WO2013084284A1 - Procédé de formation de film protecteur d'électrode pour écran tactile, composition de résine photosensible, et élément photosensible - Google Patents

Procédé de formation de film protecteur d'électrode pour écran tactile, composition de résine photosensible, et élément photosensible Download PDF

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Publication number
WO2013084284A1
WO2013084284A1 PCT/JP2011/078108 JP2011078108W WO2013084284A1 WO 2013084284 A1 WO2013084284 A1 WO 2013084284A1 JP 2011078108 W JP2011078108 W JP 2011078108W WO 2013084284 A1 WO2013084284 A1 WO 2013084284A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
photosensitive
protective film
touch panel
Prior art date
Application number
PCT/JP2011/078108
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English (en)
Japanese (ja)
Inventor
田仲　裕之
泰治 村上
笹原　直樹
向　郁夫
五十嵐　由三
雅彦 海老原
山崎　宏
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日立化成株式会社
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Publication date
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to PCT/JP2011/078108 priority Critical patent/WO2013084284A1/fr
Priority to JP2013516814A priority patent/JP5304971B1/ja
Priority to CN201280059836.8A priority patent/CN103975294B/zh
Priority to PCT/JP2012/081377 priority patent/WO2013084883A1/fr
Priority to KR1020177025927A priority patent/KR20170106655A/ko
Priority to CN201810052144.XA priority patent/CN108108072A/zh
Priority to KR1020147016028A priority patent/KR101592803B1/ko
Priority to KR1020147016024A priority patent/KR101989644B1/ko
Priority to KR1020187021801A priority patent/KR102025036B1/ko
Priority to PCT/JP2012/081365 priority patent/WO2013084875A1/fr
Priority to US14/362,716 priority patent/US20140335350A1/en
Priority to CN201610515674.4A priority patent/CN106126003A/zh
Priority to JP2013516812A priority patent/JP5304969B1/ja
Priority to CN201280059906.XA priority patent/CN104054042B/zh
Priority to TW104139042A priority patent/TWI625655B/zh
Priority to TW104135790A priority patent/TWI621671B/zh
Priority to TW101145694A priority patent/TWI512399B/zh
Priority to TW107114189A priority patent/TW201828005A/zh
Priority to TW101145687A priority patent/TWI525491B/zh
Priority to JP2013123513A priority patent/JP6212970B2/ja
Publication of WO2013084284A1 publication Critical patent/WO2013084284A1/fr
Priority to JP2017176922A priority patent/JP6540766B2/ja

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Definitions

  • the present invention relates to a method for forming a protective film for an electrode for a touch panel, and particularly relates to a method for forming a protective film suitable for protecting an electrode of a capacitive touch panel, and a photosensitive resin composition and a photosensitive element used therefor.
  • Liquid crystal display elements and touch panels are used in large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, and display devices such as OA / FA devices.
  • These liquid crystal display elements and touch panels are provided with electrodes made of a transparent conductive electrode material.
  • ITO Indium-Tin-Oxide
  • indium oxide and tin oxide are known, and these materials exhibit high visible light transmittance, so that they can be used as electrode materials for substrates for liquid crystal display elements. It has become mainstream.
  • capacitive touch panel when a fingertip (conductor) contacts the touch input surface, the fingertip and the conductive film are capacitively coupled to form a capacitor. For this reason, the capacitive touch panel detects the coordinates by capturing the change in charge at the contact position of the fingertip.
  • the projected capacitive touch panel can detect multiple fingertips, so it has a good operability to give complex instructions.
  • a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes.
  • ITO Indium-Tin-Oxide
  • the frame area of the touch panel is an area where the touch position cannot be detected, it is an important factor of the product value to reduce the area of the frame area.
  • a treatment for increasing the conductivity is performed by forming a metal layer such as aluminum / molybdenum or copper on the bus electrode.
  • a capacitive projection type touch panel in which an insulating layer is formed on metal is disclosed (for example, Patent Document 1).
  • a silicon dioxide layer is formed on a metal by a plasma chemical vapor deposition method (plasma CVD method) to prevent corrosion of the metal.
  • plasma CVD method plasma chemical vapor deposition method
  • this method uses a plasma CVD method, there is a problem that a high temperature treatment is required and the base material is limited. There is also a problem that the manufacturing cost becomes high.
  • JP 2011-28594 A JP-A-7-253666 JP 2005-99647 A Japanese Patent Laid-Open No. 11-133617
  • a protective film with a photosensitive resin composition can be expected to reduce costs compared to the plasma CVD method.
  • the resin film is formed on the electrode for the touch panel, if the thickness of the resin film is large, a step may be conspicuous between a place where the film is present and a place where the film is not present. Therefore, it is desirable to make the protective film as thin as possible.
  • the rust prevention property of the film formed from the photosensitive resin composition was studied at a level of 10 ⁇ m or less.
  • the present invention relates to a method for forming a protective film for a touch panel electrode, which can form a protective film having sufficient anti-rust properties even on a thin film on a predetermined touch panel electrode, and such a protective film. It aims at providing the photosensitive resin composition and photosensitive element which can be formed.
  • the present inventors have intensively studied, and as a result, by adjusting the hydroxyl value of the photosensitive resin composition containing a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, developability is improved. While ensuring, even if the film
  • a photosensitive layer comprising a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, and a photopolymerization initiator is provided on a substrate having a touch panel electrode.
  • Forming a protective film made of a cured product of the photosensitive resin composition, and forming a protective film for a touch panel electrode having a hydroxyl value of 40 mgKOH / g or less in the entire solid content of the photosensitive resin composition Provide a method.
  • the electrode for the touch panel includes not only electrodes in the sensing area of the touch panel but also metal wiring in the frame area. Either or both of the electrodes provided with the protective layer may be provided.
  • a protective film having a sufficient antirust property can be formed with the following thickness. According to the present invention, it is possible to form a protective film having both sufficient appearance and rust prevention property using the photosensitive resin composition, and thus it is possible to reduce the manufacturing cost in manufacturing the touch panel.
  • the binder polymer component preferably has a hydroxyl value of 50 mgKOH / g or less.
  • the hydroxyl value of the photopolymerizable compound component is 90 mgKOH / g or less from the viewpoint of further improving the rust prevention property of the protective film.
  • the photosensitive resin composition further contains a phosphate ester containing a photopolymerizable unsaturated bond.
  • the acid value of the binder polymer component is preferably 120 mgKOH / g or less.
  • the photosensitive layer preferably has a visible light transmittance of 90% or more. In this case, it is suitable for forming a protective film that covers the electrodes in the sensing region.
  • the photosensitive layer preferably has a b * in the CIELAB color system of ⁇ 0.2 to 1.0. In this case, it is suitable for forming a protective film that covers the electrodes in the sensing region.
  • the photosensitive resin composition preferably further contains one or more compounds selected from the group consisting of triazole compounds having amino groups and tetrazole compounds having amino groups. .
  • development residues can be reduced, and it becomes easy to form a protective film with a good pattern.
  • the present inventors have found that when patterning a thin photosensitive layer having high transparency, the resolution tends to decrease. The present inventors consider that the reason is that when the thickness of the photosensitive layer is reduced, it is easily affected by light scattering from the base material and halation occurs.
  • the photopolymerization initiator contains an oxime ester compound or a phosphine oxide compound, whereby a pattern can be formed with sufficient resolution.
  • the reason why the above effect is obtained is that the oxime moiety contained in the oxime ester compound or the phosphine oxide moiety contained in the phosphine oxide compound has a relatively high photodecomposition efficiency but does not decompose with slight light leakage.
  • the present inventors infer that the influence of leakage light is suppressed because of having a threshold value.
  • a photosensitive element comprising a support film and a photosensitive layer made of the photosensitive resin composition provided on the support film is prepared, and the photosensitive element
  • the photosensitive layer can be provided by transferring the photosensitive layer onto the substrate.
  • a roll-to-roll process can be easily realized, and the solvent drying process can be shortened, which can greatly contribute to shortening of the manufacturing process and cost reduction.
  • the present invention also provides, as a second aspect, a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, wherein the hydroxyl groups in the entire solid content of the photosensitive resin composition
  • a photosensitive resin composition used for forming a protective film for a touch panel electrode having a value of 40 mgKOH / g or less.
  • a protective film having sufficient rust resistance can be formed on a predetermined touch panel electrode even if it is a thin film.
  • the binder polymer component preferably has a hydroxyl value of 50 mgKOH / g or less.
  • the hydroxyl value of the photopolymerizable compound component is preferably 90 mgKOH / g or less from the viewpoint of further improving the rust prevention property of the protective film.
  • the photosensitive resin composition according to the second aspect of the present invention preferably further contains a phosphate ester containing a photopolymerizable unsaturated bond.
  • the acid value of the binder polymer component is preferably 120 mgKOH / g or less.
  • the photosensitive resin composition according to the second aspect of the present invention preferably has a visible light transmittance of 90% or more when a film having a thickness of 5 ⁇ m is formed. .
  • the photosensitive resin composition according to the second aspect of the present invention has a b * in the CIELAB color system of ⁇ 0. It is preferably 2 to 1.0.
  • the photosensitive resin composition according to the second aspect of the present invention comprises one or more compounds selected from the group consisting of triazole compounds having amino groups and tetrazole compounds having amino groups. Furthermore, it is preferable to contain. In this case, development residues can be reduced, and it becomes easy to form a protective film with a good pattern.
  • the photopolymerization initiator contains an oxime ester compound or a phosphine oxide compound. In this case, it is possible to form a thin protective layer having a high resolution and a pattern having a sufficient resolution.
  • the present invention also provides, as a third aspect, a photosensitive element comprising a support film, and a photosensitive layer comprising the photosensitive resin composition according to the second aspect of the present invention provided on the support film. provide.
  • a protective film having sufficient rust prevention can be formed on a predetermined touch panel electrode even if it is a thin film.
  • the thickness of the photosensitive layer can be 10 ⁇ m or less.
  • a protective film that covers a part or all of the electrode is formed on a substrate having a touch panel electrode by the method for forming a protective film according to the first aspect of the present invention.
  • the manufacturing method of a touch panel sensor provided with the process to perform is provided.
  • the protective film formation method of the electrode for touchscreens which can form the protective film which has sufficient antirust property even if it is a thin film on the electrode for predetermined touchscreens, and such protection
  • a photosensitive resin composition and a photosensitive element that can form a film can be provided.
  • the metal electrode of the capacitive touch panel can be protected. Furthermore, according to the present invention, it is possible to protect the electrodes in the frame region of the touch panel in which a metal layer such as copper, which is easily rusted by moisture or salt, is formed to improve conductivity.
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acryloyl group means acryloyl group or methacryloyl.
  • the (poly) oxyethylene chain means an oxyethylene group or a polyoxyethylene group
  • the (poly) oxypropylene chain means an oxypropylene group or a polyoxypropylene group.
  • (EO) modified means a compound having a (poly) oxyethylene chain
  • (PO) modified means a compound having a (poly) oxypropylene chain
  • (EO) ⁇ (PO) modified means a compound having both a (poly) oxyethylene chain and a (poly) oxypropylene chain.
  • process is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included.
  • a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive element of the present invention.
  • a photosensitive element 1 shown in FIG. 1 includes a support film 10, a photosensitive layer 20 made of the photosensitive resin composition according to the present invention provided on the support film, and the opposite side of the photosensitive layer 20 from the support film 10. And a protective film 30 provided on the surface.
  • the photosensitive element of the present embodiment can be suitably used for forming a protective film for a touch panel electrode.
  • Examples of the support film 10 include films having a thickness of about 5 to 100 ⁇ m made of polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, and the like.
  • the thickness of the support film is preferably from 5 to 100 ⁇ m, more preferably from 10 to 70 ⁇ m, from the viewpoints of ensuring coverage and suppressing a decrease in resolution during exposure through the support film.
  • An embodiment of the photosensitive resin composition according to the present invention constituting the photosensitive layer 20 includes a binder polymer (hereinafter also referred to as (A) component), a photopolymerizable compound (hereinafter also referred to as (B) component), A photopolymerization initiator (hereinafter also referred to as “component (C)”), and the hydroxyl value of the entire solid content of the photosensitive resin composition is 40 mgKOH / g or less.
  • a binder polymer hereinafter also referred to as (A) component
  • B photopolymerizable compound
  • component (C) A photopolymerization initiator
  • the hydroxyl value of the whole solid content of the photosensitive resin composition can be measured as follows. That is, first, 1 g of the photosensitive resin composition whose hydroxyl value is to be measured is precisely weighed. If the photosensitive resin composition contains a volatile component such as a synthetic solvent or a diluent solvent, the photosensitive resin composition is previously heated at a temperature about 10 ° C. higher than the boiling point of the volatile component for 1 to 4 hours to remove the volatile component. deep. 10 mL of a 10% by mass acetic anhydride pyridine solution is added to the precisely weighed photosensitive resin composition to dissolve it uniformly, and heated at 100 ° C. for 1 hour.
  • a volatile component such as a synthetic solvent or a diluent solvent
  • Hydroxyl value (AB) ⁇ f ⁇ 28.05 / sample (g) + acid value
  • A represents the amount (ml) of 0.5 mol / l potassium hydroxide ethanol solution used for the blank test
  • B represents the amount (ml) of 0.5 mol / l potassium hydroxide ethanol solution used for titration
  • f represents a factor.
  • the hydroxyl value of the entire solid content of the photosensitive layer in the photosensitive element described later can be measured as follows. That is, first, a photosensitive resin composition is formed by laminating a photosensitive element on a glass substrate a plurality of times, superimposing only the photosensitive layer of the photosensitive element, and then forming a photosensitive layer whose hydroxyl value should be measured with a metal spatula. As a kakio, weigh exactly 1 g. The precisely weighed photosensitive resin composition is transferred to an Erlenmeyer flask, 10 mL of 10% by mass acetic anhydride pyridine solution is added to dissolve it uniformly, and heated at 100 ° C. for 1 hour.
  • the hydroxyl value of the component (A) can be obtained by accurately weighing 1 g of the binder polymer whose hydroxyl value is to be measured, and then measuring the binder polymer in the same manner as the above-described measurement of the hydroxyl value.
  • the binder polymer contains a volatile component such as a synthetic solvent or a diluting solvent
  • the binder polymer is previously heated at a temperature about 10 ° C. higher than the boiling point of the volatile component for 1 to 4 hours to remove the volatile component.
  • a protective film having a sufficient antirust property can be formed with a thickness of 10 ⁇ m or less.
  • the present inventors infer the reason why the above effect is obtained as follows.
  • a thin film having a thickness of 10 ⁇ m or less is formed using the photosensitive resin composition, corrosive components such as moisture and salt are likely to be included in the film, and this tendency is caused by hydroxyl groups contained in the photosensitive resin composition, particularly hydroxy groups.
  • the present inventors consider that the size is further increased by the alkyl group.
  • the entire solid content of the photosensitive resin composition that is, the hydroxyl value of the entire component forming the protective film is within the above range, so that the reduction in rust prevention due to hydroxyl groups can be sufficiently suppressed. Conceivable.
  • the binder polymer as the component (A) any polymer can be used without particular limitation as long as the hydroxyl value of the entire solid content of the photosensitive resin composition is adjusted to 40 mgKOH / g or less.
  • the hydroxyl value of the component (A) is preferably 50 mgKOH / g or less, and more preferably 45 mgKOH / g or less.
  • component (A) for example, a polymer having a carboxyl group can be used.
  • the component (A) is preferably a copolymer containing structural units derived from (a) (meth) acrylic acid and (b) (meth) acrylic acid alkyl ester.
  • 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, and (meth) acrylic acid ester. ) Acrylic acid hydroxyl ethyl ester.
  • a (meth) acrylic acid alkyl ester containing a hydroxyl group such as the above (meth) acrylic acid hydroxyl ethyl ester
  • the hydroxyl value of the component (A) is 50 mgKOH / g or less. It is more preferable to adjust so that it may become 45 mgKOH / g or less.
  • the copolymer may further contain other monomers that can be copolymerized with the components (a) and (b) as constituent units.
  • Examples of other monomers that can be copolymerized with the components (a) and (b) include (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, and (meth) acrylic acid diethylamino acid.
  • the above monomers may be used alone or in combination of two or more.
  • the molecular weight of the binder polymer as component (A) is not particularly limited, but from the viewpoint of coating properties, coating film strength, and developability, it is usually a weight average molecular weight (a value measured in terms of standard polystyrene using GPC). ) Is preferably 10,000 to 200,000, more preferably 30,000 to 150,000, and most preferably 50,000 to 100,000. In addition, the measurement conditions of a weight average molecular weight shall be the same measurement conditions as the Example of this-application specification.
  • the acid value of the binder polymer as the component (A) can be developed with various known developing solutions in the step of selectively removing the photosensitive resin composition layer in the development step, From the viewpoint of improving resistance to corrosive components such as moisture and salt when functioning as a protective film, it is preferably 120 mgKOH / g or less.
  • the acid value when developing with an aqueous alkali solution such as sodium carbonate, potassium carbonate, tetramethylammonium hydroxide, triethanolamine, etc., the acid value is preferably 50 to 120 mgKOH / g. In terms of excellent developability, it is preferably 50 mgKOH / g or more.
  • the touch panel electrode from the viewpoint of protecting the electrode from corrosive components such as moisture and salt, it is preferably 120 mgKOH / g or less. .
  • the acid value of the binder polymer can be set to 16 to 120 mgKOH / g, development can be performed using an alkaline aqueous solution containing water, an alkali metal salt, and a surfactant. If the acid value is less than 16 mgKOH / g, development tends to be difficult, and if it exceeds 120 mgKOH / g, the electrode tends to be unable to be protected for the reasons described above.
  • the photopolymerizable compound as component (B) can be substituted without particular limitation depending on the required properties, provided that the hydroxyl value of the entire solid content of the photosensitive resin composition is 40 mgKOH / g or less. However, the hydroxyl value of the component (B) is preferably 90 mgKOH / g or less, and more preferably 60 mgKOH / g or less.
  • the hydroxyl value of the component (B) is measured in the same manner as the measurement of the hydroxyl value of the photopolymerizable compound solution after precisely weighing about 1 g of the solution of the photopolymerizable compound whose hydroxyl value is to be measured. Is required. If the photopolymerizable compound contains a volatile component such as a synthetic solvent or a diluting solvent, the volatile component is previously removed by heating at a temperature about 10 ° C. higher than the boiling point of the volatile component for 1 to 4 hours. .
  • a volatile component such as a synthetic solvent or a diluting solvent
  • a photopolymerizable compound having an ethylenically unsaturated group can be used as the photopolymerizable compound as component (B).
  • Examples of the photopolymerizable compound having an ethylenically unsaturated group include a monofunctional vinyl monomer, a bifunctional vinyl monomer, and 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 alkyl ester, and those co-polymerized as monomers used for the synthesis of a copolymer which is a preferred example of the component (A). Examples thereof include polymerizable monomers.
  • bifunctional vinyl monomer examples include polyethylene glycol di (meth) acrylate (having 2 to 14 ethoxy groups), trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate (propylene group Bisphenol A polyoxyethylene di (meth) acrylate (2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane), bisphenol A diglycidyl ether di (meth) acrylate And the like; and esterified products of polyvalent carboxylic acids (such as phthalic anhydride) and substances having a hydroxyl group and an ethylenically unsaturated group (such as ⁇ -hydroxyethyl acrylate and ⁇ -hydroxyethyl methacrylate).
  • polyvalent carboxylic acids such as phthalic anhydride
  • substances having a hydroxyl group and an ethylenically unsaturated group such as ⁇ -hydroxyethyl acrylate and ⁇ -
  • bisphenol A polyoxyethylene dimethacrylate examples include bisphenol A dioxyethylene diacrylate, bisphenol A dioxyethylene dimethacrylate, bisphenol A trioxyethylene diacrylate, bisphenol A trioxyethylene dimethacrylate, and bisphenol A pentaoxy. Examples include ethylene diacrylate, bisphenol A pentaoxyethylene dimethacrylate, bisphenol A deoxyoxyethylene diacrylate, and bisphenol A deoxyoxyethylene dimethacrylate.
  • Examples of the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, Compounds obtained by reacting ⁇ , ⁇ -unsaturated saturated carboxylic acids with polyhydric alcohols such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; trimethylolpropane triglycidyl ether triacrylate and the like Examples thereof include compounds obtained by adding an ⁇ , ⁇ -unsaturated carboxylic acid to a glycidyl group-containing compound.
  • a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups it is preferable to contain a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups. Furthermore, from the viewpoint of electrode corrosion inhibition and ease of development, it has a (meth) acrylate compound having a skeleton derived from pentaerythritol, a (meth) acrylate compound having a skeleton derived from dipentaerythritol, and a skeleton derived from trimethylolpropane.
  • (meth) acrylate having a skeleton derived from dipentaerythritol means an esterified product of dipentaerythritol and (meth) acrylic acid, and the esterified product is a compound modified with an alkyleneoxy group.
  • the above esterified product preferably has 6 ester bonds in one molecule, but a compound having 1 to 5 ester bonds may be mixed.
  • the (meth) acrylate compound having a skeleton derived from trimethylolpropane means an esterified product of trimethylolpropane and (meth) acrylic acid, and the esterified product is modified with an alkyleneoxy group. Also included are compounds. In the above esterified product, the number of ester bonds in one molecule is preferably 3, but a compound having 1 to 2 ester bonds may be mixed.
  • the above compounds can be used alone or in combination of two or more.
  • the ratio to be used is not particularly limited, but photocurability and electrode corrosion
  • the proportion of the monomer having at least three polymerizable ethylenically unsaturated groups in the molecule is 100 parts by mass of the total amount of the photopolymerizable compounds contained in the photosensitive resin composition. , Preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 75 parts by mass or more.
  • the content of the component (A) and the component (B) in the photosensitive resin composition of the present embodiment is such that the amount of the component (A) is 40 to 80 with respect to 100 parts by mass of the total amount of the components (A) and (B).
  • the component (B) is preferably 20 to 60 parts by mass, the component (A) is preferably 50 to 70 parts by mass, and the component (B) is more preferably 30 to 50 parts by mass. More preferably, the component is 55 to 65 parts by mass and the component (B) is 35 to 45 parts by mass.
  • Examples of the photopolymerization initiator as component (C) include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone.
  • substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same to give the target compound, or differently give an asymmetric compound.
  • an oxime ester compound or a phosphine oxide compound is preferable from the transparency of the protective film to be formed and the pattern forming ability when the film thickness is 10 ⁇ m or less.
  • the oxime ester compound include compounds represented by the following general formula (C-1) and general formula (C-2). From the viewpoint of fast curability and transparency, the following general formula (C-1) The compound represented by these is preferable.
  • R 1 is an alkyl group having 1 to 12 carbon atoms, an organic group containing a cycloalkyl group having 3 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, or a double bond.
  • An alkenoyl group having 4 to 6 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms or a phenoxycarbonyl group which is not conjugated with a carbonyl group is shown.
  • the aromatic ring in the general formula (C-1) may have a substituent.
  • R 1 is preferably an organic group containing an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, and an alkyl group having 3 to 10 carbon atoms. Or an organic group containing a cycloalkyl group having 4 to 15 carbon atoms, particularly an organic group containing an alkyl group having 4 to 8 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms. preferable.
  • R 2 represents a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, Represents an alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, R 3 represents an organic group containing an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, and R 4 is independently selected.
  • R 5 represents an alkyl group having 2 to 20 carbon atoms or an arylene group
  • p1 represents an integer of 0 to 3
  • p1 represents an integer of 0 to 3
  • p1 is 2 or more, a plurality of R 4 may be the same or different.
  • carbazole may have a substituent as long as the effects of the present invention are not impaired.
  • R 2 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. It is particularly preferred that
  • R 3 is preferably an organic group containing an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 4 to 15 carbon atoms, an alkyl group having 1 to 4 carbon atoms, A cycloalkyl group having 4 to 10 carbon atoms is more preferable.
  • Examples of the compound represented by the general formula (C-1) and the compound represented by the general formula (C-2) include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O -Benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.
  • 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] is EGANONE, 1- [IRGACURE-OXE01 (trade name, manufactured by Ciba Specialty Chemicals).
  • 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is commercially available as IRGACURE-OXE02 (trade name, manufactured by Ciba Specialty Chemicals) Are available. These are used alone or in combination of two or more.
  • Examples of the phosphine oxide compound include compounds represented by the following general formula (C-3) and general formula (C-4). From the viewpoint of fast curability and transparency, a compound represented by the following general formula (C-3) is preferred.
  • R 6 , R 7 and R 8 each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms.
  • R 9 , R 10 and R 11 each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms.
  • R 6 , R 7 or R 8 in the general formula (C-3) is an alkyl group having 1 to 20 carbon atoms
  • the alkyl group may be linear, branched, or cyclic
  • the alkyl group preferably has 5 to 10 carbon atoms.
  • R 9 , R 10 or R 11 in the general formula (C-4) is an alkyl group having 1 to 20 carbon atoms
  • the alkyl group may be linear, branched, or cyclic
  • the alkyl group preferably has 5 to 10 carbon atoms.
  • R 6 , R 7 or R 8 in the general formula (C-3) is an aryl group
  • the aryl group may have a substituent.
  • the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
  • R 9 , R 10 or R 11 in the general formula (C-4) is an aryl group
  • the aryl group may have a substituent.
  • the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
  • R 6 , R 7 , and R 8 are preferably aryl groups, and the compounds represented by general formula (C-4) are represented by R 9 , R 10 And R 11 is preferably an aryl group.
  • the compound represented by the general formula (C-3) includes 2,4,6-trimethylbenzoyl-diphenyl-phosphine 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. Oxides are preferred. 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide is commercially available, for example, as DAROCUR-TPO (trade name, manufactured by BASF Japan).
  • the content of the photopolymerization initiator as component (C) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B), and 1 to 10 parts by mass. Part is more preferable, and 2 to 5 parts by mass is even more preferable.
  • the photosensitivity is sufficient, and the absorption on the surface of the composition is increased at the time of exposure, and the internal photocuring becomes insufficient. Problems such as a reduction in visible light transmittance can be suppressed.
  • the photosensitive resin composition of this embodiment is one or more compounds selected from the group consisting of a triazole compound having an amino group and a tetrazole compound having an amino group from the viewpoint of suppressing the occurrence of development residue on the metal surface to be removed ( Hereinafter, it is preferable to further contain (D) component).
  • 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.
  • Examples of the tetrazole compound having an amino group include compounds represented by the following general formula (D-1).
  • R 11 and R 12 in the general formula (D-1) are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, an aminophenyl group, carbon An alkylphenyl group having 7 to 20 amino acids, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms or a carboxyalkyl group having 2 to 10 carbon atoms, wherein at least one of R 11 and R 12 represents an amino group; Have.
  • Alkyl groups include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl Group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.
  • Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • Examples of the alkylphenyl group include a methylphenyl group and an ethylphenyl group.
  • alkyl mercapto group examples include a methyl mercapto group and an ethyl mercapto group.
  • carboxyalkyl group examples include a carboxymethyl group and a carboxyethyl group.
  • tetrazole compounds represented by the general formula (D-1) 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-tetrazole, 5- (2- Aminophenyl) -1H-tetrazole, 1-cyclohexyl-5-amino-tetrazole, 1-phenyl-5-amino-tetrazole, 1-carboxymethyl-5-amino-tetrazole are preferred.
  • the tetrazole compound represented by the general formula (D-1) is preferably a water-soluble salt thereof.
  • Specific examples include alkali metal salts of 1-methyl-5-amino-tetrazole such as sodium, potassium and lithium.
  • 5-amino-1H-tetrazole and 1-methyl-5-mercapto-1H-tetrazole are particularly preferred from the viewpoints of the ability to suppress electrode corrosion, adhesion to metal electrodes, ease of development, and transparency.
  • tetrazole compounds and water-soluble salts thereof may be used singly or in combination of two or more.
  • the photosensitive resin composition is a tetrazole compound or mercapto group having an amino group. It is preferable to further contain a compound in which an amino group is substituted for a triazole compound containing. In this case, development residues can be reduced, and it becomes easy to form a protective film with a good pattern. As this reason, it is thought that moderate adhesion of the surface is expressed.
  • the photosensitive resin composition and the photosensitive element according to this embodiment are It is suitable for forming a protective film for protecting an electrode in a frame region of a touch panel in which a metal layer such as copper is formed to improve conductivity.
  • the content of the component (D) in the photosensitive resin composition of the present embodiment is 0.05 to 10.0 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B).
  • the amount is 0.1 to 2.0 parts by mass, and more preferably 0.2 to 1.0 part by mass.
  • a protective layer on a part of the ITO electrode of the touch panel, for example, a part where a protective layer is not formed in the view area, but a metal layer such as copper is formed on the ITO electrode in the frame region and the ITO electrode.
  • a protective layer is provided, unnecessary portions can be removed by exposure and development after the photosensitive layer is provided on the entire surface.
  • the photosensitive layer is required to have good developability so as not to cause development residue in unnecessary portions while having sufficient adhesion to the electrode to be protected.
  • the photosensitive resin composition of the present embodiment contains a phosphate ester (hereinafter also referred to as component (E)) containing a photopolymerizable unsaturated bond. It is preferable to contain.
  • a compound having the following structure as the phosphate ester from the viewpoint of achieving both high adhesion and developability to the ITO electrode while ensuring sufficient rust prevention properties of the protective film to be formed.
  • the compound is commercially available such as PM21 (manufactured by Nippon Kayaku Co., Ltd.).
  • the compounding quantity of phosphate ester is mix
  • an adhesion imparting agent such as a silane coupling agent, a leveling agent, a plasticizer, a filler, an antifoaming agent, a flame retardant, a stabilizer, and an antioxidant.
  • a perfume, a thermal crosslinking agent, a polymerization inhibitor and the like can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). These can be used alone or in combination of two or more.
  • the photosensitive resin composition of the present embodiment preferably has a visible light transmittance of 90% or more, more preferably 92% or more, and even more preferably 95% or more.
  • the visible light transmittance of the photosensitive resin composition is determined as follows. First, a photosensitive resin composition is applied on a support film so that the thickness after drying is 5 ⁇ m, and dried to form a photosensitive resin composition layer. Next, it laminates on a glass substrate using a laminator so that the photosensitive resin composition layer contacts. Thus, a measurement sample in which the photosensitive resin composition layer and the support film are laminated on the glass substrate is obtained. Next, after the photosensitive resin composition layer is photocured by irradiating the obtained measurement sample with ultraviolet rays, the transmittance in a measurement wavelength region of 400 to 700 nm is measured using an ultraviolet-visible spectrophotometer.
  • suitable transmittance means the minimum value of the transmittance in the above wavelength range.
  • the transmittance in the wavelength range of 400 to 700 nm which is a light ray in the general visible light wavelength range, is 90% or more, for example, when protecting the transparent electrode of the display part of the touch panel (touch sensor) or touch panel (touch).
  • the protective layer is visible from the edge of the display part when the metal layer (for example, a layer in which a copper layer is formed on the ITO electrode) is protected, the display quality, hue, A decrease in luminance can be sufficiently suppressed.
  • b * in the CIELAB color system is preferably ⁇ 0.2 to 1.0, and ⁇ 0. It is more preferably 0 to 0.7, and still more preferably 0.1 to 0.4.
  • b * is 0.8 or more or ⁇ 0.2 or less, the display quality and color tone in the display portion tend to be reduced, as in the case where the visible light transmittance is less than 90%.
  • the measurement of b * in the CIELAB color system uses, for example, a spectrocolorimeter “CM-5” manufactured by Konica Minolta, and a glass of 0.7 mm in thickness with b * of 0.1 to 0.2.
  • the photosensitive resin composition of the present embodiment is preferably used by forming a film on a photosensitive film like the photosensitive element of the present embodiment.
  • a roll-to-roll process can be easily realized, and the solvent drying process can be shortened. it can.
  • the photosensitive layer 20 can be formed by using the photosensitive resin composition of the present embodiment as a coating solution, and applying and drying the same on a support film.
  • the coating liquid can be obtained by uniformly dissolving or dispersing each component constituting the photosensitive resin composition of the present embodiment described above in a solvent.
  • the solvent is not particularly limited and known ones can be used.
  • examples include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, chloroform, and methylene chloride.
  • These solvents may be used alone or as a mixed solvent composed of two or more solvents.
  • Application methods include, for example, doctor blade coating method, Meyer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, die coating Examples thereof include a coating method.
  • the drying conditions are not particularly limited, but the drying temperature is preferably 60 to 130 ° C., and the drying time is preferably 0.5 to 30 minutes.
  • the thickness of the photosensitive layer is 10 ⁇ m or less after drying so that the step on the surface of the touch panel (touch sensor) caused by the formation of a partial electrode protective film is minimized as much as possible to exert a sufficient effect on electrode protection. Is preferably 2 to 10 ⁇ m, more preferably 3 to 8 ⁇ m.
  • the photosensitive layer 20 preferably has a visible light transmittance of 90% or more, more preferably 92% or more, and even more preferably 95% or more.
  • the photosensitive layer 20 is preferably adjusted so that b * in the CIELAB color system is ⁇ 0.2 to 1.0.
  • the viscosity of the photosensitive layer 20 prevents the photosensitive resin composition from oozing out from the end face of the photosensitive element for one month or more when it is used as a photosensitive element for forming a protective film of a roll-shaped touch panel electrode. From 30 to 100 MPa ⁇ s at 30 ° C. from the standpoint of preventing exposure failure and residual development caused by the fragments of the photosensitive resin composition adhering to the substrate when the photosensitive element is cut. More preferably, it is ⁇ 90 MPa ⁇ s, and even more preferably 25-80 MPa ⁇ s.
  • the viscosity is 1.96 ⁇ at 30 ° C. and 80 ° C. in the thickness direction of this sample using a circular film of 7 mm in diameter and 2 mm in thickness formed from the photosensitive resin composition as a measurement sample. This is a value obtained by measuring the rate of change of thickness when a load of 10 ⁇ 2 N is applied, and converting it to viscosity from the rate of change assuming a Newtonian fluid.
  • Examples of the protective film 30 include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polyethylene-vinyl acetate copolymer, and a laminated film of polyethylene-vinyl acetate copolymer and polyethylene having a thickness of 5 to 100 ⁇ m. Degree film.
  • Photosensitive element 1 can be stored in a roll or stored.
  • the photosensitive resin composition coating liquid of the present embodiment described above may be applied on a substrate having a touch panel electrode and dried to provide a photosensitive layer made of the photosensitive resin composition.
  • the photosensitive layer preferably satisfies the above-mentioned conditions of film thickness, visible light transmittance, and b * in the CIELAB color system.
  • FIG. 2 is a schematic cross-sectional view for explaining an embodiment of a method for forming a protective film for an electrode for a touch panel according to the present invention.
  • the method for forming a protective film for a touch panel electrode according to the present embodiment is a first method in which the photosensitive layer 20 made of the photosensitive resin composition according to the present embodiment is provided on the base material 100 having the touch panel electrodes 110 and 120.
  • a third step of forming a protective film 22 made of a cured product of the resin composition In this way, the touch panel sensor 200 with a protective film is obtained.
  • the substrate used in the present embodiment is not particularly limited, and examples thereof include substrates such as glass plates, plastic plates, and ceramic plates that are generally used for touch panels (touch sensors).
  • a touch panel electrode to be a target for forming a protective film is provided on this substrate.
  • the electrode include electrodes such as ITO, Cu, Al, and Mo, and TFT.
  • an insulating layer may be provided over the substrate.
  • etching photosensitive film is pasted on the metal film to form a desired resist pattern, and unnecessary Cu is iron chloride. After removing with an etching solution such as an aqueous solution, the resist pattern is peeled off.
  • the surface on which the touch panel electrodes 110 and 120 of the substrate 100 are provided while heating the photosensitive element is provided while heating the photosensitive element.
  • the photosensitive layer 20 is laminated by pressure bonding (see FIG. 2A).
  • Crimping means includes a crimping roll.
  • the pressure roll may be provided with a heating means so that it can be heat-pressure bonded.
  • the heating temperature for thermocompression bonding is preferably 10 to 180 ° C. so that the components of the photosensitive layer are not easily cured or thermally decomposed while ensuring sufficient adhesion between the photosensitive layer and the substrate. More preferably, the temperature is set to ⁇ 160 ° C., and more preferably 30 to 150 ° C.
  • the pressure at the time of thermocompression bonding is set to 50 to 1 ⁇ 10 5 N / m in terms of linear pressure from the viewpoint of suppressing deformation of the substrate while ensuring sufficient adhesion between the photosensitive layer and the substrate. Is preferably 2.5 ⁇ 10 2 to 5 ⁇ 10 4 N / m, more preferably 5 ⁇ 10 2 to 4 ⁇ 10 4 N / m.
  • the base material may be pre-heated.
  • the preheating temperature at this time is preferably 30 to 180 ° C.
  • the photosensitive resin composition of this embodiment is applied as a coating liquid to the surface of the substrate 100 where the touch panel electrodes 110 and 120 are provided and dried.
  • the photosensitive layer 20 can be formed.
  • the photosensitive layer 20 preferably satisfies the above-described conditions of film thickness, visible light transmittance, and b * in the CIELAB color system.
  • the photosensitive layer 20 is exposed to the actinic ray L in a pattern via the photomask 130 (see FIG. 2B).
  • the support film 10 on the photosensitive layer 20 when the support film 10 on the photosensitive layer 20 is transparent, it can be exposed as it is, and when it is opaque, it is removed and then exposed. From the viewpoint of protecting the photosensitive layer, it is preferable to use a transparent polymer film as the support film, and expose the polymer film while leaving the polymer film remaining.
  • a known active light source can be used, for example, a carbon arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, etc. Not limited.
  • the irradiation amount of actinic rays is usually 1 ⁇ 10 2 to 1 ⁇ 10 4 J / m 2 , and heating can be accompanied during irradiation. If the irradiation amount of actinic rays is less than 1 ⁇ 10 2 J / m 2 , the photocuring effect tends to be insufficient, and if it exceeds 1 ⁇ 10 4 J / m 2 , the photosensitive layer tends to discolor. is there.
  • the exposed photosensitive layer is developed with a developer to remove the unexposed portions, and the photosensitive resin composition of the present embodiment having a thickness of 10 ⁇ m or less covering a part or all of the electrodes.
  • a protective film 22 made of a cured product is formed. The formed protective film 22 can have a predetermined pattern.
  • development is performed by a known method such as spraying, showering, rocking dipping, brushing, scraping, etc., using a known developing solution such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, and unnecessary portions are removed.
  • a known developing solution such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, and unnecessary portions are removed.
  • Examples of the base of the alkaline aqueous solution include alkali hydroxide (lithium, sodium or potassium hydroxide, etc.), alkali carbonate (lithium, sodium or potassium carbonate or bicarbonate, etc.), alkali metal phosphate (potassium phosphate, etc.) , Sodium phosphate, etc.), alkali metal pyrophosphates (sodium pyrophosphate, potassium pyrophosphate, etc.), tetramethylammonium hydroxide, triethanolamine, etc. Among them, tetramethylammonium hydroxide, etc. are preferred. It is done.
  • an aqueous solution of sodium carbonate is also preferably used.
  • a dilute solution of sodium carbonate 0.5 to 5% by weight aqueous solution
  • 20 to 50 ° C. is preferably used.
  • the development temperature and time can be adjusted according to the developability of the photosensitive resin composition of the present embodiment.
  • a surfactant an antifoaming agent, a small amount of an organic solvent for promoting development, and the like can be mixed in the alkaline aqueous solution.
  • the base of the alkaline aqueous solution remaining in the photosensitive layer after development and photocuring is converted into an acid by a known method such as spraying, rocking immersion, brushing or scraping using an organic acid, an inorganic acid or an aqueous acid solution thereof. It can be treated (neutralized).
  • the cured product may be further cured by exposure (for example, 5 ⁇ 10 3 to 2 ⁇ 10 4 J / m 2 ) as necessary.
  • exposure for example, 5 ⁇ 10 3 to 2 ⁇ 10 4 J / m 2
  • the photosensitive resin composition of the present embodiment exhibits excellent adhesion to a metal even without a heating step after development, but if necessary, instead of exposure after development or in combination with exposure.
  • Heat treatment 80 to 250 ° C.
  • binder polymer solution (A2) Preparation of binder polymer solution (A2)
  • a binder polymer solution (solid content 45 mass%) (A2) having a weight average molecular weight of about 80,000, an acid value of 115 mgKOH / g, and a hydroxyl value of 1 mgKOH / g was obtained.
  • binder polymer solution (A3) Preparation of binder polymer solution (A3)
  • a binder polymer solution (solid content 45% by weight) (A3) having a weight average molecular weight of about 45,000, an acid value of 78 mgKOH / g, and a hydroxyl value of 43 mgKOH / g was obtained.
  • binder polymer solution (A4) In the same manner as in the above (A1), a binder polymer solution (solid content 45% by weight) (A4) having a weight average molecular weight of about 47,000, an acid value of 78 mgKOH / g and a hydroxyl value of 129 mgKOH / g was obtained.
  • binder polymer solution (A5) [Preparation of binder polymer solution (A5)] MIS-115 (methacrylic acid / N-cyclohexylmaleimide / dicyclopentanyl methacrylate / 2-hydroxyethyl methacrylate copolymer / reaction product of 2-hydroxyethyl methacrylate and methacrylic acid (2-isocyanatoethyl) (mass ratio) A 12.2 / 10.9 / 26 / 18.6 / 32.3) propylene glycol monomethyl ether acetate / methyl lactate solution was used with a weight average molecular weight of about 26,000, an acid value of 55 mgKOH / g, and a hydroxyl value. was 80.2 mgKOH / g.
  • the weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve.
  • GPC condition Pump Hitachi L-6000 type (product name, manufactured by Hitachi, Ltd.) Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., product name) Eluent: Tetrahydrofuran Measurement temperature: 40 ° C Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)
  • the acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components to obtain a solid content. Then, after precisely weighing 1 g of the polymer whose acid value is to be measured, 30 g of acetone was added to this polymer and dissolved uniformly. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula.
  • Acid value 10 ⁇ Vf ⁇ 56.1 / (Wp ⁇ I)
  • Vf represents the titration amount (mL) of phenolphthalein
  • Wp represents the weight (g) of the measured resin solution
  • I represents the ratio (mass%) of the non-volatile content in the measured resin solution.
  • the hydroxyl group was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components to obtain a solid content. Then, after precisely weighing 1 g of the polymer whose hydroxyl value is to be measured, the accurately weighed photosensitive resin composition is put in an Erlenmeyer flask, and 10 mL of 10% by mass acetic anhydride pyridine solution is added and uniformly dissolved. Heated at 0 ° C. for 1 hour. After heating, 10 mL of water and 10 mL of pyridine were added and heated at 100 ° C. for 10 minutes. Then, using an automatic titrator (“COM-1700” manufactured by Hiranuma Sangyo Co., Ltd.), 0.5 mol / L potassium hydroxide ethanol It was measured by neutralization titration with a solution.
  • an automatic titrator (“COM-1700” manufactured by Hiranuma Sangyo Co., Ltd.
  • Example 1 [Preparation of Photosensitive Resin Composition Solution (V-1) for Forming Protective Film]
  • the materials shown in Table 2 were mixed for 15 minutes using a stirrer to prepare a photosensitive resin composition solution (V-1) for forming a protective film.
  • Photosensitive Element (E-1) for Forming Protective Film A polyethylene terephthalate film having a thickness of 50 ⁇ m was used as the support film, and the photosensitive resin composition solution (V-1) was evenly applied onto the support film using a comma coater, and 3 times with a 100 ° C. hot air convection dryer. The solvent was removed by drying for minutes to form a photosensitive layer (photosensitive resin composition layer) made of the photosensitive resin composition. The resulting photosensitive layer had a thickness of 5 ⁇ m.
  • a polyethylene film having a thickness of 25 ⁇ m was further laminated as a cover film on the obtained photosensitive layer to produce a photosensitive element (E-1) for forming a protective film.
  • a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) is used for the photosensitive layer of the obtained laminate, and the exposure amount is 5 ⁇ 10 2 J / m 2 from the upper side of the photosensitive layer (i line). (Measurement value at a wavelength of 365 nm) After irradiation with ultraviolet rays, the support film was removed to obtain a transmittance measurement sample having a photosensitive layer (photocured cured film) thickness of 5.0 ⁇ m.
  • the visible light transmittance of the obtained sample was measured in a measurement wavelength range of 400 to 700 nm using an ultraviolet-visible spectrophotometer (U-3310) manufactured by Hitachi Instrument Service Co., Ltd.
  • the transmittance of the obtained photosensitive layer at a wavelength of 400 nm is 97% at a wavelength of 700 nm, 96% at a wavelength of 550 nm, and 94% at a wavelength of 400 nm.
  • the transmittance was secured.
  • the obtained photosensitive layer was subjected to an exposure amount of 5 ⁇ 10 2 J / m 2 (i-line (wavelength 365 nm) from the upper side of the photosensitive layer side using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.). )), After irradiating with ultraviolet rays, the support film is removed and further irradiated with ultraviolet rays (measured value at i-line (wavelength 365 nm)) with an exposure amount of 1 ⁇ 10 4 J / m 2 from above the photosensitive layer side. Then, a sample for b * measurement having a photosensitive layer (photocured cured film) thickness of 5.0 ⁇ m was obtained.
  • CM-5 spectrocolorimeter
  • the b * of the photosensitive layer was 0.63, confirming that it had a good b * .
  • a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) was used for the photosensitive layer of the obtained laminate, and the exposure amount was 5 ⁇ 10 2 J / m 2 (i-line ( Measured value at a wavelength of 365 nm), after irradiating with ultraviolet rays, the support film is removed, and further the ultraviolet ray is irradiated at an exposure amount of 1 ⁇ 10 4 J / m 2 from above the photosensitive layer side (measured value at i-line (wavelength 365 nm)). Irradiation was performed to obtain a sample for evaluating artificial sweat resistance in which a 5.0 ⁇ m-thick protective layer formed by curing the photosensitive layer was formed.
  • C Traces are visible on the surface of the protective layer, but copper is unchanged.
  • D There is a trace on the surface of the protective layer, and copper discolors. When the surface state of the sample for evaluation was observed, a very slight trace was seen on the surface of the protective layer, but the copper was unchanged and the evaluation was B.
  • the laminate obtained above was prepared, it was stored for 24 hours at 23 ° C. and 60%, and then the actinic ray transmitting portion and the actinic ray shielding portion were alternately patterned, and a photo with a line / space of 300 ⁇ m / 300 ⁇ m.
  • a photomask is placed on a support film, and using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.), the exposure amount is 5 ⁇ 10 2 J / m 2 from above the photomask surface. (Measured value at i-line (wavelength 365 nm)), ultraviolet rays were imagewise irradiated.
  • the support film laminated on the photosensitive layer is removed, and spray development is performed at 30 ° C. for 40 seconds using a 1.0% by mass aqueous sodium carbonate solution to selectively remove the photosensitive layer, and a protective film pattern Formed.
  • the substrate surface state of the portion of the obtained substrate with the protective film pattern where the photosensitive layer was selectively removed was observed with a microscope, and the development residue was evaluated according to the following ratings.
  • B Copper on the substrate surface is slightly discolored, but there is no development residue.
  • C Copper on the surface of the substrate is slightly discolored, and a development residue is slightly generated.
  • D Development residue is generated. When the surface state of the sample for evaluation was observed, there was no change on the surface of the substrate, and the evaluation was A.
  • a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) is used for the photosensitive layer of the obtained laminate, and the exposure amount is 5 ⁇ 10 2 J / m 2 from the upper side of the photosensitive layer (i line).
  • the exposure amount is 5 ⁇ 10 2 J / m 2 from the upper side of the photosensitive layer (i line).
  • the support film is removed, and further at an exposure amount of 1 ⁇ 10 4 J / m 2 from above the photosensitive layer side (measured value at i-line (wavelength 365 nm))
  • a cross-cut adhesion test sample in which a 5.0 ⁇ m-thick protective layer formed by curing the photosensitive layer was formed.
  • Examples 2 to 8 A photosensitive element was prepared in the same manner as in Example 1 except that the photosensitive resin composition solution shown in Tables 3 and 4 (the unit of numerical values in the table is part by mass) was used, and measurement of transmittance, salt spray test A development residue test and a cross-cut adhesion test were conducted. As shown in Tables 7 and 8, in Examples 1 to 8, all of the measurements of transmittance, salt spray resistance evaluation, and cross-cut adhesion were good results. In addition, b * of the photosensitive resin composition layers of Examples 2 to 8 was 0.62 to 0.63, and good b * was secured.

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Abstract

Le procédé de formation de film protecteur d'électrode pour écran tactile de l'invention comporte : une première étape au cours de laquelle sur un matériau de base possédant une électrode pour écran tactile, est agencée une couche photosensible constituée d'une composition de résine photosensible comprenant un polymère de liant, un composé photopolymérisable, et un initiateur de photopolymérisation; une seconde étape au cours de laquelle une portion prédéfinie de la couche photosensible est durcie par irradiation de rayons lumineux actifs; et une troisième étape au cours de laquelle la couche photosensible est retirée en dehors de la portion prédéfinie, et est formé un film protecteur constitué par le produit durci de la composition de résine photosensible de 10μm au plus d'épaisseur qui recouvre une partie ou l'ensemble de l'électrode. Le procédé de l'invention est caractéristique en ce que l'indice d'hydroxyle pour la totalité de la teneur en matière solide de composition de résine photosensible, est inférieur ou égal à 40mgKOH/g.
PCT/JP2011/078108 2011-12-05 2011-12-05 Procédé de formation de film protecteur d'électrode pour écran tactile, composition de résine photosensible, et élément photosensible WO2013084284A1 (fr)

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PCT/JP2011/078108 WO2013084284A1 (fr) 2011-12-05 2011-12-05 Procédé de formation de film protecteur d'électrode pour écran tactile, composition de résine photosensible, et élément photosensible
PCT/JP2012/081365 WO2013084875A1 (fr) 2011-12-05 2012-12-04 Film protecteur pour électrode de panneau tactile et panneau tactile
JP2013516812A JP5304969B1 (ja) 2011-12-05 2012-12-04 タッチパネル用電極の保護膜の形成方法、感光性樹脂組成物及び感光性エレメント、並びに、タッチパネルの製造方法
PCT/JP2012/081377 WO2013084883A1 (fr) 2011-12-05 2012-12-04 Procédé de formation de film protecteur d'électrode pour écran tactile, composition de résine photosensible, élément photosensible, et procédé de fabrication d'écran tactile
KR1020177025927A KR20170106655A (ko) 2011-12-05 2012-12-04 터치패널용 전극의 보호막의 형성 방법, 감광성 수지 조성물 및 감광성 엘리먼트, 및, 터치패널의 제조 방법
CN201810052144.XA CN108108072A (zh) 2011-12-05 2012-12-04 触摸面板用电极的保护膜及触摸面板
KR1020147016028A KR101592803B1 (ko) 2011-12-05 2012-12-04 터치패널용 전극의 보호막 및 터치패널
KR1020147016024A KR101989644B1 (ko) 2011-12-05 2012-12-04 터치패널용 전극의 보호막의 형성 방법, 감광성 수지 조성물 및 감광성 엘리먼트, 및, 터치패널의 제조 방법
KR1020187021801A KR102025036B1 (ko) 2011-12-05 2012-12-04 터치패널용 전극의 보호막의 형성 방법, 감광성 수지 조성물 및 감광성 엘리먼트, 및, 터치패널의 제조 방법
JP2013516814A JP5304971B1 (ja) 2011-12-05 2012-12-04 タッチパネル用電極の保護膜及びタッチパネル
US14/362,716 US20140335350A1 (en) 2011-12-05 2012-12-04 Method for forming protective film on electrode for touch panel, photosensitive resin composition and photosensitive element, and method for manufacturing touch panel
CN201610515674.4A CN106126003A (zh) 2011-12-05 2012-12-04 触摸面板用电极的保护膜的形成方法、感光性树脂组合物及感光性元件、以及触摸面板的制造方法
CN201280059836.8A CN103975294B (zh) 2011-12-05 2012-12-04 触摸面板用电极的保护膜的形成方法、感光性树脂组合物及感光性元件、以及触摸面板的制造方法
CN201280059906.XA CN104054042B (zh) 2011-12-05 2012-12-04 触摸面板用电极的保护膜及触摸面板
TW104139042A TWI625655B (zh) 2011-12-05 2012-12-05 觸控式面板用電極的保護膜的形成方法、感光性樹脂組成物與感光性元件、以及觸控式面板的製造方法
TW104135790A TWI621671B (zh) 2011-12-05 2012-12-05 硬化物的用途
TW101145694A TWI512399B (zh) 2011-12-05 2012-12-05 觸控式面板用電極的保護膜及觸控式面板
TW107114189A TW201828005A (zh) 2011-12-05 2012-12-05 觸控式面板用電極的保護膜的形成方法、感光性樹脂組成物與感光性元件、以及觸控式面板的製造方法
TW101145687A TWI525491B (zh) 2011-12-05 2012-12-05 觸控式面板用電極的保護膜的形成方法、感光性樹脂組成物與感光性元件、以及觸控式面板的製造方法
JP2013123513A JP6212970B2 (ja) 2011-12-05 2013-06-12 タッチパネル用電極の保護膜及びタッチパネル
JP2017176922A JP6540766B2 (ja) 2011-12-05 2017-09-14 タッチパネル用電極の保護膜及びタッチパネル

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