good. On the other hand, the touch panel of Comparative Example 3 did not operate normally because an abnormal resistance value was confirmed by disconnection of the touch panel sensor.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Materials For Photolithography (AREA)

Abstract

La présente invention concerne une composition de résine photosensible utilisée pour former une réserve sous la forme d'un masque devant être utilisé dans la gravure d'un substrat en verre par un acide fluorhydrique. Cette composition de résine photosensible contient un polymère liant (A), un composé photopolymérisable (B), un initiateur de photopolymérisation (C), et un composé silane (D), et le composé photopolymérisable (B) comprend un composé (B1) comportant un groupe insaturé et un cycle isocyanurique.
PCT/JP2013/058027 2012-03-23 2013-03-21 Composition de résine photosensible, procédé de fabrication d'un substrat de verre traité l'utilisant, et écran tactile et son procédé de fabrication WO2013141286A1 (fr)

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KR1020147025839A KR20140148379A (ko) 2012-03-23 2013-03-21 감광성 수지 조성물, 및 이것을 사용한 가공 유리 기판의 제조 방법, 및 터치 패널 및 그 제조 방법
CN201380015589.6A CN104204948A (zh) 2012-03-23 2013-03-21 感光性树脂组合物及使用其的加工玻璃基板的制造方法、和触控面板及其制造方法

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JP2015152726A (ja) * 2014-02-13 2015-08-24 三洋化成工業株式会社 感光性樹脂組成物
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JP2016161666A (ja) * 2015-02-27 2016-09-05 日立化成株式会社 感光性樹脂組成物、感光性エレメント及びガラス基板の加工方法
JP2017181959A (ja) * 2016-03-31 2017-10-05 日立化成株式会社 感光性樹脂組成物、感光性樹脂フィルム、硬化物の製造方法、積層体、及び電子部品
WO2017209193A1 (fr) * 2016-05-31 2017-12-07 富士フイルム株式会社 Film de transfert, motif décoratif et écran tactile
WO2022113161A1 (fr) * 2020-11-24 2022-06-02 昭和電工マテリアルズ株式会社 Composition de résine photosensible, élément photosensible, procédé de formation de motif de réserve, et procédé de fabrication de carte de circuit imprimé

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TWI570606B (zh) * 2015-08-28 2017-02-11 廣州光寶移動電子部件有限公司 透明基板與基板製作方法
CN108196426A (zh) * 2018-01-05 2018-06-22 潍坊星泰克微电子材料有限公司 用于gpp工艺的光刻胶、制备方法及其光刻工艺
CN108241259B (zh) * 2018-01-24 2021-08-10 杭州福斯特电子材料有限公司 一种具有良好孔掩蔽功能可直接描绘曝光成像的抗蚀剂组合物
CN110524724A (zh) * 2019-07-24 2019-12-03 东莞泰升玻璃有限公司 一种防止断裂的玻璃板钻孔方法

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JP2015143809A (ja) * 2013-12-25 2015-08-06 日立化成株式会社 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
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EP2889277A1 (fr) * 2013-12-30 2015-07-01 LG Display Co., Ltd. Procédé de fabrication d'un dispositif tactile et composition de résine de celui-ci
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JP2015152726A (ja) * 2014-02-13 2015-08-24 三洋化成工業株式会社 感光性樹脂組成物
WO2015156292A1 (fr) * 2014-04-10 2015-10-15 日立化成株式会社 Composition de résine photosensible, élément photosensible, et procédé de fabrication de substrat de verre traité
JP2016161666A (ja) * 2015-02-27 2016-09-05 日立化成株式会社 感光性樹脂組成物、感光性エレメント及びガラス基板の加工方法
JP2017181959A (ja) * 2016-03-31 2017-10-05 日立化成株式会社 感光性樹脂組成物、感光性樹脂フィルム、硬化物の製造方法、積層体、及び電子部品
JPWO2017209193A1 (ja) * 2016-05-31 2019-02-14 富士フイルム株式会社 転写フィルム、加飾パターン及びタッチパネル
WO2017209193A1 (fr) * 2016-05-31 2017-12-07 富士フイルム株式会社 Film de transfert, motif décoratif et écran tactile
WO2022113161A1 (fr) * 2020-11-24 2022-06-02 昭和電工マテリアルズ株式会社 Composition de résine photosensible, élément photosensible, procédé de formation de motif de réserve, et procédé de fabrication de carte de circuit imprimé
WO2022113829A1 (fr) * 2020-11-24 2022-06-02 昭和電工マテリアルズ株式会社 Composition de résine photosensible, élément photosensible, procédé de formation de motif de réserve, et procédé de fabrication de carte de circuit imprimé

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